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Mercury in the environment :

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Title:
Mercury in the environment : field studies from tampa, bolivia, and guyana
Physical Description:
Book
Language:
English
Creator:
Howard, Joniqua
Publisher:
University of South Florida
Place of Publication:
Tampa, Fla
Publication Date:

Subjects

Subjects / Keywords:
Methyl-mercury
Global mercury cycle
Fish
Gold mining
Environmental sustainability
Education
Dissertations, Academic -- Civil & Environmental Engineering -- Doctoral -- USF   ( lcsh )
Genre:
non-fiction   ( marcgt )

Notes

Abstract:
ABSTRACT: Tampa (US), Guyana (SA), and Bolivia (SA), are geographically, socially, economically, and politically unique which make them ideal sites to study issues of mercury and sustainability. Mercury's innate ability to bioaccumulate and biomagnify in aquatic and terrestrial ecosystems poses a severe threat to both human and environmental health. The most vulnerable populations affected by mercury consumption include coastal communities, children, women of child-bearing age, the indigenous poor and persons with high environmental/occupational exposure factors. Communities in the regions of Florida, Bolivia, and Guyana whose diets are high in fish and are environmentally/occupationally exposed to mercury may be at a higher risk of mercury intoxication, especially in the absence of education on the topic. Mercury loadings in rivers, streams, and mine tailing waters and sediments ranged from 0.9-114 ng/L and 29- 2891 ng/g, respectively; whilst fish mercury loadings were 0.02-1.034 mg/kg wet wt. Although mining sites had the highest mercury sediment and water loadings there were no significant differences when compared to pristine sites in Guyana. Fish loadings above recommended EPA/WHO regulatory limits were observed at all sites and none had signage, informational warnings or educational material available. A pilot study that included four elementary schools in Tampa showed that Water Awareness Research Education (WARE), a community based participatory environmental educational program, is a sustainable solution to addressing issues of mercury exposure.
Thesis:
Dissertation (Ph.D.)--University of South Florida, 2010.
Bibliography:
Includes bibliographical references.
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Mode of access: World Wide Web.
System Details:
System requirements: World Wide Web browser and PDF reader.
Statement of Responsibility:
by Joniqua Howard.
General Note:
Title from PDF of title page.
General Note:
Document formatted into pages; contains X pages.
General Note:
Includes vita.

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University of South Florida Library
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University of South Florida
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All applicable rights reserved by the source institution and holding location.
Resource Identifier:
usfldc doi - E14-SFE0003456
usfldc handle - e14.3456
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SFS0027771:00001


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Mercury In The Environment: Field Studies From Tampa, Bolivia, And Guyana by Joniqua A'ja Howard A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Civil and Environmental Engineering College of Engineering University of South Florida Major Professor: Maya Trotz Ph.D. Fenda Akiwumi, Ph.D. Mark Rains, Ph.D. Amy S tuart, Ph.D. Date of Approval: March 5, 2010 Keywords: methyl mercury, global mercury cycle, fish, gold mining, environmental sustainability, education Copyright 2010 Jon iqua A'ja Howard

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DEDICATION To the past, present, and future: Reverend Otis Howard Beulah Allen Howard Edward McArthur, Sr. Raymond Howard, Sr. Ora McArthur Leanna McArthur Loretta Howard John Howard Coach Arron Prather All of those who will be impacted posi tively by my work SANKOFA!

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ACKNOWLEDGEMENTS Hab akkuk 2:2 3 This work was supported through a University of South Florida (USF) Sustainable Healthy Communities G rant for interdisciplinary research as well as the USF Graduate School Challenge Grant. First and foremost, m y deepest gratitude and appreciation will for ever be exten ded to my major professor, Dr. Maya A. Trotz, who has been highly influential in my graduate career and guiding me through a myriad of obstacles Also, I would like to thank my committee member s f or their insight and more importantly challenging me throug hout this process For the endless support during this challenging time, I thank my family (on and off the track) close spiritual cheerleaders, students /athletes Bridge to the Doct orate Family, women in science support group (KB, Crystal Dobson, Regina E., Christina S., PT, and Nekesha W.), and lab members /motivators (Ken Thomas, Erlande Omisca, Douglas Oti) During my field travel, I give my warmest regards for supplying me with great food, a place of shelter, and great company to m y international famil ies in Bolivia and Guyana To all the staff and friends from ACDI/ VOCA, Iwokrama, SWFWMD, the miners in Ma hd ia and Boliv i a the SHC course participants thank you for all your valued assistance Special thanks to the Florida Fish and Wildlife Conservati on Commission ( J Wheaton Gigi & D Richard ), FDEP (B. Topoloski & T. Lange, ), USGS (D. Edwards) and USF NNRC ( JB and Javier ) for the guidance and training of field and analytical equipment The storm is over .. I feel as though I can make it now Psalms 18 32 3 8

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“Note to Reader” The original of this document contains color that is necessary for understanding the data. The original dissertation is on file with the USF library in Tampa, Florida.

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i TABLE OF CONTENTS LIST OF TABLE S ................................ ................................ ................................ ................ v LIST OF FIGURES ................................ ................................ ................................ ............. ix ABSTRACT ................................ ................................ ................................ ....................... x vi CHAPTER 1: INTRODUCTION ................................ ................................ ......................... 1 1.1 Motivation and Research Objective s ................................ ................................ 1 CHAPTER 2: BACKGROUND ................................ ................................ ........................... 5 2.1 Introduction ................................ ................................ ................................ ....... 5 2.2 Overview of Mercury ................................ ................................ ......................... 6 2.3 Mercury in the Environment ................................ ................................ .............. 9 2.3.1 Mercury Cycle ................................ ................................ .................... 9 2.3.2 Atmos pheric Mercury ................................ ................................ ........ 11 2.3.3 Mercury in Water and Sediment ................................ ........................ 1 3 2.3.4 Mercury in Fish ................................ ................................ ................. 1 6 2.4 Toxicity of Mercury ................................ ................................ ......................... 1 7 2.5 Mercury as a Commodity ................................ ................................ ................. 2 3 CHAPTER 3 : FLORIDA ................................ ................................ ................................ .... 2 6 3.1 Introduction ................................ ................................ ................................ ...... 2 6 3.1.1 Objectives ................................ ................................ ........................... 2 6 3.2 Mercury and Florida, USA (N.A.) ................................ ................................ ... 27 3.2.1 Tampa Bay, FL, USA (N.A.) ................................ ............................ 31 3.2.2 Hillsborough River, FL, USA (N.A.) ................................ ................ 3 3 3.3 Sampling Locations Hillsborough River ................................ ........................ 3 5

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ii 3.4 Materials and Methods ................................ ................................ ..................... 3 6 3.4.1 Glassware/Sampling Kit ................................ ................................ .... 3 7 3.4.2 Reagents ................................ ................................ ............................ 3 7 3.4.3 Water Sampling ................................ ................................ ................. 3 8 3.4.4 Sediment ................................ ................................ ............................ 39 3.4.5 Biota Sampling ................................ ................................ .................. 40 3.5 Analytical Procedures ................................ ................................ ...................... 41 3.5.1 Cold Vapor Atomic Adsorption Spectroscopy ( CVAAS) ................. 41 3.5.2 Cold Vapor Fluorescence Spectroscopy (CVAFS) ........................... 4 2 3.5.3 Brunauer, Emmett, and Teller (BET) Surface Area Analyzer .......... 4 2 3.5.4 X Ray Diffractometry, S canning Electron Microscopy Electron Dispersive Spectroscopy ................................ ................................ 4 3 3.6 General Results and Discussion ................................ ................................ ....... 4 6 3.6.1 Total Mercur y Loadings in Sediment and Water .............................. 46 3.6.2 Total Mercury Loadings in Fish ................................ ........................ 56 3.6.3 Health Implications ................................ ................................ ........... 62 3.7 Summary ................................ ................................ ................................ ........... 65 CHAPTER 4 : GUYANA ................................ ................................ ................................ ... 67 4.1 Introduction ................................ ................................ ................................ ...... 67 4.1.1 Objectives and Tasks ................................ ................................ ...... 68 4.2 Guyana (S.A.) ................................ ................................ ................................ 68 4.3 Mining in Guyana and Environmental Regulations ................................ .......... 73 4.4 Sampling Area ................................ ................................ ................................ 76 4.4.1 Mahdia ................................ ................................ ............................ 77 4.4.2 ................................ ....... 77 4.4.3 Konashen Community Owned Conservation Area ......................... 78 4.4.4 Iwokrama International Centre for Rain Forest Conservation and Development ................................ ................................ ............ 80

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iii 4.5 Materials and Methods ................................ ................................ ..................... 81 4.5.1 Glassware/Sampling Kit ................................ ................................ 81 4.5.2 Reagents ................................ ................................ .......................... 81 4.5.3 Water and Sedim ent Sampling ................................ ........................ 82 4.6 General Results and Discussion ................................ ................................ ...... 83 4.7 Summary ................................ ................................ ................................ ......... 94 CHAPTER 5 : BOLIVIA ................................ ................................ ................................ ..... 9 5 5.1 Introduction ................................ ................................ ................................ ...... 9 5 5.1.1 Objectives and Tasks ................................ ................................ ......... 9 6 5.2 Bolivia ................................ ................................ ................................ .............. 9 6 5.3 Mining in Bolivia ................................ ................................ ............................. 98 5.4 Mining and the Exploitation of the Poor and Indigenous Populations .......... 10 0 5.5 Sampling Area ................................ ................................ ............................... 10 2 5.5.1 Lago Titicaca, Bolivia (S.A.) ................................ .......................... 10 2 5.5.2 Site Description ................................ ................................ ............... 10 4 5.6 Materials and Methods ................................ ................................ ................... 10 6 5.6.1 G lassware/ Sampling Kit ................................ ................................ .. 1 06 5.6.2 Reagents ................................ ................................ .......................... 1 06 5.6.3 Water and Sediment Sampling ................................ ........................ 1 06 5.6.4 Fish Sampling ................................ ................................ ................. 1 07 5.7 General Results and Discussion ................................ ................................ ..... 1 08 5.7.1 Total Mercury Loadings in Water and Sedim ent ............................ 1 08 5.7.2 Total Mercury Loadings in Fish ................................ ...................... 11 3 5.7.3 Health Implications with Fish Consumption ................................ ... 1 17 5.8 Summary ................................ ................................ ................................ ........ 119 CHAPTER 6 : INTEGRATED EXAMINATION OF MERCURY ................................ .. 121 6.1 Introduction ................................ ................................ ................................ .... 121 6.1.1 Objectives and Tasks ................................ ................................ ....... 122 6.2 Background ................................ ................................ ............................... 123

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iv 6.2.1 Sustainability and Education ................................ ............................ 12 3 6.2.2 State of Science Education ................................ .............................. 12 4 6.2.3 Broadening Participation in Science Education in the US .............. 126 6.2.4 Community Based Participatory Research ................................ ...... 132 6.2.5 Water Awareness, Research and Education project (WARE) ......... 137 6.2.6 WARE Activities ................................ ................................ ............ 145 6.3 Methodology ................................ ................................ ............................ 148 6.4 Results and Discussion ................................ ................................ ............. 154 6.4. 1 In Class Activities ................................ ................................ 1 54 6.4. 2 Partnership Progression and Evaluation .............................. 1 60 6. 5 Conclusion ................................ ................................ ................................ 1 61 CHAPTER 7: INTEGRATED EXAMINATION OF MERCURY ................................ .. 1 6 2 7.1 Introduction ................................ ................................ ............................... 1 6 2 7.1.1 Objectives, Tasks, and Approach ................................ ..................... 1 6 2 7.2 Results and Discussion ................................ ................................ ............. 1 6 3 7.2.1 Economic Sustainability, Political Cohesion and Community Participation ................................ ................................ ..................... 1 6 8 7.3 Environmental Sustainability and Socio cultural Impacts ........................ 1 8 9 7.4 Education ................................ ................................ ................................ .. 1 99 7.5 Conclusion ................................ ................................ ................................ 20 3 CHAPTER 8: CONCLUSION ................................ ................................ ......................... 20 6 8.1 Introdu ction ................................ ................................ ............................... 20 6 8.2 Summary of Results and Conclu sions ................................ ...................... 20 6 8.3 Rec ommendations for Future Work ................................ .......................... 2 08 REFERENCES ................................ ................................ ................................ ................. 21 1 APPENDICES ................................ ................................ ................................ .................. 2 4 8

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v Appendix A ................................ ................................ ................................ ........... 2 49 Appendix B ................................ ................................ ................................ ........... 25 0 Appendix C ................................ ................................ ................................ ........... 25 7 Appendix D ................................ ................................ ................................ ........... 2 5 9 Appendix E ................................ ................................ ................................ ........... 26 0 Appendix F ................................ ................................ ................................ ............ 26 1 Appendix G ................................ ................................ ................................ ........... 26 2 Appendix H ................................ ................................ ................................ ........... 2 69 Appendix I ................................ ................................ ................................ ............ 27 1 Appendix J ................................ ................................ ................................ ........... 278 ABOUT THE AUTHOR ................................ ................................ ......................... End Page

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vi LIST OF TABLES Table 2.1 : Physical and Chemical Properties of Mercury (Taken from Benjamin 25 ) ......... 8 Table 2.2: En vironmental Mercury Fluxes from Global Mercury Models ........................ 13 Table 2.3: Current Regulatory Limits and Guidelines f or Mercury Set By Governing Agencies for the United States a nd Internationally ................................ .......... 20 Table 3.1 : Matrix Preservation Requirements and Hold Times ................................ ........ 37 Table 3.2: Total Mercury Concentrations in Unfiltered Water (uwTHg), Filtered Water (fwTHg), ................................ ................................ ................................ 4 6 Table 3.3: Water Quality Parameters Just Above the Bottom of the Riverbed (pH, Temperature (Temp.), Specific Conductance (SpC.), Dissolved Oxygen (DO), a nd Turbidity (TURB)) for Sample Sites Accessed by Boat in the Lower Hillsborough River. ................................ ................................ ............. 47 Table 3.4: Mercury Concentrations in Sediment and Water Samples from This and Other S tudies ................................ ................................ ................................ ..... 48 Table 3.5 : Pearson C orrelation C oefficients B etween T otal M ercur y in S ediment and U nfiltered S urface W ater and W ater Q uality P arameters for A ll S ites and p V alues A ssuming a O ne T ailed D istribution for T wo S amples of U nequal V ariance ................................ ................................ .............................. 49 Table 3.6 : Mineralogical and Semi Q uantitative Results Obtained by X R ay Diffract ion for Samples from Upper, Middle, and Lower Segments of the River ................................ ................................ ................................ .................. 52 Table 3.7 : Summary of Fish C haracteristics ( L eng th, W eight, F ish Body Condition(fbC), age) and T otal Hg (f THg) C oncentrations S ampled on 2/26/08 at Rotary Park # Tampa ................................ ................................ ....... 57

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vii Table 3.8: Child Hazard Index (H) and Critical Fish Con centration (C) Assuming H = 1 . ................................ ................................ ................................ ................. 64 Table 3. 9 : Adult Hazard Index (H) and Critical Fish Concentration (C) for Adults Assuming H = 1. ................................ ................................ ............................. 64 Table 4.1: Land and F orestry C overage and G old P roduction of C ountrie s of the Guiana Shield ( A dapted from Hammond DS, 2005 and USGS, 2008) ........... 70 Table 4.2. Mercury Partnerships and Programs Within Guyana Aimed to Reduce Mercury Exposure ................................ ................................ ............................ 74 Table 4.3: Sediment Total Mercury Loadings (sTH g In n g/ g Dry Weight) a nd Water Qua lity Parameters f or Samples Taken At Iwokrama Konashen Arakaka / / Port Kaituma ................................ ......................... 85 Table 4.4: Average V alues of Total Mercury L oading, sTHg (ng/g dry weight), pH, Dissolved Oxygen, DO (mg/L), and Turbidity, TURB (NTU) F ound in Each Study A r ea ................................ ................................ .............................. 87 Table 4.5. Range of Mercury C oncentrations S een in Sediment from This and Other S tudies ................................ ................................ ................................ ............... 92 Table 5.1 : Depth (DUF) Unfil tered Water Quality Parameters (pH, Temperature (Temp.), Speceific Conductivity (SpC.), Dissolved Oxygen (DO), and Turbidity (T URB) for Sample Sites Access by Rowboat in Lago Titicaca. ................................ ................................ ................................ ......................... 108 Table 5.2 : Surface Unfiltered Water Quality Parameters (pH, Temperature (Temp.), Speceific Conductivity (SpC.), Dissolved Oxygen (DO), Turbidity (TURB), and Salintiy for Sample Sites Access the B anks of R ivers and S treams (RS) ................................ ................................ ................................ 110 Table5.3 : Mercury Concentrations in Sediment and Water Samples from Lago Titicaca and Other Studies. ................................ ................................ ............ 111

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viii Table5.4 : Pearson Correlation Coefficients Between Total Mercury in Sediment and Unfiltered Surface Water and Water Quality Parameters for All Sites in Bolivia and p Values Assuming A One Tailed Distribution for Two Samples of Unequal Variance ................................ ................................ ........ 11 2 Table 5. 5 Summary of Fish C haracteristics ( L eng th, W eight, S ex, and F ish B ody C ondition (fbC)) and T otal Hg (f THg) C oncentrations S ampled on 06/2009 from the Lago Titicaca A rea in Bolivia ................................ ........... 11 4 Table 5. 6. Child Hazard Index (H) and Critical fish concentration (C) for Lago Titicaca, Bolivia A ssuming H = 1. ................................ .............................. 118 Table 5.7. Adult Hazard Index (H) and Critic al fish concentration (C) for Lago Titicaca, Bolivia A ssuming H = 1 ................................ ................................ 119 Table 6.1. Demographics for The United States, Bolivia and Guyana and The World. .. 1 26 Table 6. 2 Patents Filed In The U.S. In 1995 and 2008. Data Taken F rom The USPTO Tech nology Mon itoring Team Report, Patents By Country, State, And Year All Patent Types. Granted: 01/01/1977 12/31/2008. ....... 1 2 8 Table 6.3. Demographics o f Civil Engineering Faculty A t T he Top 50 Departments In The US For The Year 2007. ................................ ................................ ...... 1 28 Table 6.4 Elements of Community Based Participatory Research. ............................... 13 3 Table 6.5. Examples of CBPR Studies with Environmental Linkages.. ......................... 135 Table 6.6. Guiding Principles for Community Based Participatory Research. Based on the Work of Israel et al., 302 .. ................................ ................................ ..... 136 Table 6 .7 Summary of Demographic Data for Florida, The City Of Tampa, and Counties That Make Up The Tampa Metropolitan Statistical Area. Data Taken from The U.S. Census Bureau 303 ................................ ...................... 138 Table 6.8 WARE Participants As of March 2010, Their Roles and Ways in Which They Disseminate WARE Generated Materials ................................ ........... 143

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ix Table 6. 9 WARE Participants As of March 2010, Their Roles and Ways in Which They Disseminate WARE Generated Materials .............................. 144 Table 6.1 0. Water Awareness Research and Education Classroom Curriculum Overview ................................ ................................ ................................ ...... 147 Table 6.11. Sunshine State Standards Grade Level Expectations and Benchmarks for Grades 3 8 That Were Used in C urriculum Design ................................ ..... 148 Table 6.12 Example of The Reflective Journal Assessment Tool ................................ 149 Table 6.13 Reflections on WAREs incorporation of the Guiding Principles for CBPR Research Listed in Table 6.6 ................................ ............................. 15 8 Table 7. 1 Site Compa rison of Social, Environ mental, and Economic Factors in Florida, Bolivia and Guyana. ................................ ................................ ........ 16 7 Table7. 2 Summary of Information on Mercury Compounds Required in the Mercury Export Ban Act of 2008. ................................ ................................ 17 3 Table 7.3 Linking Principles of C ommunity Based Participatory Research (CBPR) ................................ ...... 1 79 Table 7.4 Gold Companies in Guyana and Bolivia. ................................ ...................... 1 8 5 Table 7.5 Environmental Analysis Performed at Field Sites in the USA, Bolivia and Guyana ................................ ................................ ................................ ............ 1 89 Table 7. 6. Mercury Results from Sites in The USA, Guyana, and Bolivia Reported for Unfiltered Water Total Mercury (uwthg) and Sediment Total Mercury (sTHg). ................................ ................................ ................................ ............ 19 2 Table 7. 7. Fish Length (L), Weight (W), and Total Mercury Loading (fTHg) from Tampa, Fl, Guyana, and Bolivia ................................ ................................ ..... 19 3 Table 7. 8. Hazard Index (H) and Critical Fish Concentration (C) for Children Assuming H = 1.. ................................ ................................ ............................ 19 4

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x Table 7. 9. Hazard Index (H) and Critical Fish Concentration for Adults (C) Assuming H = 1. ................................ ................................ ............................. 19 5 Table 7. 10. List of Activities that Contribut e to Various Exposure Pathways in Study Sites in Bolivia, Guyana and Tampa ................................ ............................ 19 7 Table 7. 11. (A) Summary of Mercury Use, Occurrence and Exposure in Bolivia, Guyana and Tampa, Florida as They Relate to the Five Pillars of Sustainability ................................ ................................ ................................ 20 4 Table 7. 12. (B) S ummary of Mercury Use, Occurrence and Exposure in Bolivia, Guyana and Tampa, Florida as They Relate to the Five Pillars of Sustainability ................................ ................................ ................................ 20 5 Table 8.1. Recommendations for Future Work Using the Pillars of Sustainability ........ 2 09

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xi LIST OF FIGURES Figure 2 1: Primary, Secondary, and Remobilized/Re emitted Natural and Anthropogenic Sources of Mercury Inputs to the Cycling of Mercury in the Ecosystem 16 ................................ ................................ ................................ 5 Figure 2. 2 : Biogeochemical Cycling of Mercury in the A tmosphere, H ydros phere, and L ithosphere 1 ................................ ................................ ............................... 10 Figure 2 3 : Global Mercury Emissions by Sector and their proportions in the top ten countries with highest emission rat es. (Modified from United Nations Environmental Programme Global Atmospheric Mercury Assessment) 16 ...... 11 Figure 2.4 : General Representation of Sorption of Mercury (Sorbate) to Natural Sediments and Soils (Sorbent) in the Presen ce of Organic Matter (OM) and salts (Cl ) ................................ ................................ ................................ ... 14 Figure 2.5: Mer cury System Flow to Humans and the Associated Adverse Health Effects ................................ ................................ ................................ .............. 18 Figure 2.6 : Geometric and Arithmetic Mean Blood Mercury (BHg) Concentrations (ugl 1) and Estimated 30 Day Mercury Inta 1 ), Respectively with a 95% CI (Taken from Kuntz et al.) 87 ................................ ..................... 21 Figure 2.7: Figure 2. 7 1998 2008 (a) Global Market Value for Mercury and Gold; an d 1998 2008 (b) US Commodities Imports and Exports derived from USGS Minerals Statistics and Information Database 20, 100 104 ....................... 24 Figure 3.1: Taken from the National Atmospheric Deposit i Depos ition Network (a) Total Mercury Concentrations (n g L 1 ) and (b) Total Wet Mercury Deposition ( g m 2 ) 109 ................................ ..................... 27 Figure 3.2: Hillsborough County Impaired W ater bodies A tlas ( Areas in R ed are C onsidered to be I mpaired) 114 ................................ ................................ .......... 29

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xii Figure 3. 3 Map of the Tampa Bay Area (Modified from Malloy et al., 119 ) and Its Geographic Segments (Old Tampa Bay, Hillsborough Bay, Middle Tampa, Lower Tampa Bay, Boca Ceiga Bay, and Terra Ceia Bay) ................. 31 Figure 3.4 Map of the Hillsborough River System Tributaries ( M odified from Pillsbury& Byrne, 2007). ................................ ................................ ................ 33 Figure 3. 5 Sampling L ocations (Noted by Red Points) A long the Hillsborough River, Tampa, FL ................................ ................................ ............................. 3 5 Figure 3.6 Sample Collection Flow Diagram with Method Analysis for Each Sediment Matrix ................................ ................................ ................................ 36 Figure 3.7 SEM/EDAX Standardless Quantification of Normalized Elements from Sediments Collected from (a) Sargent Park; (b) Rotary Park; and (c) Lowry Park ................................ ................................ ................................ ........ 5 4 Figure 3.8 SEM I mage and Element M aps for Rotary Park sediments. ............................ 55 Figure 3.9. Fish Species Collected from the Hillsborough River, Tampa, FL ................... 56 Figure 3.10 (a d): Scatterplots of Total Mercury Loadings (fThg) in mg/kg Wet Weight as a Function of Len gth, Weight, And Age, for Each Fish Species.. ................................ ................................ ................................ ............ 58 Figure 3. 11. (e g) Scatterplots of Total Mercury Loadings (fThg) in mg/kg Wet Weight as a Function of Length, Weight, and Age, for Each Fish Species. Pearson Correlation Coefficients, Rs, and P Values Are S hown. .................. 59 Figure 3.1 2. Scatterplot of Mercury Loading Versus Fish Weight for Samples Taken at Rotary Park for This Study (20 LMB out of 38 Fish Total) and By the Florida Fish and Wildlife Commission (FFWC) Between 2003 and 2007 for LMB Only. ................................ ................................ ................................ 60 Figure 1 .1 Administrative Regions of Guyana. Mahdia and Iwokrama are located in the Potaro Siparuni (8) while the Konashen District is in th e East Berbice Corentyne (6) ................................ ................................ ..................... 67 Figure 4.2 Guyana declared gold production 1979 2008 from large scale OMAI mine and small to medium scale mine s (non Omai) 184 ................................ .... 71

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xiii Figure 4.3 St Ridge/Port Kaituma (KN Kaiteur National Park ................................ ............. 75 Figure 4.4 Map of Sampling Areas Along the Essequibo River (Kamoa River, S ipu River, Acari Mountain Creek, Masakenari River) within the Konashen Community Owned Coonservation Area (COCA) ................................ ........... 7 8 Figure 4. 5 Location of Sample Sites Along the Essequibo and Siparuni Rivers Within the Protected National Park of Iwokrama, Guyana (S.A.) and Regional Borders ( M odified from Iwokrama ) ................................ .................. 80 Fig ure 4.6. Box Plot of Total Mercury Loading on Sediments and Soils, sTHg (Ng/G Dry Weight), By Area Sampled Showing Values That Fall Within the 25th and 75th Percentile (Box), the Minimum and Maximum Load ing (Line) and the Median (Diamond). ................................ ................................ ... 88 Fig ure 4. 7. Photographs of Sediment Samples Collected in Mahdia from 5 Different Mines. ................................ ................................ ................................ ............... 89 Figure 4. 8 Diagram of Mine 2 in Mahdia, Showing Main Mining Processes and Areas Sampled ................................ ................................ ................................ .. 90 Figure 5.1 Nine Department s of Bolivia With Respect to Other Sampling Locations and An Enlargement of the Sampling Area Within Bolivia, Lago Titicaca. .... 96 Figure 5.2 Total N umber of P ersons E mployed in V arious M ining S ectors in Bolivia from 1989 1998 B ased on R eports by Bocangel 236 ................................ ......... 98 Figure 5.3 Lago Titicaca (Lake Titicaca) and Its Two Southea sterly Quarters Known to the Indigenous, Quechua, as Lago Huinaymarca (2) and Lago Chucito (3) ................................ ................................ ................................ .................... 10 2 Figure 5.4 Digital Mapping of Sample Points of the Tributaries of Lago Titicaca with Enlargements of the Tin (Sn) and Lead (Pb) Mining Concessions and Lago Titicaca (from Google Earth). ................................ ......................... 10 4 Figure 5.5. Fish Species (a) Trucha ( Salmo Gaidneri ) and (b) Pejerrey ( Basilichthyes boariensis ) Collected from Lago Titicaca Area. ................................ ............. 113

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xiv Figure 5.6 (a f) Scatterplots of Total Mercury Loadings (fthg) in mg/kg Wet Weight As a Function of Length, Weight, and Age, for Each Fish Species. .............. 116 Figure 6.1. Pillars of Sustainability With Education Being the Principle Force Joining All Sectors. ................................ ................................ ......................... 12 3 Figure 6.2 2008 Data for the Number of Students Enrolled Per Education Level in Bolivia, Guyana and the United States. ................................ ......................... 12 5 Figure 6.3 Comparisons of Patents (A) Applied for, (B) Granted and (C) in Force for the United States, Japan, Germany, the United Kingdom and China from 1984 to 2001. ................................ ................................ ........................ 1 27 Figure 6.4. Demographics of Civil E ngineering Faculty at the Top 50 Departments in the US for the Year 2007 by (A) Ehnicity and (B) Ethnicity of Female Faculty.. ................................ ................................ ................................ .......... 129 Figure 6.5 Collaborative Partnerships Required to Sustainably Manage Environmental Systems With an Example of Stormwater P onds in East Tampa Used as An Example. ................................ ................................ .......... 137 Figure 6.6 Maps Of East Tampa Showing The Proximity Of Schools In East Tampa .. 1 4 0 Figure 6.7 2008 2009 Demographics of (A) Young Middle Magnet, (B) Lockhart Elementary and (C) Lawton Chiles Elementary ................................ ............ 14 1 Fi gure 6. 8. Organizational Chart for WARE, Indicating Areas of Interaction of The Members of Each of The Three Participatory Groups (Community, USF, Schools). ................................ ................................ ................................ ......... 141 Figure 6.9 Maximized Constructivist Learning Approach for the Water Curriculum Principles. ( Adopted from Christie 305 ) ................................ .......................... 145 Figure 6.10 Sketch of Educational Kiosk to be Located at the Robert S. Cole Community Lake in East Tampa. ................................ ................................ 152 Figur e 6.11. Schematic of Growth in Partnerships and The Need for Curriculum Development Gathered from Reflective Journal Entries ................................ 160

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xv Figure 7.1 The Presence of Mercury in the Global Environment ................................ ... 16 5 Figure 7.2. Associated Pathways of M ercury T hrough V ariou s R egions ( M odified from Swain et. al 1 ). ................................ ................................ ........................ 16 6 Figure 7. 3 World Consumption Behavior (a) Total Consumption 7 an d (b) Mercury Consumption from 1500 2000 ( T aken from Hylander 8 ). ............................... 17 0 Figure 7. 4 Legislation, Consumption, and Production of Mercury in the US from 1970 1997. A FLASK is E quivalent to 76lbs (34.5 kg) of Mercury ............. 17 2 Figure 7. 5. 1998 2008 US Commodities Imports and Exports Report for Mercury (Data Collected from USGS Mi nerals Database 330 332 ................................ 17 4 Figure 7. 6. 10 Year Gold Price in USD per ounce. Last Closing Price was $1,134.80 on 03/05/2010 ................................ ................................ ................................ 17 5 Figure7. 7 Declared Gold Production for (A) Guyana: 1979 2008 from Large Scale OMAI Mine and Small to Medium Scale Mines (non Oma i) (GGMC, 2009) and (B) Bolivia ................................ ................................ ...... 17 5 Figure 7. 8 Gold Reserves Above and Below Ground (Modified from Lehman Brothers and Ali 107 ) ................................ ................................ ........................ 1 8 6 Figure 7. 9. Various Players Who Influence Sustainability as it is Relate d to Mercury Use and Exposure ................................ ................................ .......................... 1 88 Figure 7. 10. Mercury Use at a Mine in Mahdia, Guyana with Posters Done by the GENCAPD Project in Conjunction with the Guyana EPA. ...................... 19 7 Figure 7. 11. Pictures from Guyana Showing Direct Exposure to Mercury.. .................... 198 Figure 7.12 Mercury Exposure from Fish.. ................................ ................................ ...... 20 1 Figure 7.13. Potential Partnership Structures with Conservation International (CI) in Guyana. ................................ ................................ ................................ ......... 20 2 Figure 7.14. Potential Partnership Structures for Guyana and Bolivia Where Bolivian Partnerships are Faded. ................................ ................................ .................. 20 2

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xvi MERCURY IN THE ENVIRONMENT: FIELD STUDIES FROM TAMPA, GUYANA AND BOLIVIA Joniqua A ja Howard ABSTRACT Tampa (US), Guyana (SA), and Bolivia (SA) are geographically socially, economically, and politically unique which make them ideal sites to study issues of mercury and sustainability s innate ability to bioaccumulate and biomagnify in aquatic and terrestrial e cosystems poses a severe threat to both human and environmental health. Th e most vulnerable populations affected by mercury consumption include coastal communities, children, women of child bearing age, the indigenous poor and persons with high environmental/occupational exposure factors Communities in the regions of Florida, B olivia, and Guyana whose diets are high in fish and are e nvironmentally/occupationally exposed to mercury may be at a higher risk of mercury intoxication especially in the absence of education on the topic Mercury l oadings in rivers, streams and mine ta iling waters and sediments ranged from 0.9 114 ng/L and 29 2891 ng/g, respectively; whilst fish mercury loadings were 0.02 1.034 mg/kg wet wt. Although mining sites had the highest mercury sediment and water lo adings there were no significant differences when compared to pristine sites in Guyana. Fish loadings above recommended EPA/WHO regulatory limits were observed at all sites and no ne had signage, informational warnings or educational material available A pilot study that included f our elementary schools in Tampa showed that Water Awareness Research Education (WARE), a community based participatory env ironmental educational program, is a sustainable solution to addressing issues of mercury exposure

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1 CHAPTER 1: INTRODUCTION 1.1 Motivation and Research Objectives The burgeoning problem related to mercury (Hg) contamination in the environment has gained worldwide attention because of its detrimental effects on human health, especially childhood developm ental disorders In fact, according to the Global Mercury Assessment Program, mercury levels have increased considerably since the on set of the industrial age 2 Its atmospheric residence time is approximately 0.5 2 years 3, 4 which results in a complex global cycling mechanism. I ts half life in the human body is 30 80 5, 6 days (whole body) which is dependent on mercury species, route of exposure, dose, and sex. The primary mechanism of Hg contamination at regional and global scales is atmospheric mercury transported chiefly from coal fired power plants and artisanal mining; however, the principle route of human and animal exposure stems from fish consumption. s ability to bioaccumulate and biomagnify in aquatic and terrestrial e cosystems poses a severe threat to the health of humans and animals 7 The most vulnerable populations affected by mercury consumption include coastal communities 8 children 9 women of child bearing age 5 the indigenous poor 10 and persons with high environmental/occupational expos ure factors (e.g. artisanal gold miners 11, 12 jewelers, fishermen 13 etc.). Despit e governmental, federal, and international agency concerns regarding the impacts of mercury on water, soil, biota, and human health, regulations and recommendations continue to provide contradictory information as well as insufficient means of disseminati well informed consumption decisions 14 15 Developing countries face even more

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2 challenges with monitoring and enforcement of environmental regulations to protect human health and the environment from mercury contamination. The main goal of this research was to improve our understanding of the factors contributing to mercury exposures in three geographically unique locations, Tampa, FL; Mahdia/Iwokrama, Guyana; and Lago Titicaca, Bolivia, and develop community oriented solutions that reduce exposure. The three objectives tested along wit h the tasks required were: 1. Objective 1: Characterize mercury loadings in three previously unmonitored freshwater bodies that represent different geologies, demographics, and regulatory frameworks. Task 1a: Identify and characterize suitable study sites for this work. Task 1b : D eter mine levels of mercury present in fish, water, and sediments located in/near some of the most vital water bodies in Florida, Bolivia, and Guyana. All sample matrices were analyzed for total mercury concentrations. Whilst sed iment samples were further characterized by BET surface area analysis, electron dispersion spectroscopy, and X ray diffractometry. Total m ercury analyses were carried out using cold vapor atomic absorption spectroscopy (CVAAS) and cold vapor atomic flores cence spectroscopy (CVAFS) Task 1c: Understand the geochemical conditions that affect the fate of mercury. 2. Objective 2: Compare results and conditions at study sites to determine the role of socioeconomic factors in mercury loadings. Task 2a : Documen t the socioeconomic, regulatory and geopolitical factors within the United States (Florida) and Internationally (Bolivia and Guyana) through a literature review

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3 Task 2b: Identify site similarities and differences in mercury loadings and human impacts Ob jective 3: Provide an Initial E valuation of an existing CBPR project, WARE, for its ability to increase awareness of environmental, environmental health and sustainability concepts as they relate to mercury exposure. Task 3a: Review educational literature and describe the WARE project. Task 3b: Assess project activities through reflective journaling in terms of their ability to increase awareness of environmental, environmental health and sustainability concepts. Task 3c: Recommend focal areas for imp roving and expanding the project to reach larger populations. This dissertation has been arranged in the following format: Chapter 2, Background. The background is divided into three main sections which principally focus on the behavior of mercury in th e environment, its usage, and toxicity. Chapter s 3 5, Sample Areas: Florida, Guyana, and Bolivia, respectively. These Chapters give an overview of each study site within Florida, Guyana, and Bolivia impeding issues) as well as the governmental policies governing mercury will be discussed. In addition, each chapter will provide a description of the targeted sampling area, the sampling protocol; materials used as well the analy tical methods carried out followed by a general discussion of the results. Chapter 6, Sustainability: Community Engagement and Active Participation in Mercury Research. This chapter discusses the pilot initiative to broaden

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4 community awareness and participation in understanding issues of mercury at the elementary level. Chapter 7 Conclusion: Integrative Examination of Mercury. This chapter summarizes all of the data results with a given framework and followed by recommendations for future research.

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5 CHAPTER 2: BACKGROUND 2.1 Introduction This chapter provides an overview of mercury and its interactions within the environment and the associated health implications from its presence in our society. The principle focus will be on understanding its interactions with the ai r, water, sediment, and flora/fauna. Furthermore, an overview of its effects on human populations especially women of child bearing age, children, and the indigenous will be discussed. Figure 2.1 Primary, Secondary, and Remobilized/Re emitted Natural a nd Anthropogenic Sources of Mercury Inputs to the Cycling of Mercury in the Ecosystem 16

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6 2.2 Overview of Mercury Mercury is a global contaminant of increasing concern. Ranked 3 rd out of 275 substances on the Agency for Tox ic Substances and Disease Registry (ATSDR) 17 it is a Grou p XII transition metal that is released into the environment through natural and anthropogenic 18 sources. These sources can be divided into primary natural, primary anthropogenic, secondary anthropogenic, and remobilized/re emitted sources (Figure 2.1). It i s commonly found in three oxidation states (Hg 0 Hg 1+ and Hg 2+ ) in the environment and can form inorganic and organic species. The most abundant naturally occurring forms are metallic mercury (Hg 0 ), mercuric sulfide (HgS), mercuric chloride (HgCl 2 ), and methyl mercury (CH 3 Hg or MeHg). Exposure to each species neg atively impacts the environment; however, methyl mercury is the most toxic form and can have detrimental effects on the human central nervous system and specific target organs 9, 19 Since MeHg is lipophlic it readily b ioac cumulates and biomagnifies in the environment. It also has a high affinity for sulfur containing compounds 20, 21 Mercuric sulfide, commonly known as cinnabar, is a red mineral that once exposed to light turns black and is further refined by heating at temperatures above 540C to form the liquid metal mercury 2 Hg 0 This is the principle production method of mercury used exist principally in Kyrgyzstan, Russia, Spain, Ukraine Algeria, and Slovenia. It is e stimated that nearly 600,000 tons of mercuric sulfide ore still exist 22 The usage of metallic and other species of mer cury ranges from fluorescent light bulbs, paints, facial bleaching creams, necklaces imported from Mexico, dental amalgams, some toys (e.g. infant teething rings, maze toys), light up shoes, switches, thermostats, industries (e.g. gold mining, pulp and pap er milling, chlor alkali) as well as in cultural and religious practices. This is due to its unique physical and chemical properties. temperature yet it is still a solid. It is an excellent electrical conductor and resistant to corrosion. Unlike other metals (e.g. Zn, Co, Ni), mercury is not essential in the human body and is very toxic thus making it ideal for usage in vaccinations, pesticides, and

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7 antisepti cs. It can form bonds with gold and silver which helps to produce a higher yield of recovery of the precious metals. As outlined in the physical and chemical properties of mercury in Table 2.1, the low aqueous solubility or low reactivity and high stabil ity of mercury allows it to have a long atmospheric residence time. However, its low vapor pressure (0.2 KPa at 38.72 C) allows it to be deposited readily as Hg 2+ and re emitted into the environment as Hg 0 via photoreduction. In addition, it can be tran sported to shallow sediment aquatic environments via particulate matter (wet or dry). Methylation of mercu ry occurs to a relatively high extent in aquatic systems 23 25 making fish consumption the leading route o f human exposure today 26 As a result several exposure and consumption regulations have been established in the U nited States and internationally. These regulations have been detailed in subsequent section in Table 2. 3 whilst the cycling of mercury in the environment has been described in Fi gure 2.2. The next section describes the cycling of mercury in the environment.

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8 Table 2. 1. Physical and Chemical Properties of Mercury (Taken from Benjamin 2 7 ). Property Valu e Atomic number 80 Electronic Configuration (n=) 1s 2 2s 2 p 6 3s 2 p 6 d 10 4s 2 p 6 d 10 f 14 5s 2 p 6 d 10 6s 2 Electronic Structure Rhombohedral Atomic mass (g/mol) 200.59 1.02/1.76 Boiling Point (K) 630 (357C, 675F) Melt ing Point (K) 234.43 ( 38.72 C, 37.7 F) Density (g/cc @ 300K) 13.546 Vapor Pressure (Pa @ 38.72 C)) 0.0002 Enthalpy of Automization (kJ/mol @ 25 C) 61.5 Specific Heat (J/gK) 0.139 Electronic Potential ( eV) 28.2 Hardness Scale (Mohs) 1.5 Molar v olume (cm 3 /mol) 14.81 Flammability Noncombustible liquid Description Silver colored transition metal Alternate names Mercurio, Quicksilver, Hydragyrum, Azogue Stability Constants for metal ligand complexes (Log k) HgSO 4 HgCl HgCl 2 HgCl 3 HgCl 4 Hg(HS) 2 1.39 6.75 13.12 14.02 14.43 37.72 Solubility Values of Solids(Log K s0 ) Hg(OH) 2 (s) HgCO 3 (s) HgS (cinnabar) 25.40 22.52 52.01 Gibbs Free Energy, G f (kJ/mol) Hg (l) Hg 2 2+ (aq) Hg 2+ (aq) Hg 2 Cl 2 (calomel) HgO (red) HgS (cinnabar) HgI 2 (red) HgCl + (aq) HgCl 2 (aq) HgCl 3 (aq) HgCl 4 2 (aq) HgOH + (aq) Hg(OH) 2 (aq) Hg O 2 (aq) 0 153.6 1 64.4 210.8 58.5 43.3 101.7 5.44 173.2 309.2 4 46.8 52.3 274.9 190.3

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9 2.3 Mercury in the Environment 2.3.1 Mercury Cycle The earth can be divided into four main spheres or layers: (1) atmosphere; (2) hydrosphere; and (3) lith osphere. These spheres are interconnected and each has its own unique property and ability to transport and retain heavy metal constituents (e.g. Pb, Hg, entering i nto the food chain several interactions occur within and between layers at the interfacial layer. The interfacial layer can be defined as the infinite thin boundary separating two phases or layers thus when a heavy metal constituent crosses this boundary it is considered to have been transferred to the other phase or enters into different spheres 28 In the hyrdosphere, lithosphere, and pedosphere the speciation of mercury is influenced by various abiotic (e.g. sorption, precipitation, photo induced volatilization, dissolved oxygen, pH, temperature, sediment surface char acteristics, carbon dioxide levels) and biotic (methylation or demethylation) processes. Extensive research has been underway using both model and real conditions to understand th is complexity. The biogeochemical processes thought to be involved in the c ycling of mercury across these spheres is shown in Figure 2.2

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10 Once emitted into the environment through natural or anthropogenic activities as gaseous mercury, it resides in the air for up to 0.5 2 years 3, 4 It is transported and dist ributed to the land and water bodies via wet, particulate, and dry deposition. In the hydrosphere mercury undergoes biogeochemical and photo oxidation transformation. It is then distributed between chemical species of inorganic divalent mercury (II) and organic mercury (methyl mercury CH 3 Hg) with its dominant species being HgCl 2 HgCl 4 2 Hg 2+ Hg, Hg species sorbed onto mineral oxides, and organo mercurial species 29 Organo mecurial species are the most toxic. Mercuric mercury in particular, is then uptaken by phyto plankto n which are consumed by zoo plankton thus entering into fish as it further bioaccumulates and biomagnifies to top predatory species (e.g. humans). Mercury also forms solid HgS (s) which is usually, but not always, found under reducing environments (either in sediment or in biofilms in the water column). In the litho spheres microorganisms exist. These microorganisms such as sulfur reducing bacteria (SRB) and methanogens are essential in the methylation and demethylation of mercury. In plants, uptake of me rcury has been found to be plant specific. In general, mercury has the tendency to accumulate in roots, indicating that the roots serve as a barrier to mercury uptake; however, m ercury concentration s in abo veground parts of plants appear to depend largely on foliar uptake of Hg 0 volatilized from the soil 30 Figure 2. 2. Biogeochemical Cycling of Mercury in the A tmos phere, H ydrosphere, and L ithosphere 1 Residence time: 0.5 2 yr Wet/dry Deposition

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11 2.3.2 Atmospheric Mercury Figure 2 3. Global M ercury Emissions by Sector and T heir P roportions in the T op T en C ountries with H ighest E mission R ates. (Modified from United Nations Environmenta l Programme Global Atmospheric Mercury Assessment) 16 Natural and anthropogenic emissions from volcanic eruptions, soil degassing/erosion, sea venting/evaporation, fossil fuel combustion, smelters, municipal/medical incine rators, are the main sources that introduce mercury into the atmosphere. Being a toxin as well as a commodity, Western Europe exports about 100 tons of mercury to Brazil each year, where it is latter emitted over the Amazon and undergoes trans boundary di spersion 31 According to the Global Mercury Assessment Program, atmospheric mercury levels have increased considerably since the on set of the industrial age 2 During the last 100 years, anthropogenic sources have contributed approximately 70% of the total mercury input to the environment 32 Global me rcury emissions by sector and their proportions are shown in Figure 2.3. Most of the mercury emission is derived from industrial or mercury processing sources which can be divided between 45.6% for fossil fuels (e.g. coal fired power plants), 18.2% artis anal and small scale gold production, 16.3% for cement waste incineration and 10.4% metal production. However, Lacerda and Marins argue that out 1 ), gold mining contributes 67.3% (77.9

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12 1 ) to the at mosphere 33 In 1997, i t was reported that China, Venezuela, Philippians, and Indonesia are the countries with the greatest reported mercury inputs into the global atmospheric mercury load 33 The dominant species of mercury rele ased into the atmosphere from anthropogenic activities include Hg 0 (vapor), Hg 2+ Hg particle, and HgO. Eighty percent of the total mercury that remains in the atmosphere is 20% Hg 0 whilst 60% is Hg 2+ 34 As it is distributed throughout the world by vertical wind dispersion it resides in the air for up to 0.5 2 years 4, 32 The atmospheric transport of toxic chemicals, such as mercury, to other 35 In large, it is still highly debated whether atmospheric Hg deposition is due to local, regional, or global sources 32 However, it is certain that atmospheric mercury deposition is the primary route by which mercury enters into most freshwater systems. Water bodies in close proximity to mercury emitting sources such as coal fired power plants and gold mining directly influence aq ueous and fish mercury levels 36 Such regio nal mercury emitters, have contributed to global mercury pollution due to the mobility of mercury in the air 31 Comparative studies of mercury emission rates on gold mining in c ontrast to other industries and practices (e.g. chlora alkali plants, agriculture, slash and burn, etc) in South America described by Lacerda and Marins shows that gold mining is the greatest contributor 33 Recent estimates suggest that China is by far the largest contributor to atmospheric mercury load due to anthropogenic sources from coal combustion and gold mini ng, whilst the U.S. is the third although its emissions, are estimated to account for roughly th ree percent of the global total 16, 37

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13 Table 2.2. Environmental Mercury Fluxes from Global Mercury Models 16 Globally, environmental mercury fluxes from global models suggest that total mercury emissions from land, oceanic, and primary anthropogenic sources have decrease d from 2002 to 2008 (Table 2.2 ) 2.3.3 Mercury in Water and Sediment As mercury is deposited in the hydrosphere, it can be mobilized by physical perturbations, chemical or biogeochemical mechanis ms (e.g. surface charging and dissolution), low ionic strengths or conductivity and the presence of strong sorbing ions in solution. According to model calculations by Duursma, tropical estuaries at steady state can act as sinks or sources for contaminant s depending on the time period 38 Their projections showed that at the onset of con tamination the estuary would act as a sink whereas after a period of years it will begin to act as a source. The total inflow and distribution of dissolved and particulate contaminants from the river is not equal to the discharge along the estuary to the sea. Therefore, contaminants become immobile allowing bottom sediments to act as a buffer.

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14 Natural sediments are a complex mixture of minerals/solid phases that exhibit a range of characteristics which influence heavy metal behavior. According to Lindse y 39 surface sediments in aquifers, lakes, and rivers principall y contain minerals of iron, aluminum, and silica which also represent the most abundant mineral oxides in the environment Mineral oxides (e.g. iron and aluminum oxides like goethite and gibbsite respectively) play an important role in the speciation of mercury. Hence s ediments and soils can act as potent ial sources or sinks for Hg Figure 2.4. General Representation of Sorption of Mercury (Sorbate) to Natural Sediments and Soils (Sorbent) in the Presence of Organic Matter (OM) and S alts (Cl ) When in contact with water, mineral oxides form amphoteric surface groups (e.g. positive, negative or neutral surface charges); therefore, they can accept or lose protons depending on the pH of the water bodies. If acidic conditions exist, the overall number of positively charged surface sites would increase thus making mercury sorption to the mineral oxides decrease. This would allow mercury (Hg + or Hg 2+ ) species to remain in solution or the aquatic environment where they can be further transformed to the mo st the positive sites would diminish and vice versa would occur for negatively charged surface sites. Therefore, m ercury (II) sorption to clays 40 42 mineral oxides of iron 43 47 aluminum 46 48 and silicon 48 50 would typically increase as a function of pH until it reaches a maxima then decrease in higher pH regions. As a result, the excess mercury will sorb and/or interact with other sediment constituents (e.g. ions, heavy metals), attach to particulate matter/colloids (e.g. organic matter), transform to methyl mercury, or remain in the aqueous solution as Hg 2+ and/or Hg (Figure 2.4) Soil s high in clay, total iron, and carbon from the pristine forested area of French Guyana exhibited maximum

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15 mercury concentrations in upstream parts of the watershed that reached up to 500 ng g 1 51 Methyl mercury sorption to mineral oxide surfaces of goethite and kaolin, on the other hand was found to be much lower than inorganic Hg 2+ sorption 40 In addition, the presence of chloride, sulfate, phosphate, other heavy metals (e.g. Ni(II), Pb(II)), and/or organic matter can influence m ercury sorption to mineral oxide surfaces through various processes including competition for surface sites, changes in the surface charge, formation of ternary surfaces and formation of more stable aqueous complexes 45, 48 50, 52, 53 Sediments containing high organic content or natural organic matter can form extremely strong complexes with mercury 54 56 thereby affecting the desorption or removal of mercury from the mine rals as well as its bioavailability 57, 58 Studies by Han et al. on the chemical speciation of dissolved mercury in surface waters of Galveston Bay determined that almost all of the dissolved mercury (> 99%) in Ga lveston Bay was complexed by natural ligands associated with dissolved organic matter 56 Fur thermore, the study determined that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. Thereby suggesting that sulfide limits production and accumulation of MeHg in river systems. Similar findings were determined in the study of the behavior and fate of mercury in sediment and water samples collected from the estuarine Patuxent River 59 These effects onc e again can vary depending on such factors as the temperature, pH, alkalinity, salinity, dissolved oxygen content, the form of mercury present, the geologic area, and the type of natural organic matter (NOM). NOM or decaying waste from homes, industria l plants, animals, or run off that contain carbon compounds (e.g. plants, trees, leaves, grass clippings, peat,) is divided into two distinct groups, fulvic and humic acids. Fulvic acid, the hydrophilic or water loving fraction of NOM, increases mercury s orption on iron oxide surfaces (e.g. goethite) 43 but decreases sorption of both Hg(II) and methyl mercury from aluminum silicate surfaces (e.g kaolin) 40 NOM has different functional groups (e.g. carboxylic, phenolic, thiol) that play important roles in complexing mercury thereby causing a distribution of b inding affinities 60, 61 Researchers found that dissolved organic matter (DOM) influenced the abiotic, photo induced methylation rates of mercury 62 Recent studies on mercury volatil ization to Hg(0) found that the presence of NOM decreased volatilization in

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16 aqueous solutions, but that mercury volatilization in real lake samples was significant in sunlight 63 Organic acids can dissolve silicon, Al, and Fe bearing minerals which potentially can cause the mobiliza tion and transport of metal contaminants. Temperature and dissolved oxygen which are inversely proportional to each other are also important in controlling the mobilization of mercury. According to Ho and Wang 64 by increas ing the temperature of your system there will be a net increase in chemisorption and diffusion processes, thereby playing a significant role in the overall sorption process 64 It was further suggested that typically sharing and/or exchanging of electrons between the sorbent and sorbate is an endothermic process thus increasing temperatures which would enable metal ions to penetrate i nto n ew active sites of sorption on the sorbent surface. 2.3.4 Mercury in Fish Overtime mercury does not degrade, it bioaccumulates and biomagnifies. In fish, methyl mercury accounts for greater than 90% of the total mercury present 65 Mercury bioaccumulation usually occurs in the fatty tissue of fish and is larg ely magnified in large predatory fish. The maximum contamination level determined by the US EPA and WHO for fish is 0.5 g/g 66 and 2.5 g/g 67 wet wt., respectively. Mercury concentrations vary by the fish species, fish size, t ype of water body (e.g. fresh, salt, pond, lake, river, ocean, bay), the specific geographic location, and atmospheric mercury deposition levels; however, it is well known that specific fish species such as salmon, shark, and King Mackerel, globally contai n elevated levels of mercury. In certain locations like Florida high levels of mercury have been found in largemouth bass and other freshwater gamefish 68 In studies of the Ro Ramas, the largest tribu tary of the Lake Titicaca watershed on the Pe ruvian side in South America, pejerrey (Basilichthyes) and carachi (Orestias) exceed US EPA fish tissue 1 66 A lso, Guyanese fish samples collected from two gold mining areas exceed these limits as fish total mercury levels ranged from 0.018 0.798 1 10

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17 Mercury accumulation in f ish has been associated with many factors. Dittman and Driscoll found that in remote lakes the watershed area, elevation, and change in fish body condition influence fish total mercury loadings 69, 70 Hutcheson et al. determined that mercury levels found in the dorsal muscle of largemouth bass (n=138) and yellow perch (n=97) from 15 lakes in Massachusetts were impacted from local mercury sources (e.g. medical and municipal waste incinerators) 69, 71 Other researchers argue that there is a weak association between inorganic mercury loadings from the atmosphere and the accumulation of methyl merc ury in aquatic biota and mosquitoes would be a more useful indicator for atmospheric mercury deposition to aquatic systems 70 threat to humans has been d irectly linked to rate of consumption, species, age, and body weight. It has also been suggested that coastal communities which may consume larger amounts of seafood exhibit higher levels of methyl mercury than inland populations 72 2.4 Toxi city of Mercury Mercury has been found to seriously impact human health. Human exposure to mercury can occur through inhalation, ingestion, and absorption through the skin but the principle route of exposure is through fish consumption 73 75 The resulting effects of mercury depend on mercury species, duration, and source of exposure. The three forms of mercury (elemental, in organic, and organic) each have its own unique profile of toxicity. For example, mercury exposures from fish and marine mammals/crustaceans contribute to elevated methyl mercury levels whilst contact from dental amalgams, gold mining (other occupational ex posures), Afro Latin religious ceremonies, fossil fuels, and incinerators would be from elemental mercury 6 In all, s ome effects may include dysarthria 76 loss of vision/hearing 9, 76 tremors, neurological/reproductive disorders 9 coma, kidney failure 77, 78 lung cancer 79, 80 congestive heart disease 81 as well as death in some cases 6 With such tragedies like that in Minamata, Japan where over 3,000

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18 Jap anese residents died of methyl mercury poisoning due to the consumption of mercury laced fish, researchers have delved into understanding the complex nature of the pollutant. Figure 2.5 Mercury System Flow to Humans and the Associated Adverse Health Eff ects. Once inhaled inorganic aerosols deposit in the respiratory tract and are absorbed depending on particle size. According to the Agency for Toxic Substances and Disease Registry (ATSDR) organisms retain approximately 80% of inhaled metallic mercury w hilst 100% of the mercury is absorbed in the lung alveolus 82 Thus the threshold limit 3 83, 84 While in the respiratory tract, m ercury immediately begins to bind to specific target organs and target cells or sites w here hormones bind. The target organs for mercury accumulation are primarily the brain, liver, and kidneys; however, distribution in the human body varies according to species and route of exposure. According to the World Health Organization (WHO) 85 daily c onsumption levels may be higher in contaminated areas as well as in locations

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19 where fish constitute a high proportion of the diet. Since methyl and elemental mercury are lipophilic 86 they are readily distributed throughout the entire body. On the other hand, mercuric mercury (Hg 2+ ) is accumulated extensively in the kidneys 6, 75 In all, mercury targets the kidneys, thyroid, central nervous system, heart, and brain 29 Thus transport of inorganic mercury across the intestinal tract depends on solubility, dissociation in the gastrointestina l tract, intestinal pH, and the presence of essential nutrients (Cu 2+, Zn 2+ ). During the transport process t arget cells that bear receptors are capable of res ponding to the metabolic functions of ho rmones. These hormones (e. g. amines, thyoxine, peptides, proteins, etc.) help to regulate metabolic functions of other cells in the body and float in the blood or lymphatic fluid until they reach their target cell. I t is believed that during this process mercury that is present within the blood stream or cells may bind to the hormones and/or inhibit proper flow of the regulatory chemicals th ereby potentially leading to neurological damage and other health impairments such as myocard ial infarction, lung disease renal failure among other disorders and diseases In pregnant women, mercury can cross the blood placenta barrier thereby entering into the brain of the developing fetus 5 Mercury and inorganic constituents are then excreted via the kidneys (bile), liver, intestinal mucosa, sweat glands, salivary glands, feces, urine, hair, and breast milk. In particular, prior to elimination methyl mercury is metabolized to inorganic mercury 87 Its half time in the whole body is 70 80 days. Therefore, at an excretion rate of less than 1% of the body burden per 24 hours, half of the body bur den of mercury is eliminated 5 Thus it will take approximately 365 days given a whole body half time of 70 days of regular intake of m ethyl mercury to attain a steady state balance between uptake and excretion of methyl mercury 5 The effects of mercury vary depending on geographical location, sex, age, exposure routes, and pre existing conditions. Health effects of mercury from various exposures and the effects on present health conditions in popula tions have been widely studied. Most of the literature examines the e ffects of MeHg due to fish consumption such as the Seychelles Islands, Faroe Islands, and Minamata, Japan. These studies have helped to establish the maximum contamination guidelines set by the US Environmental Protection Agency and the World Health Organ ization as seen in Table 2.3.

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20 Table 2.3. Current R egulatory L imits and G uidelines for M ercury S et by G overning A gencies for the United States and I nternationally. USEPA WHO Drinking Water MCL ( g/L inorganic Hg) [4] 2 6 67 Recommended Surface Water (ng/L) 12 Pe r missible Hair ( g/g) 11.1 10 20 88 Urine ( g/g) below 10 P Fish ( g/g) dry weight (fish type dependent) 0.5 2.5 67 *Same for US Food and Drug Administration USEPA United States Environmental Protection Agency WHO World Health Organization Distributions of blood mercury levels within US census regions and coastal/noncoastal areas among women of childbearin g age (18 40) differed according to region. Mahaffey detailed the regional differences in blood mercury levels in increasing order as 89 : Northeast > South and West > Midwest Even within a particular regional area levels can vary. For instance, as summarized in Figure 2.6 day mercury intake is higher than ric mercury deposition rates being centrally focused in the southwestern portion of the state which has been shown to negatively impact the water and fish quality. This directly impacts women, children, and coastal communities. One in six women of child bearing age living in the coastal areas of the United States are more likely to have elevated blood mercury levels than non coastal residents 89

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21 Figure 2 6 (a) Geometric and (b) Arithmetic Mean Blood Mercury (BHg) Concentrations (ugl 1) and Estimated 30 Day Mercury Intake (ug kg 1 ), Respectively with a 95% CI (Taken from Mahaffey et al. ) 89 Moreover, race/ethnicity, knowledge, occupation and income are also seen as factors asso ciated with whole body mercury levels. The Centers for Disease Control suggest that across racial groups, minorities and Native Americans are at a higher risk of having elevated mercury levels 90 Ethnic differences in fish consumption patterns and knowledge studied by Burger et al. suggest that African Americans in Florida 91, 92 are at a higher risk of having elevated mercury levels 91 This may be due to fish consumpt ion patterns 92, 93 preparation practices 93 and limited knowledge on fish advisory warnings 92 Whilst studies by Karouna Renier et al. 8 determined that coastal communities and indigenous populations were more susceptible to mercury intoxication due to incre ased consumptive behaviors of mercury laced foods. However, a cross sectional study of fish consumption behavior within an inland American Indian reservation determined that 80% s thereby suggesting that risk communication and educational workshops are needed. 94 The examination of hair mercury levels from four coastal communities in Malaysia by Hajeb et al. 95 also showed similar positive correlations between hair mercury concentrations and fish consumption patterns for coastal commun ities as seen in the study by Karouna Renier et al. 8 In addition, in many remote and urban areas around the world fishing is an important aspect of recreation, culture, and tradition which may also influence consumption behavi or 96

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22 Outside of US borders, staple foods (e.g. cassava, potato, and rice) and fish consumption as well as rit ualistic and occupational mercury pollution, mainly due to gold mining, has been seen to directly affect community MeHg levels. In Hindu, Asian, Afro Latin Caribbean, and Brazilian based traditions such as Santeria, Palo, Voodoo, Babalao, and Espiriti smo mercury is prescribed for various spiritual healings and health ailments. Mercury, often referred to as azogue or vidajan, can be bought easily in local markets in developing countries. Although banned in certain products, it can be readily bought in amulets or capsules over the counter in the United States from botanicas and bodegas, stores that sell spiritual and traditional items. Azogue, as it is commonly referred, requires religious participants to ingest, sprinkle, burn, or carry in sachets mercu ry for treatment of gastrointestinal/health problems, spiritual cleansing, protection from evil spirits, and good fortune as well as love 97 On the other hand, Obiri 98 revealed that the consumption of cassava contaminated with mercury due to being grown in a gold mining area in Ghana may caus e cancer in 10% of adults and children which is above acceptable cancer risk range (0.1% or one case of cancer out of one million people). Furthermore, Iraqi residents who consumed grains treated with a mercury fungicide during a famine in the 1970s died f rom mercury poisoning 85 In Minamata, Japan, over 3,000 people suffered from physical deformities, emotional disorders, and death due to the consumption of fish that were contaminated from a chlor alkali plant that release d mercury directly into Minamata Ba y. Singh et al. observed that residents with elevated levels of mercury resided in gold mining communities located in the interior regions of Guyana (Isseneru and Kurpung) 99 Due to elevated mercury levels in the body many researchers suggest that there is a need for increased risk communication and education measures. Fish according to the American Heart Association (AHA) and other national and international health agencies, has nu merous nutritional benefits, such as containing an excellent source of protein, vitamins, minerals, and especially omega 3 polyunsaturated fatty acids (PUFAs). These nutritional benefits are described to protect against several adverse health effects (i. e. coronary heart disease, stroke, and pre term delivery) 100 ;

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23 however, it can lead to the over consumption of mercury laced fish. In fact, the AHA suggests that people with or without a known cardiovascular disease (CD) consume a variety of mainly oily fish at least twice a week which is more than the USEPA and WHO suggested consumption rates in terms of mercury in fish. A ccording to the EPA and WHO, consumption of fish containing meth yl mercury should be limited to an intake of less than 0.5 g/g and 2.5 g/g drey weight, respectively which is based on three factors: (1) fish size and type (2) r egular dietary intake and (3) location. The agencies recommend that pregnant woman and ch ildren reduce their intake of mercury laced fish However, conflicting intake limits exist across the US and abroad despite the uniform guidelines set forth by the World Health Organization (which are not enforce able). These contradictions pose as a problem in conveying information to the general public so they can make informed decisions. 2.5 Mercury as a Commodity Despite its properties as a toxin it is also a highly mined commodity. Its properties as previ ously mentioned in Section 2.1, make it ideal for usage in various products such as gold mining. In mining, mercury is used to recover gold. Its ease of availability, higher yield than simple gravitational techniques and inexpensive nature make it lucrati ve for small medium scale miners to use 101

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24 Figure 2. 7 1998 2008 (a) Global Market Value for Mercury and Gold; and 1998 2008 (b) US Commodities Imports and Exports D erived from USGS Minerals Statistics and Information Database 22, 102 106 The average price for a single flask (35 kg or 76 lb) of mercury on the free market has nearly doubled since 2004 to its present historical high value of US$600 per metric ton 101, 105 This rising price in mercury may be a direct result to the rising price of gold US$874.00 per ounce ton 101, 106 ( ozt) as seen in Figure 2. 7 The environmental and social implications of gold mining raise important questions on environmental sustainability. Almost 50% of gold is mined from indigenous lands and processed using mercury or cyanide 107 which is detrimental to the health of the environment and the people. It has been seen that the usage, handling, and management of tailings as well as the quantity of mercury used in small scale gold mining are principle issues of concern. It is commonly and conservatively estimated that for every 1 g of gold recovered there is 1 2 g of mercury lost to the environment 108 The historical h igh prices of mercury and gold, it can be estimated that for every 2 g of mercury used the cost of mercury for a miner would only represent 0.1% of their revenue which is a negligible loss. At the mptive behavior and the capitalist economies hoarding of gold bullions as culprits to this environmental devastation. The United States formerly backing its money by gold has a surplus of gold in its banking reserves and could use this to supply the global demand for gold instead of the world continuously mining depleting underground sources. To help minimize the usage and environmental impact of mercury, governmental, non governmental organizations (NGO), and large scale mining companies are addressing t hese issues.

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25 Governmental agencies have set bans, limits, and increased governmental regulations on the mining industry within its borders. On the other hand, non governmental organizations are attempting to educate the public via campaigns like Oxfam A more socially and environmentally responsible during the production of gold and (2) that consumers take responsibilities of their actions in the global distributi on of mercury.

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26 CHAPTER 3: FLORIDA 3.1 Introduction In this chapter, a top down approach has been used to gain an understanding of the issues associated with mercury in the state of Florida as a whole to the isolated issues within the study site ar ea, the Hillsborough River. Furthermore, the sampling approach, methodology, and data results from total mercury analyses, scanning electron microscopy/electron dispersion, x ray dispersion, and surface area analysis will be presented and discussed. 3.1 .1 Objective and Task The objective of this chapter is to characterize mercury loadings in the Hillsborough River of Tampa, Florida as well as address the role that socioeconomic factors play in mercury loadings. The tasks to accomplish this objective i nclude: Task 1a: Identify and characterize suitable study sites for this work. Task 1b : D eter mine levels of total mercury present in fish, water, and sediments by using cold vapor atomic absorption spectroscopy (CVAAS) and cold vapor atomic florescence sp ectroscopy (CVAFS) Task 1c: Identify the geochemical conditions that affect the fate of mercury by using BET surface area analysis, electron dispersion spectro scopy, and X ray diffractometry. Task 2a: Document the socioeconomic, regulatory and geopolit ical factors within the United States (Florida) and Internationally (Bolivia and Guyana) through a literature review

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27 3.2 Mercury and Florida, USA (N.A. ) With a population of approximately 16 million, Florida is the fourth largest state in the US 109 A tropical area 110 a ttracting more than 70 million tourists per year, it is the leader in commercial fish ing in terms of fish catches per day (e.g. shrimp, lobster, scallops, etc.) 1 In recent years, mercury has become a pollutant o f increasing concern for the state. Figure 3.1 Taken from the National Atmospheric Deposit i tion Network (a) Total Mercury Concentrations (n g L 1 ) and (b) Total Wet Mercury Deposition ( g m 2 ) 111 In the past six years, the Mercury Deposition Network (MDN) of the National Atmospheric Deposition Program (NADP) h as reported the highest levels of total wet mercury deposition in the Florida Panhandle and Florida Peninsula 8 In 2008, the total mercury concentrations in the United States de t ermined that hot spots for mercury (areas cont aining >12 g/m 3 Hg) are principally in Missouri, Indiana, Nevada, New Mexico, and Florida (Figure 3.1) 111 However, wet mercury deposition was by far the greatest in Flori da and Missouri. This may be due to weather conditions (e.g. heavy rains), local sources, as well as dispersion factors which are known to affect mercury deposition. Mercury deposition is still not well understood 112 According to the Florida emissions inventory, municip al solid waste combustors (MSW), electric utility industries (coal fired power plants), and medical incinerators are the major local sources of atmospheric mercury for the entire state of Florida 113 In 1994, the

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28 Florida Atmospheric Monitoring Study (FAMS ) initiated monitoring of wet and dry mercury deposition. revealed that background mercury levels were high and relatively constant throughout the state; however, the magnitude of depositio n is considered to be seasonal with highest levels of deposition exhibited during the summer months of May through October 113, 114 In 1996, the FDEP teamed with the Florida Center for Solid and Hazardous Waste Management (Center) to conduct mercury emission surveys within Florida hospit als to develop best management practices (BMPs) for handling mercury. compliance with state mercury rules and recommended practices for properly handling and disposing of mercury/mercury containing devices; and (2) proper education and training for all hospital employees is drastically needed to accomplish a significant used mercury (87%); sphygmomanometers (75%); high pressure sodium lamps (56%); thermometers (53%); mercury vapor lamps (46%); and metal halide lamps (44%) 115 Research has indicated that not all of Florida hospitals were in compliance with applicable rules and r ecommended practices for properly handling and disposing of mercury and mercury containing devices 115 Therefore it was recommended that proper educational training of all personnel was needed to accomplish a significant overall reduction in the amount of mercury in Florida.

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29 Figure 3. 2. Hillsborough County Impaired W ater B odies A tlas (Areas in R ed are C onsidered to be I mpaired) 116 In addition to atmospheric mercury deposition, entire coastline as well as every lake and river in the state, is subjected to mercury consumption advisories. Historically, mercury has been a statewide issue for Florida fish especially for its marine (e.g. shark and king mackerel) and freshwater fish (e.g. largemouth bass) 117 This has negatively impacted the fis hing industry (sport and commercial fishing) in Florida. In 1999, the US need of total maximum daily loads (TMDLs). Currently more than two million acres of freshwater sourc es, mainly in the Everglades, have advisories recommending limited to no consumption of the large predatory fish 118 Figure 3.2 outlines the impaired water main contributor to increased local atmospheric pollutants of carbon dioxide and mercury is coal fired power plants 119 In addition, municipal and medical incinerators known contributors to the release of mercury to the environment are a concern to Florida 115 In recent years, mercury has also become a pollutant o Fish and Wildlife Commission (FFWCC) given its deleterious effect on human health, especially due to fish consumption. Approximately forty eight mercury consumption advisories have been issued in the state of Florida for popular fish such as Snook, Gag

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30 Grouper, R edfish, Cobia, Spotted Sea Trout, Flounder, Pompano, and King M ackerel 120 The presence of extremely high levels have been reported in game fish found in the Florida Evergl ades (>1.5 g g 1 ) as well as in Large mouth bass within the Hillsborough River, Tampa Bay, FL (>1.8 g g 1 ). In 1995, the US Geological Survey (USGS) initiated and sponsored the Aquatic Cycling of Mercury in the Everglades (ACME) project, in order to understand the mercury problem in the Everglades alone. However, minimal studies have been conducted within the state for rivers in urban areas. For examp le, the Hillsborough River which originates at the Green Swamp and travels through urban areas before emptying into the Hillsborough Bay serves as a nursery and spawning location for over more than 100 species of fish The FFWCC found it to have elevated m ercury levels in largemouth bass species.

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31 Figure 3. 3. Map of the Tampa Bay Area (Modified from Malloy et al., 121 ) and Its Geographic Segments (Old Tampa Bay, Hillsborough Bay, Middle Tampa, Lower Tampa Bay, Boca Ceiga Bay, and Terra Ceia Bay). 3.2.1 Tampa Bay, Florida, USA (N.A.) ent 122 located along the south wes tern coast of Florida is the seventh largest commercial port in the United States and is one of the largest estuaries in Florida, encompassing more than 1000 square kilometers 123 The Tampa Bay watershed supports the cities of Tampa, St. Petersburg, Clearwater, Bradenton and surrounding suburban communities 124 Its seven segments depicted in Figure 3.3 (Old Tampa Bay (OTB), Boca Ciega Bay (BCB), Middle Tampa Bay (MTB), Hillsboroug h Bay (HB), Lower Tampa Bay (LTB), and the Manatee River(MR)) serve s as a nursery and spawning location for over more than 100 species of fish 125

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32 Approximately 90% of all the species in the Gulf catch are estuarine dependent, and spend all or a portion of their life in the estuarine zone 126 If these waters become polluted or impaired then aquatic species will not mature and death is likely to occur. In an estuary, salt water and fresh water mix. This mixing as well as a sufficient amount of fresh water flow into the estuary is quintessential for the survival of aquatic fauna and the overall health of the river. Therefore, h ydrologic and water quality changes caused by cumulative withdrawals and low flows from the Tampa Bay tributaries may generate negative impacts to freshwa ter and estuarine habitats and organisms especially in the Hillsborough, Alafia, and Palm/Tampa Bay Canal Rivers that drain into the Hillsborough Bay 127 The shorelines of Hillsborough Bay are mostly impacted by high industrial and u rban land use thus making it most impai red segment or tributary 127 Historically, the Tampa Bay area has been affect ed by poor water quality conditions due to decades of pumping raw or barely treated sewage into the bay 124 The highest levels of sediment associated contaminants have been measured in coastal areas that are influenced by point sources of pollution, primarily from m unicipal and industrial sources 128 Due to public concerns and a USEPA grant, Tampa established a water quality monitoring program that included the construction of a wastewater treatment plant and the Environmental Pr otection Commission of Hillsborough County (EPC) in the 1960s 124, 129 In 1996, the Tampa Bay National Estuary Program determined that Tampa Bay sediments contained elevated levels of chromium, copper, mercury, nickel, and silver and were to be designated as pri ority contaminants of concern 130 The primary sources of metallic contaminants to Tampa Bay have been identified as urban runoff, atmospheric deposition, and point sources ( i.e. coal fired power plants and medicinal incinerators) 130 Currently, efforts have been ma de to continue to minimize poor conditions as well as revitalize/restore Tampa Bay through the establishment of the Tampa Bay Estuary Program (SWFWMD) Surface Water Improvement and Management Project, as well as hospital BMPS for properly managing mercury and reducing its usage in the hospitals It is also interesting to note that spatial and seasonal distributions of colored dissolved organic matter (CDOM) in Tampa Bay conducted by Chen et al. 129 showed that the Alafia and

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33 Hillsborough River s were dominant CDOM sources. CDOM is important in controlling the attenuation of light. Natural organic and dissolved organic carbon (DOC) have been know n to affect the transport and bio availability of mercury 54, 55, 131 and organic pollutants. These factors highly influence the mobility/fate and transport of heavy metals in sediments, thereby affecting desorpti on kinetics from mineral oxides as well as its bioavailability 57, 132 For example, Siciliano et al. found that d issolved organic matter (DOM) influenced the abiotic, photo induced methylation rates of mercury 62 This may be the cause for elevated fish mercury concentrations that exceed the USFDA health based standards of 0.5 ng/g in 50 67% of all the lakes and streams in Florida 133 Figure 3.4 Ma p of Hillsbor ough River System Tributaries (M odified from Pills bury and Byrne 134 ). Shaded Area Denotes the Hydrologic System for the Hillsborough River. 3.2 .2 Hillsborough River, FL USA (N.A.) The Hillsborough River serves as the principle source of water for agriculture and drinking water for the residents of Tampa and its adjacent areas 135 It is approximately 87 km and contains several freshwater (Crystal and Sulphur Springs) and non freshwater (Black Water, Trout, and Flint Creek) sources or tributaries. The Hillsborough watershed or drainage basin spans a total of 379.9 m 2 136

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34 system have b een depicted in Figure 3.4. Its headwaters originate at the Green Swamp which provides inputs to the Withlacoochee, Peace, and Ocklawaha Rivers. The Green Swamp, a centrally located 870 sq. mile wetland and upland, is very important in recharging the gro undwater supply providing flood protection during rainfall events, and acting as a na tural treatment for runoff. Thus a pproximately 25% of its land area is protected by the Southwest Florida Water Management District (SWFWMD). As the river travels sout hwest towards Hillsborough Bay, it begins to take form as several tributaries and springs add to the rivers flow. At Crystal Springs, despite recent reports of declining flow (9.1x10 4 m 3 /day), it accounts for approximately 80% of the freshwater input to th e upper Hillsborough River. Next, the river receives inputs from Blackwater Cre ek, an area known for phosphate mining and agriculture production. Once the river reaches Trout Creek it enters the Floridian aquifer as a direct result of a sink hole. Also at this location, the river is connected to the Tampa Bypass Canal. The Canal serves as a flood control measure for residents of the city of Temple Terrace before terminating at the Palm River (Figure 3.5). As the Hillsborough River travels south west towa rds Rowlett Park it begins to widen and the river flows under several bridges/overpasses allowing urban run off to easily enter into the river. At Rowlett Park, there is the Tampa Hydroelectric Dam. Just before the dam, the river serves as the reservoir f or Tampa Bay Water and Veolia Water North America, the drinking water treatment facility that supplies potable water to nearly 2 million residents of Tampa. Freshwater inputs from this point into the river are low as the dam is only periodically released. This poses a threat to aquatic life in the estuarine zone. From this point to just before draining into the modifications to its shores by the filling of wetland habitats and increasing r esidential development. Reports from SWFWMD have indicated that the upland and riparian habitats along the river have been fragmented by agricultural and urban development. With an increasing urban population and tourism, the watershed s abi lity to serve as a water supply source for many recreational opportunities for area residents and tourists are in grave danger of pollution

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35 Figure 3.5 Sampling L ocations ( N oted by R ed P oints) A long the Hillsborough River, Tampa, FL Divided Into R iver Distinctions (Lower, Middle, and Upper) with Important River Dynamics Emphasized 3.3 Sampling Locations Hillsborough River Nineteen sites along the Middle and Lower Hillsborough River (Figure 3.5 ) were selected for the collection of water, sedime nt, and fish between early 2008 and late 2009 Sampling events occurred after extreme weather events (e.g. extreme cold, heat, or rain events). In addition, sample collection was conducted over a two day period during the morning hours. In this study, t he area was divided into three zones as depicted in Figure 3.5 The areas south of the dam were known as the Lower Hillsborough whilst regions north of the dam

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36 up to Lettuce Lake where known as Middle Hillsborough. Although, not truly part of the design ated Upper Hillsborough, the state parks located at Trout Creek up to the Hillsborough River State Park were deemed as Upper Hillsborough River in this study. Water and sediment sampling of the Upper and Middle segments were carried out by traveling to ea ch site by car whilst the Lower reaches were onboard a flat bottom Sea Ark 2472MVCC Jon boat. Fish samples were collected only from Middle Hi llsborough River at Rotary Park. This site is a designated FDEP /FFWCC annual fish sampling location for Environmental and Monitoring Assessment Program (EMAP). Fish species selection was based on community consumption patterns and state regulatory target (FFWC) and EMAP protocol. 3.4 Materials and Methods S (FDEP) sampling protocol. The sampling method described below has been divided into sections according to the sample matrix while the sampling sequen ce has been outlined in Figure 3 6 Figure 3 6 Sample Collection Flow Diagram with Method Analysis for Each Sediment Matrix

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37 The materials used in this work have been described in detail in the subsequent subsections. The matrix ho ld times and preservation requirements have been detailed in Table 3.1. Table 3.1. Matrix Preservation Requirements and Hold Times Matrix Type Preservation required Hold Time Air Vapor phase: 1 week Particle phase indefinitely Water Total and D issolved Hg: 5 mL/L 12N HCl or 5 mL/L BrCl Dissolved Hg: filtered through 0.45 m capsule filter Preserved with HCl : 90 days Preserved with BrCl: 300 days Unpreserved: 48 hours Tissue, Sludge, Sediment, and Soil Biota (e.g. tissue) homogenize or freeze whole Dry: indefinitely Wet: 1 year (if aliquoted) Biota: 1 year (if finely chopped or homogenized to a fine paste frozen ) 3.4.1 Glassware/Sampling Kit All Teflon bottles and glassware were cleaned using cleaning techniques described by the FDEP Metho d Hg 021 2.8, Procedure for High Level Mercury Glassware Cleaning 137 This procedure has been outlined in Appendix C. 3.4.2 Reagents Inorganic standards for trace level total mercury analysis were prepared in clean 1 ) NIST certified standard in 10% HNO 3 purchased from SPEX Centriprep 1 ) and a working standard of 1 ppb were prepared and preserved with BrCl The working standard was used to make daily calibration standards. Standard reference materials of NIST1641d 1 ) DORM 1 ) and NIST3133 3 (3.4 mg/L) for water, fish, and sedi ment, respectively, were used for quality control and quality assurance purposes. Acid and reductant solutions for cold vapor atomic absorption analysis were 5% HCl and 10% w/v stannous chloride (LabChem Inc LC25180 1), respectively. Reductant for CVAFS wa s a 3% w/v stannous chloride solution prepared by slowing

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38 mixing trace metal grade hydrochloric acid with reagent grade di hydride stannous chloride crystals (SnCl 2 2H 2 O) and purged with N 2 gas for at least 1 hour prior to sample analysis to dispel any traces of mercury in solution. A bulk volume of 5% hydrochloric acid solutions were made with 32% w/v HCL (Fisher brand) and diluted with MilliQ water. All reagents and calibration standards for CVAFS and CVAAS THg analysis were prepared fresh daily. 3 4.3 Water Sampling Prior to in field water collection, field equipment and sampling train kits underwent preparation procedures in the laboratory. Field equipment fo r water sampling consisted of coolers, Quanta hydrolab, Solinst Model 410 peristaltic pump, 12V pump battery, a Trimble GPS system, and a La Motte JT 1 bottom water sampler (van Dorn). On the other hand, t he sampling kit contained in a double sealed clean polyethylene storage bag was composed of (1) a 500 mL glass sampling bottle, (2) sample tubing (1 C Flex, 1 silicon, and 1 Teflon), (3) 0.45 m Whatman or Gilman filter, and (4) an extra clean storage bag. Before packaging, sampling kit tubing was rigoro usly cleaned following procedures outlined in Section 5.4 5.5 of the FDEP Method HG 015 2.10 (The Preparation of Sampling Kits for the Collection of Trace Level Mercu ry Water Samples, see Appendix ). All sampling kits were placed in a clean dark lined cool er. The cooler used to transport the clean sampling gear was not used for the transport of environmental samples. Glass bottles did not require any pre field or laboratory treatment as they were certified as clean from the manufacturer. For international sampling, 125 mL certified pre cleaned I Chem glass bottles were used to avoid total sample loss in case of acc idental breakage during shipment to the USF Trotz Water Quality laboratory. In addition, since only total mercury analysis was conducted clear glass bottles were used for all water samples as amber bottles are expensive and are predominately used for methyl mercury analysis. Although the use of amber bottles is important for methyl mercury analysis, dark lined coolers were used to avoid any poss ible photo degradation of total mercury concentrations.

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39 Using the ultra clean sampling approach, surface grab by sampling train (filtered and unfiltered), surface grab without train, and depth water samples taken using a La Motte JT 1 were collected in 50 0 mL clear glass bottles (150 mL for international samples) and stored in a dark lined cooler. For samples that were grab collected without the use of a train, the mouth of the bottle was submerged into the water in the direction of the river flow. After w ater collection, simple water quality parameters (pH, DO, temperature, conductivity, salinity, TDS, and turbidity) were taken using a Quanta Hydrolab Pro. Samples were transported using ice packs. Upon arrival to the laboratory, water samples were preserve d with BrCl produced in situ. In situ BrCl was produced within each sample by pipetting 5 mL of certified mercury free HCl per one liter of sample and 20 mL of potassium bromide/potassium bromate (KBr/KBrO 3 ) per one liter of sample. Sample hold time for total mercury analysis is recommended to be 90 days ; however, if samples are stored in glass or Teflon bottles and BrCl is used as a preservative the hold time can be up to 300 days 138 The addition of bromine monochloride to water samples reduces Hg loss that ma y occur due to organic matter in the sample as well condense mercury from sorbing to the walls of the bottle. 3 4 4 Sediment Sampling Surface and bottom sediment samples were collected using a stainless steel bowl with a hand scoop and a Wildco 196 B15 Eckman bottom sediment grab sampler or van Veen, respectively. A clean hand dir ty hand or ultra clean sampling approach was employed for both surface and depth sampling. Depth and surface sediment samples were not collected at every sampling point. Prior to sample collection at each point, the equipment was rinsed three times with wa ter from the sampling location. For easy transport, sediment samples were placed in doubly sealed plastic bags and stored in a dark lined discarded whilst the remainin g 10 cm of sediment from the bottom of the water body were collected All samples were stored on ice until arriving at the Trotz W ater Q uality L aboratory Once in the laboratory, samples were weighed (before and after drying),

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40 decanted for excess water, dried in laboratory oven at 30C for 24 36 hours ground in a mortar and placed in doubly bagged plastic storage bags until further analysis. Sediment samples were digested following FDEP modified EPA Method 245.5 and 7471 for Total Mercury Analysis of Sludge, Sediment, and Tissue, sediment s, then samples were analyzed for total mercury 139 During the digestion phase, approximately 1.0 g of sediment was dissolved in 30% hydrogen peroxide and trace metal grade (TMG) nitric acid This allowed the sediment matrix to breakdown any organic mercury present in the sample to its oxidized me rcuric ion form (Hg +2 ). Then, to ensure that complete oxidation to the Hg +2 state has occurred the liquid sediment wa s heated with 6% potassium permanganate and 6% potassium persulfate Next, 4 mL of 20% hydroxylamine hydrochloride was added to each sampl e to reduce any excess potassium permanganate remaining in the digestate which can negatively interfere with mercury levels. Finally, the digestate was analyzed on a Varian 240FS coupled with a VGA77. 3.4 5 Biota Sampling Biota samples containin g Largemo uth B ass ( Micropterus salmoides target species) Bluegill ( Lepomis macrochirus ) and Redear S unfish ( Lepomis microlophus ) were collected from a vessel off of the middle Hillsborough River using electroplate shocking techniques employed by the Florida Fish and Wildlife Conservation Commission (FFWC C ). To avoid spawning issues only mature fish were retained for analysis. In the field, samples were processed for their species, sex, weight, and length. In addition, otoliths were carefully removed and placed in secure envelopes for age identification and migratory pattern studies for the FFW C C. Furthermore, fish samples were carefully filleted, placed in doubly sealed plastic storage bags, and transported on ice to the laboratory for total mercury analysis Tissue or fillet samples were carefully extracted to avoid contact with epidermal, dermal, and scales. Upon arrival to the laboratory whole samples were frozen until analysis. Thawed fish

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41 fillet aliquots of 0.2 g were collected using a stainless steel knife while rinsing with aqua regia (HCl:HNO 3 ; 3:1) and deionized water between samples. Aliquots of the preserved samples were then weighed into 60 mL Teflon (FEP) bottles for UV assisted digestion prior to analysis using a Tekran Model 2600 total mercu ry cold vapor atomic fluorescence spectroscopy (CVAFS). Standard digestion procedures, Method HG 007 1.9, adopted from the Florida Department of Environmental Protection Agency 140 in accordance with the US Environmental Protection Agency (US EPA) Method 1631 were followed to conve rt all mercury (Hg 0 HgCl 2 complexes, Hg + Hg bound to organics, Hg bound to minerals, etc.) in the sample to Hg 2+ Concentrations of mercury are expressed as mg/kg wet weight. 3.5 Analytical Procedures 3 5 .1 Cold Vapor Atomic Adsorption Spectroscopy (CVAAS) A Varian 240FS AAS coupled with a Varian VGA77 attachment was used for the analysis of sediment and flora samples for total mercury THg, analysis by the cold vapor technique also known as cold vapor atomic absorption spectroscopy (CVAAS ). M e th yl mercury or mercury speciation was not conducted in this study. Before salinity samples were analyzed using the manual CVAAS technique, all samples were acidified with 0.5% HCl. Sediment and flora samples were also prepared before analyzing (see Section 4.3.2). C Due to the analytical sensitivity when testing for trace levels of mercury extreme precautions were exercised. C apillaries for the acid, reductant, and sample lines of the continuous vapor flow VGA77 were flushed with DI water before adjusti ng to an uptake rate of 1 mL/min, 1 mL/min, and 8 mL/min respectively A mercury flow through cell attached to a Mark V burner head of the Varian 240FS was cleaned with 0.5% nitric acid, rinsed with DI water, and allowed to air dry for 24 hours before e ach analysis set Optimal working conditions for the Varian 240FS AAS equipped with a VGA77 have been outlined in Appendix A

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42 3 5 .2 Cold Vapor Atomic Fluorescence Spectroscopy (CVAFS) Water and biota samples as described in Fig 3.6, were analyzed using t he Tekran Model 2600 following the US EPA Method 1631. Some of the possible interferences with matrix analysis have been outlined below and special precautions were taken to reduce damage to the analytical instrum ent. G old and iodide are known to reduce mercury recovery from 100% to 0%, water samples collected from possible mining regions (mainly in Bolivia and Guyana) were pre reduced with stannous chloride (SnCl 2 ) prior to analysis on the CVAFS. In addition, excess BrCl in each digested sample was red uced by the addition of 10 % hydroxylamine hydrochloride before sample uptake by the Model 2600. The Tekran CVAFS, automatically adds a strong reductant, 3 % stannous chloride (SnCl 2 ), to produce Hg 0 In solution, the Hg 0 is stripped to form a gaseous phase using ultra high purity (UHP) argon (Ar), a carrier gas. The gaseo us mercury is then concentrated onto the dual gold coated sand traps to form an amalgam to be detected by the UV mercury analyzer within the Tekran Model 2600. To reduce potential negativ e interferences by oxygen and water vapor, UHP grade ar gon gas and soda lime traps are used, respectively. In addition, fluid lines from t he Tekran Model 2600 were routinely purged with aqua regia (3:1HNO 3 to HCl) then flushed with DI water followed by h eating of the dual gold traps before and after any sample runs to remove any excess mercury that might be in the system. 3 5 .3 Brunauer, Emmett, and Teller (BET) Surface Area Analysis Sediment samples collected from the Hillsborough River were analyzed for surface area characteristics at the University of South Florida Energy Research Center Before performing gas sorption or BET analysis on samples, degassing. Thus using a Quantachrome Autosorb 1 analyzer an aliquot (0.2 0.8 g) of

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43 each sediment sample was placed in its own glass cell and heated at 105C under vacuum for up to 3 hours. Then after each sample was brought to a constan t temperature the mass was recorded. Next, the sediment sample was placed back into the Quantachrome Autosorb 2 ) gas, the adsorbate. Since a multi point BET analysis was performed, a dditional N 2 gas was introduced into the sample chamber to form a multilayer of absorbate onto the adsorbent. Once chemisorption was complete, the number of active surface sites which promote chemical reactions or strong chemical bonds between the adsorba te to specific surface locations or chemically active sites within the adsorbent were determined. Thus the proportionality between residual gas pressure and the saturation pressures at equilibrium (p/P 0 ) were used to generate cumulative areas. 3 5 .4 X R ay Diffractometry, Scanning Electron Microscopy/Electron Dispersive Spectroscopy X ray diffraction is a non destructive analytical method used to determine the properties of solid matter and requires minimal sample preparation. The mineralogy of bulk and 38 m sized fractionated sediments and tailings were characterized using powder X ray diffraction with a Bruker D4 Endeavor equipped with a LYNXEYE, a super speed detector. The D4 Endeavor was set to automatically load sixty six samples and perform qualit ative and quantitative crystalline phase and peak analysis with sample rotation enabled. Bulk and sized fractionated sediments were prepared by drying at room temperature in a Thelco laboratory grade oven for approximately 24 hours. An aliquot of the bulk sample was removed whilst the remaining sample was sieved using a series of ASTM E11 stainless steel sieves (mesh size 400) followed by grinding into a fine powder. Samples were then loaded into an 8.5 mm height, 25 mm sample reception specimen holder r ing using a top loading technique. Two types of s pecimen holder rings were used which were made of (1) low silicon and (2) steel (Bruker AXS holder # C79298A3244D82 and C79298A3244D84 respectively ). Excess samples were stored in doubly sealed plastic bag s and placed into a HDPE container. Once in the specimen holder ring, samples were smoothed and pressed to ensure uniform distribution, volume,

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44 and consistency for optimal analysis. Each sample completed a full scan at room temperature (25 C) with a step rate of 0.0125 step s/s = 2 to 120. Once all samples were examin ed, their diffraction patterns were analyzed using the results obtained from the Bruker D4 E ndeavor to the International Centre for Diffraction 4/PDF 2 reference files). Surface characteristics and elemental composition analyses of sedimen t samples were determined using a Hita chi FE SEM M odel S 800/EDAX. The Hitachi field emission scanning electron microscope has a magnification power of 300,000 times the actual size of the specimen The image is generated by scanning a very small electron beam over the sample As the electr ons are scattered from the surface, they are then collected by the detector thus generat ing an image and/or chemical characterization o f microstructures less than 1 m using an x ray spectrometer This spectrometer is commonly referred to as an energy dispersive spectrometer (EDS) or EDAX The EDS collects x rays that are generated from the scanned area by the electron beam Since the atom of each element releases a unique amount of energy, the acquired x rays are then used to determine the quan tity of each element present in the sample This is done by measuring the amounts of energy or peak intensities present in the x ray beams being released by the scanned image of the sample.

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45 To prepare samples for SEM/EDAX analysis, dried bulk samples wer e evenly distributed onto a thin strip of carbon tape that w as adhered to the surface of a SEM designated 25 x 6 mm metal specimen mounting plate (Hitachi catalog # 16327). To minimize sample loading time and maximize sample analysis time, four thin strips of carbon tape were applied to the mounting plate. To avoid cross contamination between each sample application, a glass slide was used as a divider followed by light tapping of the specimen plate to remove any loose particles. After sample mounting, the specimen plate was then attached to the specimen holder. Following procedures outlined in the SEM/EDS protocol for the University of South Florida Nanomaterials & Nanomanufacturing Research Center (NNRC), samples were carefully loaded into the Hitachi F E SEM M odel S 800/EDAX system. Since the Hitachi works under a high pressure vacuum of 90 torrs the w orking conditions for the SEM were set between 17 to 20 k eV to reduce the amount of particle charging at the surface and this eliminated the need for gold plating the sample using an Anatech Hummer X Sputter Coater.

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46 3.6 General Results and Discussion 3.6.1 Total Mercury in Sediment and Water T otal mercury concentrations of filtered and u nfiltered surface water samples, total mercury loadings in sedimen t and other water quality parameters (pH, Temperature, Conductivity, Turbidity, Dissolved Oxygen) for t he 18 different sampling points have been summarized in Table 3.2 On the other hand, depth water quality characteristics from the Lower reaches of the river below the dam have been summarized in Table 3.3. Table 3. 2 Total Mercury Concentrations in Unfiltered Water (uwTHg), Filtered Water (fwTHg), Sediment (sTHg) and Water Quality Parameters (pH, Temperature (Temp.), Specific Conductance (SpC.), Turbi dity (Turb.) and Dissolved Oxygen (DO)) for Sample Sites. Water Quality Data is Reported for Surface Samples. Sampling Was Conducted June 2008. Samples that were below the detection limit were considered 0 ng/L. ND not de termined.

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47 Table 3 .3. Water Quality Parameters Just Above the Bottom of the Riverbed (pH, Temperature (Temp.), Specific Conductance (SpC.), Dissolved Oxygen (DO), and Turbidity (TURB)) for Sample Sites Accessed by Boat in the Lower Hillsborough River. Sampling Was Conducted on June 2008. Site pH Temp. Spc DO TURB Depth ( o C) (mS/cm) (mg/L) (NTU) (m) Plant Park 8.0 29.7 46.30 2.4 4 14.00 Curtis Hixon 8.0 29.9 44.50 2.8 ND 10.50 Riverfront 7.9 29.9 43.90 2.9 ND 8.30 Waterworks 7.7 29.9 39.00 1.3 4 5.00 River Blvd 7.5 29.8 38.30 0.8 0 6.60 Epps 7.3 29.3 34.00 1.2 0 8.00 Lowry Park 7.3 29.2 31.40 1.2 0 6.70 Average 7.7 29.7 39.6 1.8 0 8.4 Stdev 0.3 0.3 5.60 0.9 0 3.0 ND Not determined. Average total mercury concentrations of unfiltered su rface water of all sites was 3.6 1.6 ng/L with the average of the upstream Middle Hillsborough (4.5 1.4 n g/L) being higher than that of the Lower Hillsborough river (2.6 1.3 ng/L). THg values ranged from 3.7 to 59.3 ng/L. The limited number of filtered s amples yielded average concentrations in the Middle Hillsborough river (0.2 0.2 ng/L) were lower than those downstream (0.8 0.1 ng/L) and on average, the particulate associated mercury accounted for over 70% of the total mercury in water samples. The filt ered THg concentrations seen in this study were relatively low compared to studies by others like Brigham et al. 141 who found filtered concentrations as high as 14.2 ng/L for the St. Marys R iver in the northe astern part of Florida. H igher dissolved mercury concentrations have been linked with higher percentages of wetlands in a given basin 141, 142 Higher total mercury concentrations in unfiltered water in the middle Hillsborough was expected to be more i mpacte d by nearby wetlands. However, lower levels tended to be exhibited in filtered water samples, though the sample size is small. Total mercury loadings in sediment averaged 68 18 ng/g and ranged from 48 to 119 ng/g with Middle Hillsborough loadings be ing 63.37.6 n g/ g and the Lower Hillsborough loadings being 7324.6 ng/ g Table 3.4 compares the results obtained here with data from other places around the world

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48 A part from the fact that the minimum sediment loading is higher than the minimum seen in m ost places, the data is within the range observed by others. Table 3.4. Mercury Concentrations in Sediment and Water Samples from This and Other Studies. Location Sediment Unfiltered Surface Water Hg (ng/g) Methyl Hg (ng/g) Hg (ng/L) Methyl Hg (ng/L) Hillsborough R iver (this study) 48 119 0.9 7.8 Artisinal Au mines, Suriname 143 mine wastes streams below mines u ncontaminated baselines 5.5 200 110 150 14 48 <0.02 0.83 1.2 1.4 0.03 0.08 11 930 6.4 10 0.05 3.8 0.08 0.28 Amazon basin 144 146 streams affected by mining upstream from mining 24 406 67 93 0.0 7 1.9 2.9 33 2.2 2.6 0.2 0.6 Antarctica streams and lakes 147 0.27 1.9* Mobile Alabama river basin 148 3.1 104 0 3.8 0.2 3.8 0 1.5 US Streams 142 0.84 4520 0.01 15.6 0.27 446 <0.01 4.11 Florid a Bays 149 1 219 3 7.4* filtered water samples The average pH for all of the sites was 8.30.2 and ranged from to 8. 1 to 8.9. The average temperature was 28.91.7 o C, and ranged from 24.4 to 31.6 o C. DO levels averaged 8.2 1.8 mg/L and ranged from 6.1 to 12.2 mg/L. For all sites the average specific conductivity was 11.3315.22 and ranged from 0.34 to 44.2 mS/cm. Th e s pecific conductivity of the Middle Hillsborough ranged from 0.3 4 to 0.4 6 mS/cm and for the Lower Hillsborough R iver it ranged from 1.92 to 44.2 mS/cm. Turbidity averaged 3495 NTU and ranged from 0 to 412 NTU with the average turbidity in the Middle Hi llsborough being 60 132 NTU whereas in the Lower Hillsborough it was 8 10 NTU. The sites in the Lower Hillsborough River ranged in depth from 5 to 14 ft when sampled and water quality was also tested close to the bottom for these sites. The results showe d that specific conductance ranged from 31 to 46.3 mS/cm and averaged 39.6 5.6 mS/cm, and DO levels ranged from 0.8 to 2.91 mg/L and averaged 1.8 0.9 mg/L. Temperature and pH values averaged 29.7 0.3 o C and 7.7 0.3 pH units respectively. Differenc es in values between the two regions may be explained by several factors. Sampling in the Lower Hillsborough was done from a boat in the center of the river whereas in the

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49 Middle Hillsborough it was done from the sides of the banks or from bridges over th e center of the river Additionally, s ampling for each location was performed at different time s of day as reflected in the varying temperatures and DO levels at the surface Photosynthesis, respiration and gas exchange influence DO levels and depend on variables like light, temperature, and nutrient availability and generally peak in the late afternoon 15 0, 151 Table 3.5. Pearson Correlation Coefficients Between Total Mercury in Sediment and Unfiltered Surface Water and Water Quality Parameters for All S ites and p Values Assuming a One Tailed Distribution for Two Samples of Unequal Variance. Parameter THg Sediment (ng/g dry weight) THg unfiltered surface water (ng/L) r s p value r s p value Conductivity (mS/cm) 0.27 <0.001 0.75 <0.050 pH 0.16 <0.001 0.20 <0.001 Turbidity (NTU) 0.13 <0.100 0.05 <0.100 DO (mg/L) 0.07 <0.001 0.25 <0.001 THg S ediment (ng/g dry weight) 0.12 <0.001 To understand the relationships between mercury loadings and water quality, Pearson correlation coefficients between total mercury in sediment and unfiltered surface water and water quality parameters for all sit es were calculated and reported in Table 3.5. The largest correlations were found with conductivity. The total unfiltered surface water mercury concentration decreased with conductivity whilst total sediment loadings increased with conductivity. Lange e t al. 152 also found negative correlations between total unfiltered surface water concentrations and co nductivity for lakes. Here, our sample sites ranged from low conductivity freshwaters to very brackish waters in the Hillsborough Channel, spanning an over 2 order of magnitude difference. Given that mercury forms complexes with chloride which influence sorption behavior to mineral oxide surfaces the correlation with specific conductivity is not surprising. Mercury (II) sorption to clays and mineral oxides of iron, aluminum and silicon, some of the most common sediment constituents, typically increases a s a function of pH until it reaches a maxima then decreases in the higher pH regions 42, 47, 48, 50 Kim et al. 46 found that at pH 6 mercury sorption decreased in the presence of sodium chloride due to the formation of

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50 aqueous mercury chloro complexes, uncharged HgCl 2 in particular. Therefore, it would be expected that as the condu ctivity increases, the mercury loadings would decrease. The results show, however, that as the conductivity increases, the amount of mercury associated with the sediment increased and the amount in the water decreased. The presence of competing ions and n atural organic matter, especially for the river sediments, likely play a role in loading behavior observed 40, 61 60 Complexation of mercury with chloride and subsequent sorption to parti culate fractions may explain the trend seen in this study. Although the entire river is fished, advisories are based on samples from the Rotary Park upstream of the dam and in the part of the river with more wetlands and forest coverage as well as lower c onductivity. Since downstream THg and sTHg are not significantly greater than those upstream, it is likely that fish concentrations sampled in the Middle Hillsborough River probably give the most conservative estimate of mercury loadings. M ineralog y and composition of complexing ligands in sediments and soils are also important factors that influence mercury mobility in the environment. Table 3.6 describes the mineralogical results of some of the samples and has been divided according to their sampling lo cale (e.g. Lower, Middle, and Upper Hillsborough River). All sample miner alogy can be found in the Appendix According to X ray diffraction analysis data, quartz (SiO 2 ) and berlinite (AlPO 4 ) represent the domina nt minerals for most of the samples from along the river. This is typical of natural sediments and similar to river bottom sediments obtained in other studies in Florida 153 Samples collected from the lower reaches showed the presence of clays. Lowry Park, located just below the dam, showed a high semi quantitative percent of kaolinite, (Al 2 Si 2 O 5 (OH) 4 ,79%). On the other hand, gypsum, representing 25% of the composition of the USF Riverfront Park sample, contained 15% sodium chloride, and 5% mercury, chromium, and barium. The presence of mercury in this sample may be attributed to the site being in the vicinity of possible point sources of mercury (e.g. medical incinerator and coal fired power plants) as well as the process by which gypsum is formed. Gypsum is fo rmed by roasting calcium with sulfur dioxide that may have

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51 originated from sulfides such as mercuric sulfide. Similar findings were seen in the examination of the physicochemical characterizations of an abandoned mine area in Spain 154 Gypsum is also a naturally occurring sediment in F lorida. Zhong and Wang 155 observed that sediments with increased clay content reflected an increase in sediment mercury loadings whilst sediments containi ng quartz and calcium carbonate had minimal effects on mercury loadings. In comparison with sTHg levels based on river divisions, the Lower, more urbanized areas having higher average loadings (73 ng/g) contained the presence of strong ligands (e.g. Cl, S O 4 PO 4 ) and other metals influence which have been seen to affect sorption of mercury (II) to quartz and gibbsite 48 Kim et al. 46 found that mercury sorption to Fe ,Al oxides in the presence of sulfates is greatly enhanced as a result of the accumulation of sulfate ions at the substrate interface thereby reducing the positive surface charge that would inhibit mercury (II) sorption. The presence of phosphates in the upper reaches of the river may be due to inputs from the phosphate mines or agricultural run off from local farms close to the rivers headwaters. Phosphates tend to increase mercury loadings in sediments and fish. The study of mercury present in rock ph osphate by Jackson et al. 156 determined that discharges of mercury liberated during the manufacturing of fertilizer caused mercury levels in sediments to increase to (<1. 7 mg / kg) whi t e mollusks (<50 mg / kg) and fish (pelagic and demer sal, 7.6 mg / kg) levels were greater than US EPA permissible limits This may be the reason for increased levels of mercury in largemouth bass collected at Rotary Park.

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52 Table 3.6 Mineralogical and Semi Q uant itat i ve Results Obtained by X ray Diffractio n for Samples from Upper, Middle, and Lower Segments of the River. Sample Name SemiQuant [%] Compound Name Chemical Formula Upper Sargent Park 42 Berlinite AlPO 4 58 Quartz SiO 2 HR State Park 40 58 1 Silica Berlinite Tin Selenide Si O 2 AlPO 4 SnSe Rotary Park 50 50 Quartz low Berlinite, syn Si O 2 AlP O 4 Middle Riverhills 98 2 1 Quartz Silver Telluride Aluminum Uranium Si O 2 Ag 2 Te Al 3 U Rowlett Park* 100 Quartz, syn SiO 2 Lower Lowry Park 79 21 Kaolinite Quartz, syn Al 2 Si 2 O 5 (OH ) 4 Si O 2 Riverfront 15 48 5 25 6 Sodium Chloride Quartz PHC Gypsum MCB, Platinum Z inc (1%) Na Cl Si O 2 K 5 H (CN 2 ) 3 Ca(SO 4 ) 2 H 2 O Hg, Cr, Ba 2 Pt 3 Zn Curtis Hixon 61 36 4 Quartz Berlinite, syn Magnetite Si O 2 AlP O 4 Fe 3 O 4 SEM/EDAX analysis conf irmed that silica and oxygen, the elements that form quartz, as being the most abundant or major constituents in most of the samples. Constituents within a sample containing greater than or equal to 10% of the weight percent are considered major whilst th ose between 1 and 10% are minor and all others are trace. Based on weight percentages for silicon and oxygen a 1:2 (Si:O) ratio exist thus assuming that indeed SiO 2 is the dominant mineral in most of the samples which was confirmed by XRD analysis. The s emi quantitative results for each major, minor, and trace constituents were examined for a single sampling location within each of the river divisions (e.g. Upper Sargent Park; Middle Rotary Park; and Lower Riverfront Park) and are shown along with SE M high resolution images in Figure 3.7 All SEM images captured at low and high resolution s showed that the sediments along the rivers course before emptying into Tampa Bay were different but all were anamorphous and porous. All in all, b ulk fractions of sediments exhibited large grains of quartz with aggregates of Fe (hydro) oxides and aluminum (hydro) oxides which was in agreement with X ray diffraction results.

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53 Scanning electron spectroscopy and energy dispersion spectroscopy is not popularly used fo r elemental determination in sediment or soil sample characterization Although, Roach et al. 157 was unable to show the phy sical distribution of hea vy metals in kaolin soils using EDX, Bautier et al. 158 successively used it to directly characterize elemental constituents within amporphous phase soils mainly composed of Fe and A l oxyhydrides using TEM EDX In Figure 3.7 a, Sargent Park characteristic x ray peaks were associated with Si, C, O, Al, and Ca, where calcium and aluminum were minor constituents. In addition, the sediments contained large pores measuring about 48.9 m i n diameter which means that there are more surface sites available for possible sorption of mercury. Rotary and Riverfront (Figure 3.7b c) normalized element quantification results show the presence of trace amounts of mercury and tellurium (Tl). Element s 80 and 81, mercury and t ellurium respectively, have relatively similar electron energies and are distinguishable at energy is above 15 keV; however, to prevent particle charging and the need to gold coat sediments peaks were not collected at higher ener gy levels. In addition, car 40% C) for most of the samples and considered major constituents. This uniform c arbon weight percentage c an be attributed to the presence and use of carbon tape for mount ing samples to th e specimen holder. The SEM image of bulk characteristics from Riverfront Park were obtained at a magnification of x70 but when magnified to x800 the skeletal remains of a microorganism was present which increased carbon weight percent to 48.55%.

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54 Figure 3.7 SEM/EDAX Standardless Quantification of Normalized Elements from Sediments Collected from (a) Sargent Park ; (b) Rotary Park; and (c) Lowry Park (a) (b) (c) Mag 70x Mag 10 0x Mag 70 0 x

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55 Figure 3.8 SEM I mage and Element Maps for Rotary Park S ediments. (a); Magnificati on x150 of SEM I mage; and S pot I mages of M ajor and M inor C onstituents of (b) Al; (c) Ca; (d) Fe C lusters; (e) Hg; and (f) AlCaFeHgO Furthermore, SEM imaging and quantification software can be used in combination with elemental mapping with EDX to determ ine heavy metals and elemental aggregates or dispersal within a sample Elemental maps for select samples were collected and Figure 3.8 correspond s to sediments collected from Rotary Park, the annual site for the FFWCC Al Fe Al Hg O Ca Al Ca O Fe O Al Ca Fe Hg O Al O SEM (b) (a) (c) (d) (e) (f)

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56 E nvironmental M ercury A ssessment P rog ram. The distribution of each major and minor element was independently overlaid with oxygen in order to clearly see the single element in each of the maps (Figure 3.8b e); however, the last spot map is an overlay of all of the major and minor elements (F igure 3.8f). From the SEM semi quantification results it was determined that silicon was most abundant in the samples so no elemental map was created for it. Elemental maps for aluminum, iron, and calcium showed that the elements were in clusters. Alumi num and calcium tended to be clustered within the voids whilst iron was seen to group together at the surface. Mercury was scattered throughout the samples. 3.6.2 Total Mercury Loadings in Fish Figure 3 .9 Fish Species Collected from the Hillsborou gh River, Tampa, FL Include (a) Bluegill, (b) Redear Sunfish, and (c) Largemouth Bass. Looking mainly at lakes, researchers have correlated fish loadings with water quality parameters and found alkalinity, calcium, chlorophyll a conductance, magnesium, pH, total hardness, total nitrogen, mercury concentration in water and total phosphorus to be some main factors of influence 159, 160 Scudder et al. 142 found that total mercury loadings in LMB found in streams across th e US were positively correlated with amount of wetlands present, amount of methyl mercury in water and sediment, specific UV absorbance and negatively correlated with dissolved sulfate concentrations and pH of unfiltered water. Fish were only sampled from one location in this st udy which was upstream of a dam; however, water quality parameters and sediment loadings were collected along a wider selection of the river, including areas below the dam which were

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57 also heavily fished by local residents. Fish spe cies of largemouth bass, redear sunfish, and bluegill are depicted in Figure 3.9. Table 3.7 summarizes the characteristics and total mercury loadings associated with fish species and body condition Average mercury loadings in LMB (n=20), bluefish (n=10) and red ear sunfish (n=8) were 0.56 0.22 mg/kg, 0.17 0.4 mg/kg and 0.1 0.07 mg/kg wet weight, respectively. After categorization by species, these loadings were compared with fish length, weight, and age data. Scatterplots and correlation data are show n in Figure s 3.10 and 3.11 Positive associations were found with both weight and length for all species. The largest correlations were found for the LMB. Mercury loadings were also positively associated with age for the largemouth bass (age data was onl y available for this species). Historical data from the FFWC at the same sample location ( for 2003 2007 and a total of 154 fish) also show strong correlations of f THg with largemouth length, weight and age (r s = 0.72, 0.56 and 0.45 respectively with p < 0 .001) F ish data compared (mercury loading versus fish weight) with historic FFWC data is plotted in Figure 3. 1 2 Table 3.7. Summary of Fish Characteristics ( Length, Weight, Fish Body C ondition (fbC), Age) and Total Hg (fTHg) Concentrations S ampled on 2/26/08 at Rotary Park # Tampa, Florida. LMB Largemouth bass, BLUE Bluefish, RESU Redear sunfish # 28.05406 LAT and 82.36419 LONG Age was determined by the Florida Fish and Wildlife Commission ND Not determined.

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58 Figure 3.10 (a d) : Sc atterplots o f Total Mercury Loadin gs (fThg) in mg/kg Wet Weight as a Function o f Length, Weight, a nd Age, f or Each Fish Species. Pearson Correlation Coefficients, r s a nd p Values Are Shown. p Values Were Calculated Assu ming a Two Tailed Distribution for Two Samples o f Unequal Variance. 0.00 0.20 0.40 0.60 0.80 1.00 1.20 200 300 400 500 600 fTHg (mg/kg wet weight) Length (mm) (a) r s = 0.66; p < 0.001 Largemouth Bass 0.00 0.05 0.10 0.15 0.20 0.25 120 140 160 180 200 220 240 260 fTHg (mg/kg wet weight) Length (mm) (c) r s = 0.09; p < 0.001 Redear Sunfish 0.00 0.05 0.10 0.15 0.20 0.25 160 180 200 220 fTHg (mg/kg wet weight) Length (mm) (b) r s = 0.18; p < 0.001 Bluegill 0.00 0.20 0.40 0.60 0.80 1.00 1.20 0 1000 2000 fTHg (mg/kg wet weight) Weight (g) (d) r s = 0.62; p < 0.001 Largemouth Bass

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59 Figure 3.1 1 (e j) : Scatterplots o f Total Mercury Loadings ( fT hg) i n m g/ k g Wet Weight a s a Function o f Length, Weight, a nd Age, f or Each Fish Species. Pearson Correlation Coefficients, r s a nd P Values Are Shown P Values Were Calculated Assuming a Two Tailed Distribution f or Two Samples o f Unequal Variance 0.00 0.05 0.10 0.15 0.20 0.25 50 100 150 200 fTHg (mg/kg wet weight) Weight (g) (e) r s = 0.18; p < 0.001 Bluegill 0.00 0.20 0.40 0.60 0.80 1.00 1.20 0 2 4 6 8 fTHg (mg/kg wet weight) Age (years) (g) r s = 0.45; p < 0.001 Largemouth Bass 0 0.05 0.1 0.15 0.2 0.25 0.3 0 1 2 3 fTHg (mg THg/kg wet fish) Fish Body Condition (fbC) Bluegill (i) r s = 0.46; p >0.05 0.00 0.05 0.10 0.15 0.20 0.25 30 130 230 fTHg (mg/kg wet weight) Weight (g) (f) r s = 0.09; p < 0.05 Redear Sunfish 0 50 100 150 200 250 300 0 0.1 0.2 0.3 fTHg (mg THg/kg wet fish) Fish Body Condition (fbC) Red Sunfish (h) r s =0.05; p>0.05 0 50 100 150 200 250 300 0 0.1 0.2 0.3 fTHg (mg THg/kg wet fish) Fish Body Condition (fbC) Largemouth Bass (j) r s =0.43; p>0.05

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60 Figure 3 1 2 Scatterplot of Mercury Loading Versus F ish W eight for S amples T aken at Rotary Park for T his S tudy (20 LMB out of 38 Fish T otal) and B y the Florida Fish and Wildlife Commission (FFWC) B etween 2003 and 2007 for LMB O nly. LMB Largemouth Bass; BLUE Bluegill; RESU Redear Sunfish (Weight of BLUE and RESU A re A ll Less T han 262 g). A r ecent mercury survey of concentrations in fish in the Weste rn United States found that average concentration of piscivorous fish was 0.26 mg/kg wet weight for 161 This is lower than the average LMB concentrations seen at the site studied in the Hillsborough River. Others hav e found average LMB loadings similar to those observed in this study in other rivers, streams and lakes as well as their correlation with fish length, weight and age 142, 152, 159, 160 A long term study of fTHg i n the middle Savannah River, from 1971 to 2004 found average LMB concentrations of 0.55 mg/kg wet weight which is similar to that found here 162 Paller et al. 162 observed decreased concentrations when a Chlor Alkali point source input ceased, but subsequent increases in fish loadings were attributed to atmospheric deposition and releases from tributaries draining wetland areas. There are no known industrial sources that drain into the Hillsborough River and the most upstream portion, referred to in this work as the Upper Hillsborough River, starts in the Green Swamp (it was not studied because of its public inaccessibility). The higher methylation 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0 500 1000 1500 2000 Mercury Loading (mg Total Hg/ kg wet fish tissue) Total Weight (g) This Study (LMB, BLUE and RESU) FDEP LMB (2003 2007)

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61 rates attributed to wetland areas combined with the damming of the river could contribute to the concentrations of LMB observed in this study 142, 160, 163 Additionally, in fishery studies, researchers use weight, length, and body condition as an index to assess fish nutritional well being, fitness as well as the relativ e suitability of its habitat 164 which has the ability to potentially reflect seasonal and longer term nutritional trends. Equation 2 best explains the calculati on for body condition (K) 165 K = 10 5 W L 3 ; Equation 1 where W is the body weight (g) and L is the standard length (cm). Therefore, i f K is greater than or close to 1 it is assumed that the fish is in good condition or receiving sufficient food and nutrition. Researchers have shown that fish body conditions can be comparable to the levels of stored fat as well as th e incidence of disease 166, 167 In addition, various factors (e.g. sex, body shape, sample collection method, environmental pollution, seasonal changes, disease, and parasites) can affect fish body conditions. S uns and Hitchin have shown that higher mercury levels tend to decrease enzyme protein synthesis where as Lizama 168 argues that fish condition affects mercury levels. Average fish body conditions were 1.27, 1.46, and 1.65 for largemouth bass, red sunfish, and bluegill, respectively. Largemouth bass average fish body conditions wer e similar to those found by Lizama et al. 168 Negative correlations existed b etween fish body conditions and total mercury concentrations. Striped bass fish conditions studied by Hinner 169 were negatively correlated with total mercury concentrations as was seen by Cizdziel 170

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62 3.6.3 H ealth Implications The US Environmental Protectio n Agency 171 suggests consumpt ion of fish with methyl mercury concentrations in the range 0.12 0.47 mg/kg wet weight should be limited to one meal (227 g or 8 oz. of cooked fish) per week for the average adult. Fish containing 0.47 0.94 mg/kg wet weight should be limited to consumptio n once per month and levels greater than 0.94 mg/kg should not be consumed 171 Since the majority of mercury seen in fish is methyl mercury 172, 173 total mercury concentrations can be assumed to be equal to methyl mercury. Therefore, 86% of all of the fish (n=38) seen in this study had total Hg loadings that would warrant a fish advisory and 32% having loadings that should limit consumption to once per month if using the EPA fish consumption guidelines stated above. The Florida Department of Agriculture and Consumer Services (2009) issued a joint statement with oth er state agencies (Department of Health, Department of Environmental Protection) emphasizing the benefits of eating fish soon after the release of a 2009 USGS survey of mercury levels of fish in streams across the US 174 That USGS survey was picked up by mainstream media because of the high percentage of fish found with mercury levels above EPA recommended limits. Whilst the EPA recommends acceptable mercury exposure through fish consumption based on toxicologic al tests, state and local agencies are responsible for protection of their own populations. The Florida Department of Health issues annual fish consumption advisories (where one meal refers to 170 g of uncooked fish) for specific fish in a given water body tested, and the county agencies use that information to best protect human health. The 2008 Florida fish consumption advisories for LMB and Bluegill in the Hillsborough River recommend a maximum one meal per month for everyone and for the Redear Sunfish, the consumption could be one meal per week for all, except women of child bearing age and young children who should only consume one meal per month 175 For the purposes of this study 227 g is used to refer to fish weight where this can be treated as either uncooked or cooked given that some forms of preparat ion like boiling do

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63 not alter fish weight 176 The following discussion uses the data collected in this chapter to evaluate the efficacy of the above fish consumption advisory. Toxicological and epidemiological studies are u sed to develop a reference does (RfD) which is an estimate of the daily exposure to a certain chemical that would likely not pose any appreciable risk of deleterious effects in the human population and sub groups of at risk individuals over a lifetime 171 Hence, a comparison of actu al dose to the RfD can be used to determine the deviation from the safe value. This is captured by a Hazard Index (H) which is the ratio of Dose (D) to Reference Dose (RfD) and is generally used to determine the toxic effects of fish consumption where val ues less than 1 are considered non toxic. H can be calculated using Equation 2: Where C is the concentration of mercury in fish (mg/kg wet weight of fish); D is the dose of mercury from fish (mg/kg.day); I is the ingestion rate o f fish (g/day); W is the average body weight which is 70 kg for an adult and 16 kg for a child, RfD is the estimated single daily chemical intake rate that appears to be without risk if ingested over a lifetime. EPA 171 recommends a RfD value for methyl mercury loadings of 1 x 10 4 mg /kg day. Using this equation, we calculated the hazard index for a range of fish Hg loadings and ingestion rates relevant to this study. The three ingestion rates used represent a 227 g portion of fish consumed on a monthly (~8 g/day), weekly (32 g/day) an d daily basis which were based on findings by Halfhide 177 on the Hillsborough River.

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64 Table 3.8 Child Hazard Index (H) and Critical Fish Concentration (C) Assuming H = 1. Calculations Assumed a Rfd = 1 X 10 4 m g/kg Day for Different Ingestion Rates (I, g/day), Fish Mercury Concentrations (C, mg/kg Wet Weight) and Body Weights (16 kg for a Child). Ingestion rates of 8, 32 and 227 g/day correspond to a meal of fish once per month, week and day respectively. Child Hazard Index (H) Ingestion H H H C (mg/kg) Rate (g/day) C = 0.1 m g/kg C = 0.27 mg/kg C = 0.97 mg/kg H =1 8 0.47 1.28 4.59 0.21 32 2.03 5.47 19.66 0.05 227 14.19 38.31 137.62 0.01 Table 3. 9 Adult Hazard Index (H) and Critical Fish Concentration (C) A ssuming H = 1. Calculations Assumed a Rfd = 1 X 10 4 mg/kg Day for Different Ingestion Rates (I, g/day), Fish Mercury Concentrations (C, mg/kg Wet Weight) and Bo dy Weights (70 kg for an Adult ). Ingestion rates of 8, 32 and 227 g/day correspond to a meal of fish once per month, week and day respectively. Adult Hazard Index (H) Ingestion H H H C (mg/kg) Rate (g/day) C = 0.1 mg/kg C = 0.27 mg/kg C = 0.97 mg/kg H =1 8 0.11 0.29 1.05 0.93 32 0.05 1.25 4.49 0.22 227 0.32 8.76 31.46 0.03 Table 3.8 and 3.9 provides the results of these calculations. The last column in each table lists the mercury loadings in fish C (mg/kg wet weight) that would be considered hazardous for the given ingestion rate. Using the measured fish loadings observed in this study, n one of the Bluegill or Redear Sunfish would be considered hazardous at an ingestion rate of 227 g/month for adults; however, at this ingestion rate children should not eat anything greater than 0.21 mg/kg which would represent fish 16% of those fish samp led. For the LMB, all would be considered hazardous for children at an ingestion rate of 227 g/month. This suggests that the published advisory is under protecting children. At an ingestion rate of 227 g/week, fish above 0.01 mg/kg and 0.22 mg/kg should not be consumed by children and adults respectively and the local advisory adequately protects both populations and possibly overprotects adults in the case of Bluegill consumption. All of the fish sampled in this study would be considered hazardous if i ngested at 227 /day for children and all of the LMB would be considered

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65 hazardous to adults if ingested at 3 5 g/day (not shown in the table) The outcomes do not change much if we used concentrations that were 95% of the values measured to represent the m ethyl mercury fraction or if a meal was treated as 170 g. For example, at 170 g, 90% of the LMB would be considered hazardous to children as opposed to all for an ingestion rate of 1 meal per month. These results are particularly problematic in light of e vidence from our concurrent study of fishing habits and knowledge along the river 177 Results of that study indicate that a large proportion of the population surveyed fishes multiple times per week and have not s een any fish consumption guidance. Hence, it is likely that exposures to mercury exceed recommended levels. Whilst statewide fish consumption advisories based on mercury loadings provide guidance to reduce human exposure, these are not necessarily easil y translated to local scales and may miss vulnerable populations. As shown above the advisories may also limit consumption unnecessarily. Regardless, the lack of signage at the areas sampled and the high percentage of fisherfolk unaware of advisories for the given water body 177 imply that more effective forms of outreach are needed to impact human health. The challenge is to design this process so that the public can make informed decisions based on personal habits and the local characteristics of the water body. Further studies are needed to measure fish mercury loadings in other parts of the river which are heavily fished and which have different characteristics than the Rotary Park site of this study. Below the dam in the lower Hillsborough river where parameters like conductivity may be influential. 3.7. Summary Nineteen sites along the Hillsborough River were selected for analysis because of ease of access and in larger scope water and sediment mercury lo adings are not regularly monitored. The a verage unfiltered surface water total mercury concentrations were 3.61.6 ng/L with the average of the upstream Middle Hillsborough (4.51.4 ng/L) being higher than

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66 that of the Lower Hillsborough River (2.61.3 ng/ L). Total mercury loadings in sediment averaged 68 18 ng/g and ranged from 48 to 119 ng/g with Middle Hillsborough loadings being 63.37.6 n g/ g and the Lower Hillsborough loadings being 7324.6 ng/ g ). Average LMB loadings were similar to those observed in other water bodies in the US ; however, 86% of all of the fish (n=38) seen in this study had total Hg loadings that would warrant a fish advisory and 32% having loadings that should limit consumption to once per month if using the EPA fish consumption guidelines. XRD analysis confirmed that sediments exhibited large grains of quartz with aggregates of Fe (hydro) oxides and aluminum (hydro) oxides which may affect the mobility of mercury in soils.

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67 CHAPTER 4: GUYANA Figure 4. 1 Administrative Regions of Guyana. Mahdia and Iwokrama are located in the Potaro Siparuni (8) W hile the Konashen District is in the East Berbice Corentyne ( 6 ). 4.1 Introduction This chapter examines the use of mercury in the gold mining region of Guyana and its associ ated environmental and health implications. A presentation of the sampling approach and total concentrations in water, sediment, and fish samples collected from pristine and mined areas will be discussed.

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68 4.1.1 Objectives and Tasks Overall, the object ive of this chapter is to characterize mercury loadings in select areas within Guyana, South America to assess the impact of gold mining activities. The tasks to accomplish this objective include: Task 1a: Identify and characterize suitable study sites fo r this work. Task 1b : D eter mine levels of total mercury present in fish, water, and sediments by using cold vapor atomic absorption spectroscopy (CVAAS) and cold vapor atomic florescence spectroscopy (CVAFS) Task 1c: Identify the geochemical conditions that affect the fate of mercury by using BET surface area analysis, electron dispersion spectro scopy, and X ray diffractometry. Task 2a: Document the socioeconomic, regulatory and geopolitical factors within the United States (Florida) and international ly (Bolivia and Guyana) through a literature review. 4.2 Guyana (S.A.) Guyana located between Suriname and Venezuela is a tropical climatic area known for its biodiversity, extensive rainforests, and many rivers. Its name in Amerindian means the old leading export and accou 178 In addition, timber, bauxite, and diamond represent other major exports 179 Being the only English speaking country in South America it has a population of about 772,298 of which 90% of the population reside on the Atlantic coastal region which has most of the arable land (2% of total land area) The dominant religion is Hin du and is composed of four ethnic groups (East Indian, 43.5%; African descent, 30.2%; mixed 16.7%; and Amerindian, 9.1%). On the other hand, t he interior regions are mainly inhabited by the indigenous. Guyana is divided into ten distinct regions and furth er separated into six mining districts. Figure 4.1 depicts the regions placing special emphasis on the Potaro

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69 Siparuni (Region 8) and East Berbice Coretyne (Region 6) locations studied within this work. Whilst in Figure 4.3, the location of the sample si tes and the delineations for the mining districts are depicted The six mining districts in Guyana are as follows : Berbice Mining District 1, Potaro Mining District 2, Mazaruni Mining District 3, Cuyuni Mining District 4, Northwest Mining District 5, and Rupununi Mining District 6 with the bulk of gold mining currently occurring in Districts 2 to 4. The approximately 960 km long Essequibo R iver starts in the Acarai Range located in the southernmost part of the country (on the border with Brazil) in Distri Districts 2, 3, and 4 prior to emptying into the Atlantic ocean. The Essequibo drainage basin is approximately 50,000 km 2 and has a maximum depth of about 40 m with an average annual rainfall of 3 000 mm/yr 180 181 The Essequibo R iver and its tributaries drain two current protected areas in central Guyana, the Kaieteur National Park and Iwokrama International Centre for Rain Forest Conservation and are the main surface waters of an even larger biodiversity conservation c orridor proposed by Conservation International Guyana. The Guiana Shield refers to a belt of greenstone underlying 21% of the total land area of Brazil, Colombia, French Guiana, Guyana, Suriname and Venezuela combined (Table 4. 1). The area is bounded by the Amazon River and Japura Caqueta River in the south, the Sierra de Chiribiquere to the west, the Orinoco and Guaviare R ivers to the north, and the Atlantic Ocean to the east. Sixty three percent of the total land in these six South American countri es remains as intact forests (76% of which are tropical forests), with the smaller Guianas French Guiana, Guyana and Suriname showing the least amount of deforestation 182

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70 T able 4.1. Land and Forestry C overage and G old P roduction of C ountries of the Guiana Shield ( A dapted from Hammond DS, 2005 and USGS, 2008) Country Total Land (km 2 ) Land in GS % Land as IF % 2006 Gold Production (kg) Brazil 8,456,510 14 64 45,000 Colombia 1,038,710 16 47 15,700 French Guiana 88,150 100 90 2,000 Guyana 214,980 100 79 6,406 Suriname 156,000 100 90 9,362 Venezuela 882,060 51 56 12,400 Total 10,836,410 21 63 90,868 GS refers t o Guiana Shield and IF refers to Intact Forest. Biological diversity, especially of endemic species, has driven the establishment of conservation areas in the region, including World Heritage Sites like the Central Suriname Nature Reserve that covers 10% underway to protect the standing forests through international payment mechanisms established to combat global climate change within Strategy. The Guiana Shield is also rich in gold, having one of the largest lower grade deposits, and it ranks one of the fastest growing regions of gold production where the scale of mining ranges from large (> 500, 000 t ore/yr) to medium (50 500,000 t ore/yr) to small (<50 t ore/yr) 182 In the case of Guyana, classifications are made according to property size: 2 52 km 2 large, 0.6 4.9 km 2 med i um, and 0.1 km 2 small 183 Rising gold prices has led to the spread of mining activities throughout areas of the Guiana Shield which have had, and continue to have detrimental social and environmental impacts, many times in, or close to areas considered protected or inhabited by indigenous gro ups 182, 183 18 4 185 In countries like Guyana which experienced significant increases in gold exports from the large OMAI mine which used the cyanide heap leaching procedure and operated there for ten years, gold production from small and medium scale m ines which use mercury amalgamation procedures, are rising sharply as are the number of mining permits disbursed versus the use of more efficient procedures and safe practices or the discovery of richer deposits (Figure 4.2 ). Gold mining, logging, and the opening of new roads threaten biodiversity and mined areas have shown extremely slow rates of recovery under current practices 184, 186

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71 Figure 4.2 Guyana D eclared G old P roduction 1979 2008 from L arge S scale OMAI Mine an d S mall to M edium S cale M ines ( N on Omai) 187 Brazil is the only country in the Guiana shield to ban mercury use in gold mining, and the miners and their excessive mining habits have migrated to the Guianas where environmental regulation on mercury use is lacking or lacks proper enforcement mechanisms 183, 185 Small scale gold mining was estimated to contribute more than 10% of annual global anthropogenic Hg loading to the atmosphere in 2005 188 Mercury is recognized as a global contaminant know n to cause deleterious neurological, developmental and other health effects 9 Based on toxicological studies, the following guidelines have been esta blished for mercury: 1 g/L for drinking water 67 1 g/m 3 for air 189 0.77 g/L for the protection of aquatic life through chronic exposure 190 and 0.3 mg methyl mercury/kg wet weight of fis h for human consumption 190 Epidemiological studies indicate neurological damage when total mercury concentrations are greater than 50 g/g in adult hair or 10 20 g/g in maternal hair 191 Higher mercury concentrations in hair and urine samples have been found in or close to small to medium scale mining communities in the Guiana Shield 10, 192 and in some instances correlated with neurocognitive outcomes 193 Higher hair mercury loadings seen in indigenous populations, many times in areas upstream from mining, have been linked to fish consumption habits 194, 195 although very little work has looked at contributions from

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72 thimerosal preserved vaccinations or nutritional deficiencies 196 or other local environmental conditions (e.g. slash and burn agricultu re or wood fires in homes). Early work in Brazil found higher concentrations of mercury in fish, sediment and water around small and medium scale gold mining communities when compared to non mining areas 144, 197 11, 198, 199 Hilson 200 summarizes other studies that support these observations around th e world. Others have also found some upstream non mined environments to have higher loadings in Brazil 201 and Wasserman 202 argues that mercury releases from actual amal gamation are too insignificant to be the cause of loadings seen in soils in the Amazonian environment and that it is human induced activity, some from gold mining like land clearing, that releases mercury from soils into aquatic systems ( 203, 204 Though limited by its exclusion of the impact of mercury deposition, Beliveau et al. (2009) found that slash and burn agriculture altered the fractions of soil mercury was associated with, but did not result in and major loss of mercury to waterways. Deforestation and other land use changes are indeed being used as indicators for increased mercury levels in carnivorous fish 2 05 Miller et al. 206 describes the ensuing d ebate within the scientific journals on whether the high mercury levels seen in Brazil resulted from gold mining or deforestation (and soil erosion) since both activities were prevalent and the soils from the area naturally had high background mercury leve ls compared to other parts of the world 207 Some studies in the less deforested Guianas also found higher mercury loadings closer to, or downstream from mining although localized deforestation would have been an issue at mining sites 143, 206, 208, 209 Mercury loadings in forest soils, river sediment and lateritic soils along the Sinnamary River in French Guiana did not show any significant variations around mining sites 210 whilst the type of soil (o xisol versus utisol) found in the ECEREX reserve in French Guiana influenced mercury loadings with oxisols having higher values 211 Tessier et al. 51 found that during a rainfall event, atmospheric mercury distribution in the pristine Amazonian forested area of French Guyana exhibited concentrations from 2 100 ng/m 3 This was significantly higher than previous background levels determined by the Centre National de la Recherche Scientifique (CNRS) thereby suggesting that the

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73 exchange of gaseous mercury between the forest canopy and free atmosphere pl ay a key role in the cycling of mercury in tropical environments 51 Furthermore, rainforest ecosystems naturally emit large amounts of reactive gases and aerosols that can enhance the oxidation of mercury and precipitation washout. 4.3 Mining in Guyana and Environmental Regulations In Guyana, ar tisinal gold miners make up approximately 95% of all the miners whilst the remaining is from large scale operations. Although, representing only 5% of the mining operations, large scale and multinational companies from major production industries (e.g. bau xite, diamond, timber, and sugar) account for 80% of the domestic economy 212 In the large scale mining sector, miners use sophisticated equipment and cyanide (HCN) to extract gold from ore such as the former OMAI Gold LTD located in Region 8. Th is method of extraction is quite costly. Therefore, due to economical factors, limited technology, and eas e of availability, small and medium scale miners principally use the more primitive technologies which employ the use of el emental mercury for gold extraction and gravitational agitation or whole ore amalgamation social economics and environment. Since the rise in gold prices in the late 19 80s, small scale operations in Guyana have increased significantly 206 As of 2005, Guyana had 3,715 medium scale prospecting permits and 41 prospecting licenses for large scale operations 213 However, a ccording to the Household Income and Expenditure Survey described by Ifil 212 regi ons 1, 2, 5, 8, and 10 where increased mining activities are present and most Indigenous groups reside, the highest unemployment rates of 16.7, 15.5, 14.6, 19.4, and 15.2 percent, respectively, exist. Of the total population, women within these regions represent the highest in unemployment 212 Efforts to reduce mercury released in small and medi um scale g old mines have been underway in Guyana since 2004. I n accordance with the United Nations Environment UNEP) Governing Council Decision 23/9 IV of the International Chemic al

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74 Programme, Guyana has established mercury partnerships within the Amazonia, Guiana Shield, Caribbean Region, and nationally to reduce environmental contamination and health effects asso ciated with mercury exposure. These partnerships have been outlined in Table 4.2. Historically, the use of mercury has been seen to impair waterbodies within Guyana. Some of the programs advocate the use of alternative mercury technologies that propose t he use of cyanide which may develop even more environmental issues than mercury. In 2001, the tailings dam breach by OMAI Gold Ltd. a large cyanide leaching facility, caused an immense amount of damage to the riverine communities along the Essequibo Rive r, the principle drinking water supply for these communities 214 Th e partnership programs have focused solely on addressing mercury handling practices, heightened awareness. However, most of the programs with the exclusion of some of the World Wildlife Federation (WWF) Guianas programs, have focused on key stake holders, miners, and governmental/university officials thus minimizing the importance of women, children, and the indigenous, the most vulnerable populations to mercury poisoning Table 4.2. Mercury Partnerships and Programs Within Guyana Aimed to Reduce Mercury Exposure. Partnership/Program Partnership Countries Focus Regional Awareness Raising Workshop on Mer cury Caribbean Region PPC*: Basel Regional Centre, CARICOM, CEHI*, UWI* workshops developed to raise magnitude of problem and address strategies to address mercury issues Regional Action Plan for the Prevention and Control of Mercury Contamination in th e Amazon Ecosystems Amazon Cooperation Treaty Organization Proper handling of mercury, clean technologies, and sustainable economic develop of gold production Use of Mercury Free Technologies in Mining Guyana Shield (Guyana, Suriname, and French Guiana) and WWF** Workshops, demonstration projects, panel discussions, and public awareness video aimed at reducing impacts of small and medium scale mining on the environment General Environmental Capacity Development Mining Project (GENCAPD) CIDA, GGMC, Guya na EPA, Guyana Gold and Diamond Miners Association, IAST, Ministry of Health, UG *** Human and fish mercury studies in some mining districts; regulations and codes of practices (e.g. use of retorts and illegal mining concessions prohibited), public video, miner workshops *PPC Proposed Partnership Communities requested that they play more integral part of awareness campaign ; CEHI Caribbean Environmental Health Institute; UWI University of the West Indies ** WWF World Wildlife Federation. ***CIDA C anadian International Development Agency; GGMC Guyana Geology Mines Commission; EPA Environmental Protection Agency; IAST Institute of Applied Science and Technology; and UG University of Guyana.

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75 Figure 4.3 ns of Konashen District and Iwokrama and Mine (KN Kaiteur National Park)

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76 4.4 Sampling Area The study sites for Guyana depicted in Figure 4.3 include four distinct areas: Mahdia, Iwokrama Owned Conservation Area. The sites within Guyana were chosen based on several factors which include areas centrally located in gold mining regions and those that are considered pristine and protected from anthropogenic activities. 4. 4.1 Ma hd ia Ma h d ia is the central town for mining and is currently the largest mining area in the country. a s a major source of income for resident s and migratory workers. The area is undergoing severe deforestation and soil erosion possibly as a result of extensive mining activities. The small scale mines within Mah d ia as well as other small and medium scale mines in Guyana use the following conven tional gold mining process: (1) clearing of the concession by logging; (2) land dredging or the use of hydraulic pressure to extract low grade gold bearing ore thus forming large pits; (3) collection of ore placed on a sluice box for manual or mechanical g ravitational agitation to settle gold deposits; (4) metallic mercury is combined with the final concentrate (settled gold/ore deposits) oftentimes directly on the sluice mats or with the concentrate that is shaken off of the sluice mats ; (5) followed by a roasting technique or the recovery of gold by burning off of mercury from the gold Safety precautions during the recovery phase (e.g. use of retorts to limit atmospheric releases of mercury ) and practices of mercu ry application during the mining process ( directly o n the mat or after the mat is shaken) vary by each concession or mine camp It has been estimated that for every 1 kg of concentrate there is 14 grams of mercury required to form an amalgamate 215 ; however, oftentimes approximately 30 grams of mercury is rubbed directly on to the mat or the final concentrate retained on the sl uice mats 108 which is considered an illegal mining practice

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77 Within the town center of Mahdia, mercury can be easily bought over the counter in the local market. In addition, there is limited amount of paved access roads as well as no access roads to the mine sites Along the outskirts of town are local garbage dump sites where several plastic and Styrofoam containers are seen lining the streets. 4.4.2. Arak The 21,755 km 2 with populations less than 1000 persons, have been mined extensively for manganese, diamond, and gold; however, the dominant commerce today is gold mining 108 This area is a part of Mining District 5 and small medium scale gold mining occurs in Arakaka on of residency for many of the miners and their families. Port Kaituma served as the port for manganese cargo when the mine was operating and is now another residence for many in the mining industry. Residents and workers surveyed within this area depen d extensively on rain catchments and springs for potable water, consume fish from the rivers and the majority of those involved in the mining business used mercury 216 Hair and fish samples have also been found to have hi gh levels of mercury 216, 217 Sediment and soil samples were collected from Port odies in Arakaka as well as from an active gold mine in Arakaka in April 2005 in conjunction with the Institute of Applied Science and Technology (IAST) under a WWF Guianas sponsored project.

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78 4. 4. 3 Konashen Community Owned Conservation Area Figure 4 .4. Map of Sampling Areas Along the Essequibo River (Kamoa River, Sipu River, Acari Mountain Creek, Masakenari River) W ithin the Konashen Community Owned C onservation Area (COCA). The Konashen Community Owned Conservation Area (COCA) sampling sites have bee n outlined in Figure 4.4. COCA is comprised of 6,250 km 2 of some of the most pristine expanses of evergreen forests in the northern part of South America with over 319 species of birds, and 119 species of fish, including four that may be new to science (Alonso et al., 2008). The area is primarily underlain by sedimentary rocks and sand and houses the headwaters of the Essequibo River, and drains the Kassikaityu, Kamoa, Sipu ashore, Kamoa and Kaiawakua with elevations reaching 1 200 meters above mean sea level. The Konashen District supports 200 Amerindians known as the Wai Wai who rely heavily on the Essequibo and its tributaries for daily water activities (e.g. drinking, ba thing, eating, and cultivating the land) and who have teamed up with the GOG via the Ministry of Amerindian Affairs and Conservation International Guyana (CI Guyana) to develop and implement a sustainable management plan for the area. It is the second lar gest out of five mining or industrial development in the area COCA however, the local population

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79 speculated on certain areas being old mining sites and also on the exi stence of illegal mining activities. Hammond et al. 182 indicates that registered mines exist less than 200 km east of the CO CA along the Brazilian border in Mining District 1. In October 2006, during the dry season, sediment samples were collected from the banks of the Sipu R iver (SR), Acarai Mountain C reek (AM), Kamoa R iver (KR), and Essequibo R iver (ER), the sites have been identified in Figure 7 and have been described in more detail elsewhere (Trotz, 2008). Samples were also collected in creeks and swamps in these areas. This sampling was done during a Conservation International Rapid Assessment Program (Alonso et al., 2 008) and sample sites coincided with the various camp locations. In 2007 a COCA managed water quality monitoring program was established using a subset of the sampling sites identified in this study.

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80 4 4 4 Iwokrama International Centre for Rain Forest C onservation and Development Figure 4.5. Location of Sample Sites Along the Essequibo and Siparuni Rivers Within the Protected National Park of Iwokrama, Guyana (S.A.) and Regional Borders (M odified from Iwokrama) Iwokrama is located in the heart of the Guiana Shield and is the home to the Makushi Amerindian trib e as well as a diverse species of flora and fauna. It is one of four protected areas in Guyana, and by far the largest Encompassing approximately 3 710 square kilomet e rs (1 430 mile) it borde rs the Pakaraima Mountains to the west, the Essequibo River to the east, the Siparuni River to the north while the Burro Burro River runs through its center. The Iwokrama International Centre for Rain Forest Conservation and Development (IIC) was establish ed following the IIC Act (1996) to provide for the sustainable management and utilization of the rainforest. The highest point on the Iwokrama M ountain is close to 1 000 m. In addition to being the home of the Makushi indigenous group totaling roughly 2 50 people in Fairview Village (15 communities south of the Iwokrama forest combine to give a total indigenous population greater than 5000 people ) IIC is known for its extensive biodiversity which includes 475 species of birds, over 400 species of fish, a nd over 90 species of bats 218 As one of the few protected

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81 lowland tropical rainforests in the Amazon, IIC serves as an ecotourism site and research area for sustainable livelihoods, biodiversity and ecosystems services research. The site supports a sustainable utiliz ation area which includes certified logging operations under the Forest Stewardship Council (FSC). The Iwokrama Reserve is partly bordered by rivers and more in the north is surrounded by areas designated for small to medium scale gold mining (land mining on opposite side of rivers) although regulations are in place preventing this activity given its proximity to Iwokrama. Sampling of five locations occurred in March 2009 on the Siparuni and Burro Burro rivers, although not as far as the mining creeks (Fig ure 4.5) Based on observations and recollections of Iwokrama staff, sampling was done at areas that may have been illegally mined and at areas that will be consistently monitored for water quality under an environmental monitoring program established in 2009. 4.5 Materials and Methods In compliance with the United States Department of Agriculture (USDA) and the for foreign importing soils and sediments, all sediment a nd water samples were handled with proper care. 4.5.1 Glassware/Sampling Kit All glassware and sampling kits were prepared as discussed in Chapter 3.4.1. 4.5.2 Reagents All reagents and lab instrument calibration standards were prepared with trace met al grade (TMG) solutions supplied from Fisher Scientific. Mercury soil standard reference material (NIST SRM 1944, 3.40 mg/kg dry wt.) and freshwater standard reference material (NIST 1641 d, 200 x dilution; 8010 ng/L THg) were used for quality control an d quality assurance. Stock solutions for mercury calibration were made from a 10 mg/L

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82 mercury nitrate standard preserved in 5% nitric acid (Fisher Scientific). A more detailed understanding of r eagent preparation has been described in Chapter 3.4.2. 4 5 .3 Water and Sediment Sampling Water and s ediment sampling was conducted along the Essequibo R iver and in tributaries at its main northern and southern watersheds. The areas covered included (1) unmined land (Konashen and Iwokrama) and (2) actively mined areas (Mahdia and ). Mahdia Kaituma samples were collected directly from mining pits and tailings ponds. A Quanta HYDROLAB multi sensing system was used to measure depth ( 0.003 m), pH ( 0.2 pH units), dissolved oxygen ( 0.2 mg/L), specific conductance (1% of reading 1 count), temperature ( 0.2 o C), and turbidity (5% of reading 1 NTU) in the field and was calibrated using Fisher Scientific standards for pH, conductivity and turbidit y and temperature stable air saturated water for 100% DO sat Sediment samples collected from Iwokrama were carried out using a Wildco 196 B15 standard Ekman bottom grab sampler and transferred in Ziploc bags for easy transport In Konashen and Mahdia, s ediments from the edge of rivers or from select area s within individual mining sites, respectively were collected in Ziploc bags using a stainless steel scoop. All of the samples were stored on ice or refrigerated in the field and shipped on ice to the U SF laboratory. The sediment was dried at 35C in a THELCO Laboratory oven prior to homogenization using a pestle and mortar and stored in Ziploc bags in the laboratory. All sediment samples were analyzed on a 240FS VARIAN DUO Atomic Absorption Spectromet er (CVAAS) coupled to a VGA77 Cold Vapor Accessory. Using the FDEP SOP # HG 020 5.12 digestion procedure 219 samples were predigested followed by CVAAS analysis procedures outlined in the FDEP HG 008 3.16 Method 219 for total mercury concentrations in sediment and waste by Cold Vapor Atomic Absorption Spectrometry (CVAAS). This method is based on US EPA Method 245.5/7471 220

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83 4.6 General Results and Discussion Total mercury loadings in sediment and soil samples and surface water quality data are provided in Table 4.3 with aver ages for the different areas given in Table 4.4 (value standard deviation (SD)) Fifty three sediment and soil concentrations ranged from 29 to 1200 ng/g and averaged 215187 ng/g for all sites. Twenty seven samples taken from active gold mining areas ( Arakaka and Mahdia) had sediment and soil concentrations that ranged from 29 to 601 ng/g and averaged 226171 ng/g. Thirty five samples taken from concentrations that rang ed from 29 to 1200 ng/g and averaged 229223 ng/g. Eighteen sediment and soil samples taken from conservation areas (Iwokrama and Konashen) had mercury loadings that ranged from 53 to 301 ng/g and averaged 18777 ng/g. The highest loadings seen in the Iw okrama samples (IWO2, IWO3 and IWO4) were actually taken at locations which local staff suggested might be old mining camps which might e xplain why sample IWO1 was only 53 ng/g. Some soil and sediment samples were taken from places which prevented the collection of water quality data because of high solids density. For the water quality data collected, pH values ranged from 3.9 to 7.3 pH units with lowest values observed around tailings ponds in Mahdia. The pH of water samples in Iwokrama and Konashen ranged from 4.8 to 6.3 pH units with the lower values observed in small creeks and swamp environments. The average pH for these conservation areas was 5.70.5 pH units. In the Mahdia mining samples, pH ranged from 3.9 to 7.3 pH units and averaged 6.61 .1 pH units. Dissolved oxygen levels for Iwokrama and Konashen varied between 1.2 and 10 mg/L and averaged 6.51.7 mg/L. The lower value of 1.2 mg/L dissolved oxygen was associated with a seasonal pool in Konashen. Dissolved oxygen levels measured in Ma hdia varied from 3.5 to 5.7 mg/L and averaged 4.70.8 mg/L. Turbidity values for Iwokrama and Konashen varied from 0 to 51 NTU and averaged 1415 NTU and for Mahdia it ranged from 12 to 178 NTU and averaged 7055 NTU. Mercury sediment and soil loadings w ere slightly positively correlated with pH (correlation co efficient = 0.2 ; p value < 0.001) whereas no significant correlations were found with dissolved oxygen or turbidity.

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84 Mercury (II) sorption to clays and mineral oxides of iron, aluminum and silicon some of the most common sediment constituents, typically increases as a function of pH until it reaches a maxima then decreases in the higher pH regions 42, 48, 50, 221 and may explain the observed correlation. The presence of competing ions and natural organic matter, especially for the river sediments, likely play a role in loading behavior observed 40, 222, 223 X ray diffraction analysis revealed that sediment s and soils collected from pristine locations were mainly quartz and Al oxides whilst mining areas in Mahdia were rich in clays (kaolinite and Halloysite), phosphates, and Al and Fe oxides (goethite). In natural aquatic systems, lakes and rivers particul arly abundant in Fe Al (hydr)oxides are effective at uptaking mercury 224 Mercury peroxide (HgO) peaks were obtained in samples collected by hydrologic pumps and in tailings. No mercury was observed in samples collected from within the pits which suggest that mercury was being added, most likely from the miners. It has been generally observed that the formation of Hg(OH) 2 is pH dependent 224 The presence of mercury around these areas may further indicate that miners are not recovering mercury using appropriate technologies or applying mercury directly onto gravitational sluice box mats which is an illegal practice. Appendix F highlights all of the minerals determined from most of the sites.

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85 Table 4.3. Sediment T otal M ercury L oadings (sTHg in ng/g dry weight) and W ater Q uality P arameters for S amples T Area sTH g (ng/g) Surface Water Longitude La titude pH DO (mg/L) TURB (NTU) Iwokrama Iwokrama IWO1 53 5.42 6.91 19.1 N04.78912 W058.87139 IWO2 225 5.60 6.85 13.0 N04.73200 W058.85048 IWO3 298 5.70 7.62 32.2 N04.76645 W058.88126 IWO4 120 5.95 10.00 28. 8 N04.74021 W058.92834 Konashen Essequibo River GR ER 11 209 6.28 5.29 11.6 N01.62.976 W058.62.447 GR ER 12 176 6.34 5.97 12.1 N01.64.733 W058.61.826 GR ER 16 198 6.04 5.7 0 N01.68.102 W058.62.934 Acarai Creek GR AM 01 290 4.74 1.2 0 N01.42.180 W0 58.95.221 GR AM 02 131 5.74 7.59 10.7 GR AM 03 121 5.50 7.5 0 GR AM 04 301 5.20 8.25 2.5 N01.38.989 W058.94.489 Kamoa River GR KR 02 220 6.01 6.53 28 N01.53.189 W058.82.967 GR KR 04 121 6.09 6.91 51 GR KR 05 163 6.05 6.62 34 GR KR 06 92 5.19 6.36 5.7 N01.53.427 W058.82.692 GR KR 07 262 4.78 6.22 8.6 GR KR 12 115 N01.53.193 W058.81.922 Sipu River GR SR 06 271 5.65 7.43 5 N01.43.072 W058.92.941 Arakaka S270405 0103 130 N0735.4 31 W059.58.714 S270405 0401 180 N07.35.761 W060.00.260 S270405 0805 61 N07.34.784 W060.00.186 S270405 0704 98 N07.35.193 W060.01.188 S270405 110 N07.35.574 W059.59.378 S270405 0302 41 N07.34.799 W060.00.130 M ine tailings 300 Ridge RidgeRidge S030505 2107 1200 S020505 1804 200 N07.29.448 W060.08.452 S020505 1602 190 N07.29.359 W060.11.120 S040505 2309 200 N07.28.956 W060.09.238 S030505 2006 290 N07.30.129 W060.08.044 S020505 1703 583 N07.29.448 W060.09.214 Port Kaituma S050507 2502 168 N07.41.881 W059.55.450 S050507 2704 364 N07.41.917 W059.53.559 S070505 142 N07.42.517 W059.53.223

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86 Table 4.3 ( C ont in ued ) Sediment Total Mercury Loadings (sTHg in ng/g D ry W eight) and Water Quality Parameters for Samples Taken at Mahdia. Mahdia Mine 1 11, by pump 331 6.59 4.28 47.7 N05.380.23 W059.13596 12, sluice box 127 12B, LHS, sluice box 143 12C, RH S, sluice box 81 12D, camp 134 Diosmp 114 Topsoil 253 Topsoil B 111 Mine 2 14, pit 29 7.33 3.85 14.5 N05.29134 W059.13186 14B, tailings 2 150 7.25 4.07 12.3 N05.29117 W059.13206 15, tai lings 1 222 3.87 3.51 178 N05.28982 W059.13229 16, sluice box 49 5.95 4.25 14.6 N05.29007 W059.13061 17, tailings 3 66 7.05 4.99 34 N05.26475 W059.13805 Mine 3 18, tailings 409 7.31 5.66 116 N05.26437 W059.13745 19, by pump 443 Mine 4 20 508 6.73 5.45 80.2 N05.26443 W059.13791 21, by pump 471 7.11 5.5 95 N05.25819 W059.13311 Tailings 601 7.21 5.59 104 N05.25814 W059.13308 Mine 5 22, by pump 72 N05.27391 W059.13372 22b, sluice box 127

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87 Table 4.4. Average Va lues of Total Mercury Loading, sTHg (ng/g dry weight), pH, Dissolved Oxygen, DO (mg/L), and Turbidity, TURB (NTU) Found in Each Study Area. Location (# samples) sTHg SD (ng/g) Surface Water pH SD DO SD TURB SD (mg/L) (NTU) Iwokrama (4) 17410 9 5.70.2 7.81.5 239 Essequibo River (3) 19417 6.20.1 5.60.3 67 Acaria Creek (4) 21198 5.30.4 6.13.3 35 Kamoa River (6) 16267 5.60.6 6.50.3 2519 Sipu River (1) 271 5.65 7.43 5 Arakaka (7) 11687 Mathew's Ridge (5) 416440 Port Kaituma (3) 225128 Mine 1 (8) 16285 6.59 4.28 47.7 Mine 2 (5) 10381 6.31.5 4.10.6 72116 Mine 3 (2) 42624 7.31 5. 7 116 Mine 4 (3) 52792 7.00.1 5.51.7 936 Mine 5 (2) 10039 All sites (53) 215187 Conservation Areas (18) a 18777 5.70.5 6.51.7 1514 Gold Mining Areas (27) b 226171 6.61.1 4.70.8 7055 Mining Areas (35) c 229223 a Conservation areas include Iwokrama and Konashen only. b Mining areas include Arakaka and Mahdia (Mines 1 5). c Mining areas include Ara 5).

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88 Fig ure 4.6 Box Plot o f Total Mercury Loading on Sediments a nd Soils, sTH g (Ng/G Dry Weight), By Area Sampled Showing Values That Fall Within the 25th and 75th Percentile (Box), the Minimum and Maximum Loading (Line) a nd t he Median (Diamond). Close To Pumps, Sluice Box, a nd Tailings Are Averages f or Samples f rom Active Gold Mining Areas ( Arakaka a nd Mines 1 5 i n Mahdia ). Conservation Areas Include Iwokrama Konashen ( Essequibo Acarai Kamoa a nd Sipu ), a nd Gold Mining Areas Include Arakaka a nd Mahdia ( Mines 1 5). Figure 4.6 shows a box plot of the sediment and soil total mercury loadings by site. The water source the manganese oxides in the soil and sediment serve as sorption sites or sinks for mercury 225 mining and non mining areas in this study all lie between 29 and 364 ng/g with no significant difference seen between loadings found in conservation areas versus mining areas or areas close to mining. If only active gold mining areas are compared with the conservation areas higher loadings are seen in the gold mining areas. Arakaka and Mines 1 5 were the sites with active gold mining and samples were taken from the sl uice boxes and/or other areas around each of those sites. Mines 3 and 4 had the highest sediment loadings for the active gold mining sites studied in Mahdia. Figure 4 .7 shows an image of the sediments representative of these mines as well as the average 0 200 400 600 800 1000 1200 1400 Location sTHg(ng/g dry weight)

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89 mercury loadings observed. The iron oxides were clearly prevalent in Mines 3 and 4 and to a lesser degree in Mine 5 Further spectroscopic analyses of collected samples are currently under investigation. In Thailand, Pataranawat et al. 226 surveyed areas around an active gold mining site that uses mercury amalgamation methods and found extremely high localized levels in soils, especially close to recovery areas (~ 10,000 ng/g) which they attributed to volatilization of Hg and dry deposition nearby The mine sampled in Arakaka, and Mines 1, 2, and 5 in Mahdia, were also larger than Mines 3 and 4 and hence the recovery process was done fairly far from the pits and sluice boxes sampled. In addition to ore type and mine size, other factors like mercury handling and practices could influence the loading s observed At each mining site it was observed that varying degrees of management practices and worker awareness and attention to handling of mercury were carried out; however, through informal discussions at all sites it was stated that retorts were used during recovery. Unfortunately, no soil samples were taken from the retort stations or mercury recovery areas Fig ure 4.7. Photographs o f Sediment Samples Collected i n Mahdia f rom 5 Different Mines. The Average Sediment Loadings o f t he Various Sites a t Mines 1 5 Were 16285, 10381, 42624, 52792, and 10039 n g/ g Respectively. Figure 4.6 also plots data for specific areas around the mining sites, directly under the sluice box, in various tailings ponds, and close to hydraulic pumps. The sediment close to the sluice box had the lowest average mercury loadings of these three categories and the sediment close to the diesel powered hydraulic pumps had the highest average loadings. The pump samples were taken at the points where water was first pumped into the mining pit and included water recycled from tailings areas and water collected in flooded forest floors or creeks. Hence, the higher loadings seen close to the pump samples could be due to the fact that, 1) they burned diesel which could be a local s ource of mercury; 2) they received water and likely fines from tailings which may have been exposed to mercury

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90 during the mining process; and 3) they inundate a forest floor which could provide an environment conducive to mercury release from topsoil. Fig ure 4.8. Diagram o f Mine 2 i n Mahdia Showing Main Mining Processes a nd Areas Sampled Including: 1) The Pit Where High Pressure Water i s Used t o Make A Slurry With t he Ore; 2) Sluice Boxes Fitted With Mats That Trap Gold Bearing Ore As Slurry Passes Ove r; a nd 3) Tailings Ponds Where Sediment i s Allowed t o Settle, Sometimes With t he Help o f Flocculants. For one mine in Mahdia samples were taken from the pit, sluice box and tailings ponds and the sediment total mercury loading increased at each stage as shown in Figure 4.8 The designations used here to identify different tailings areas may not match those designations used by miners, however, it reflects various locations within the mine site that are separated by some type of makeshift boundary/earthen dam. Researchers have found that forest soils in the Guianas have total mercury loadings in the range of 30 to 800 ng/g 210, 211 Forest and overburden removal constitutes one of the first steps in the mining process and the low loading seen in the pit (29 ng/g) likely re flects the low background concentration of mercury in the ore. Between the sluice box and the first tailings pond area the loading increased from 49 ng/g to 222 ng/g and this could be due to inputs of mercury from the sluice box, atmospheric deposition, o r an increase in the concentration of finer particles. The sample from the sluice box was taken prior to passing over the black mat which collects denser gold bearing ore. Although the application of mercury to this mat is illegal in Guyana, miners somet imes apply mercury

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91 to increase gold recovery. However, s urveys of miners done simultaneously with this sampling exercise did not reveal this practice in Mahdia. The turbidity of the water sampled in the first ponded area was high (178 NTU) indicating a high percentage of fines which have been positively correlated with mercury loadings downstream from artisinal gold mines in Suriname and Guyana 143, 153 Miners are encouraged to apply flocculating agents to their tailings and this likely occurred at Mine 2, prior to the last two tailings pond locations (Guyana Geology and Mines Field Officer, Colin Mathis, Personal Communication). This c ould explain the observation that as the tailings moved further away from the sluice box, from one pond area to the next, the mercury loading decreased as did the turbidity.

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92 Table 4.5. Range of Mercury Concentrations Seen in Sediment from This and Other S tudies. Location sTHg (ng/g) Arakaka ( this study ) Mathews Ridge (this study ) Port Kaituma (this study ) 41 300 190 1200 142 364 Mahdia mine wastes (this study) 29 601 Konashen river and creek sediments (this study) 92 301 Iwokrama river sediments (this study) 53 298 US Streams (2009) 174 unmined basins mined basins 0.90 2480 0.84 4520 Brazil Summary (2003) 206 channel sediments a soils b <20 19800 30 406 French Guiana Sinnamary River (2000) 210 forest soils r iver sediment lateritic soils 50 480 10 1550 40 180 French Guiana ( 2008) 211 oxisol at ECEREX reserve utisol at ECEREX reserve 300 800 30 300 French Guiana (2003) 209 coastal and ECEREX non mining area upstream from mines streams below mines <150 <400 50 6200 French Guyana (2003) 208 Litany R iver (uncontaminated) mining tributaries 74 150 254 350 Artisinal Au mines Suriname 143 mine wastes streams below mines uncontaminated baselines 5.5 200 110 150 14 48 Essequibo and Mazaruni rivers, Guyana (2003) 206 Essequibo R iver (mining) Mazaruni R iver (mining) 4 225 5 707 a Summa ry of studies done up to 1995, b summary of studies done up to 2000. Table 4 .5 summarizes the more recent studies on mercury loadings in the less deforested Guianas where the highest sediment loadings observed have been in tributaries of small or mediu m scale mining activity 143, 206, 208 but where high levels have also been recorded at remote areas 209 For the most part, the hig her end of the range of sediment loadings in US streams 174 and in Brazil (as summarized by Miller et al. 206 ) are greater than values

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93 observed in the sediments from the Guianas, even in active gold mining sites that use mercury. The upstream sediments and unc ontaminated baselines found in other studies of the Guianas in Table 4 .5 includes coastal areas and the range of loadings varies from 14 to 150 ng/g whereas the sediments from mining sites or tributaries downstream from mining sites ranged from 5.5 to 6200 ng/g 143, 206, 208, 209 Soil loadings in the ECEREX reserve area and Sinmarry river in French Guiana ranged from 30 to 800 ng/g with higher loadings seen in forest soils and more specifically in oxisols 210, 211 The mercury l oadings of sediment and mine tailings observed in this study fall within the range of loadings observed in similar sites throughout the Guianas 143, 206, 208 210 however, the loadings observed at the conservation areas were not as low as those seen in some uncontaminated baselines for river sediments in this region 143, 208, 209 The Iwokrama samples were taken from the rivers on its periphery where mining likely occurs on lands outside its jurisdiction. The three highest samples were identified by staff as areas where they thought may be impacted by some sort of historical mining activity. Hence, it is very likely that the levels reflect mining and it may be un fair to cla ssify th ose samples as representative of an uncontaminated baseline. It does serve as a baseline from which future and more extensive monitoring programs can reference. Sampling for mercury within the site itself will provide important information on the impact of various income generating activities like the sustainable logging and can be used to better understand the dynamics of coupled human natural systems. Samples in Konashen were taken from areas where the Wai Wai had relatively little recollection of mining activity and in the Essequibo headwater region with low population density (0.032 persons/km 2 ) and not much through traffic. These samples can therefore be considered an uncontaminated baseline for sediment loadings in the southern drainage are a of the Essequibo River Though the Wai Wai practice slash and burn agriculture which also could release mercury rich topsoil to the rivers, most of the sample sites were taken upstream of village plots in areas considered amongst the most pristine in th e world. It should be noted that Konashen borders the Brazilian gold producing state of Para (mining activity concentrated some distance away) and also lies approximately 200 km west of registered mines in Guyana, and the influence of atmospheric releases from those areas on

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94 Konashen is unknown. Using published geospatial data on registered gold mines and logging activity in Guyana, Konashen is the farthest from registered gold mines and logging activity of all sites sampled 227 4.7 Summary The Essequibo R iver as well its northern and southern tributaries were identified as collection sites due to limited data for the areas Moreover the sites represented lands that were considered protected and pristine (Konashen and Iwokrama) and actively mined (Mahdia and Arakaka/Ma Preliminary findings show that mercury concentrations from f ifty three sediment and soil samples ranged from 29 to 1200 ng/g and averaged 215187 ng/g for all sites. Eighteen sediment and soil samples taken from conservatio n areas (Iwokrama and Konashen) had mercury loadings that ranged from 53 to 301 ng/g and averaged 18777 ng/g which confirmed suspected presence of old mining camps and sites A ctive gold mining areas had sedime nt and soil concentrations that ranged from 29 to 1200 ng/g and averaged 229223 ng/g. X ray diffraction analysis revealed that sediments and soils collected from pristine locations (Iwokrama) were mainly quartz and Al oxides whilst mining areas (Madhia) were rich in clays (kaolinite and Halloysi te), phosphates, and Al and Fe oxides (goethite). Mercury peroxide (HgO) was observed in XRD analysis of s amples collected from mine area hy drologic pumps and in tailings.

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95 CHAPTER 5: BOLIVIA Figure 5.1. Nine Departmen ts of Bolivia With Respect to Other Sampling Locations and An Enlargement of the Sampling Area Within Bolivia Lago Titicaca 5.1. Introduction This chapter highlights the social and economic benefits of mercury to Bolivia. In addition, a presentation of the sampling approach and analysis of water, sediment, and fish samples for total mercury concentrations and mineralogy are presented Study sites Bolivia Guyana Florida

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96 5.1.1 Objectives and Tasks The objective of this chapter is to investigate mercury loadings in Lake Titicaca, a wa ter body in Bolivia with little characterization with respect to mercury as well as address the role that socioeconomic factors play in mercury loadings. The tasks to accomplish this objective include: Task 1a: Identify and characterize suitable study sit es for this work. Task 1b : D eter mine levels of total mercury present in fish, water, and sediments by using cold vapor atomic absorption spectroscopy (CVAAS) and cold vapor atomic florescence spectroscopy (CVAFS) Task 1c: Identify the geochemical condi tions that affect the fate of mercury by using BET surface area analysis, electron dispersion spectro scopy, and X ray diffractometry Task 2a: Document the socioeconomic, regulatory and geopolitical factors within Bolivia through a literature review 5.2 Bolivia Bolivia, one of the poorest countries in South America is landlocked with an area of 679, 619 km 2 and is bordered by Argentina, Brazil, Chile, Paraguay, and Peru 228 W ith a population of 9.7 million 229 and approximately 70% of its population classified as poor and indigenous 230 it is the world's third largest cultivator o f coca and producer of cocaine 229 Divided into nine departments (Beni, Chuquisaca, Cochabamba, La Paz, Oruro, Pando, Potosi, Santa Cruz, and Tarija), it is ethnicall y, linguistically, and geographically diverse (Figure 5.1) 230, 231 Ethnically, Bolivia is composed of many indigenous tribes and mestizos (mixed racial ancestry, Spanish and indigenous background). In terms of l inguistics, the primary language is Spanish; however there are over 40 indigenous languages which Quechua and Aymara represent the two dominate indigenous dialects and tribes 229, 231 Geographically, its highland plateau or A ltiplano (elevation of over 6,000 m) rests within the rugged Andes Mountains where weather

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97 conditions are frigid and semiarid 229 Located in this area is the world highest and ke Titicaca. On the other hand, its lowlands experience humid tropical conditions as it resides in the Amazon Basin. It is also volcanically and tectonically active 230, 232 The indigenous groups (Aymara and Quechua) traditionally live in the Altiplano and the valley of the high Andes. It is ranked 113 th out of 177 countries on the UN Human Development Index and a large proportion o f its population has limited access to education, health, and affordable housing 233 F ish protein consu mption accounts for 62% of the diets of rural inhabitant s residing i n the Peruvian Amazon which is similar to other Andean Amazon basin communities 234 Additionally, the A ndean A mazon R ivers A nalysis M onitoring (AARM) I nstitut de Recherche pour le Development (I RD ) Bolivia have initiated Hg measurement s in water of the Bolivian catchment 235 ; however, minimal results are published but it is believed Hg contamination of fish resource in the Andean Amazon could impact the health of Bolivians. During the early 1980s, the country experienced an economic crisis. Therefore to help stimulate economic growth, cut poverty rates, as well address issues of inequality, Bolivia enacted several reforms to spur private investment. In the 1992 US Commerce Business Report, it was estimated that the United States imported trading partner 236 This accounts for more than one exports. The report further concluded that the US made over $100 million in the sale of mining equipment to Bolivia which has since doubled 236 Since this w as in large a success to the US economy, US investors with the assistance of Bolivian partners have built several businesses directly involved in mining of tin, gold, and silver. Mining contributes 4.5% to the GDP 237 of Bolivia and has impacted its environment due to unregulated and unsustainable practices Hig h mercury concentrations and fluxes have been estimated to be highest during the dry seasons i n t he Bolivian Amazon basin at the Andean piedmont as well as along the upper Madeira Rivers where gold mining activities occur 238 In addition, s tudies on the Peruvian si de of Lake Titicaca suggest that the lake

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98 is impaired by mercury. S tudies have found up to 0.4 mg/kg of Hg are in mackerel fish 66 in Peru's Puno Bay. The Boliv ian side of Lake Titicaca, fed by the Ro Suches, has yet to be analyzed for total mercury content. 5.3 Mining in Bolivia In Bolivia, less than 4% of the forty eight percent of rural land is usable for cultivation due to the arid lands thus the people depend on mining as a means of economic survival 236 From 1900 1980 tin (Sn) was the principle commodity of high regard because of its usage in weaponry during war. This industry was operated by the 1985, the exploitation of other precious metals, principally gold, increased significantly. Figure 5.2. Total N umber of P ersons E mployed in V arious M ining S ectors in Bolivia from 1989 1998 B based on R eports by Bocangel 239 With t he United States as the single largest investor in Bolivia, the import and export of mining equipment and supplies regained momentum. Number of People Employed in Various Mining Sectors (Sn, Au, and Zn) 1989 1998 0 5000 10000 15000 20000 25000 30000 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 Years Total Number Co Op Mines Small Scale Mines Medium Scale Mines State Mines

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99 From 1971 to 1980, the mining sector employed over 20,000 workers and began to increase until 1986 when the economic crisis took a toll on the Bolivian economy and tin demand dropped (Figure 5.2) However, o ver the past fifteen years mining coop eratives have grown steadily. With a mining workforce of over 45,000 registered miners, Bolivian mining cooperatives contains about 506 mines of which 376 mines are associated with extraction of alluvial gold, tin, and tungsten (La Paz Department), 109 in base metal (zinc, lead, and cooper) (Oruro and Potos), and 21 mines recovering ulexite (hydrated sodium calcium borate hydroxide) and non metallic minerals (Uyuni Salt Flats) 237 These cooperatives belong to the Federacin Nacional de Cooperativas Mineras (FENCOMIN). On the other hand, medium scale miners ma inly associated with mining and smelting employs approximately 3,500 miners and belongs to the Medium Scale Miners Association whilst private small scale miners are affiliated with the National Mining Chamber (Cmara Nacional de Minera) and employs 3,500 miners as well 237 by a sharp emergence in employment within mining cooperatives. Cooperative mines or co ops are composed of many teams or cuadrillas, groups of one to ten miners that are in operation independent of the cooperative. They produce, process, and trade their own findings. The cooperative, organized into groups by the mineral being extracted, is the lead organization that supplies essential mining supplies and equipment such as compressed air, technical assistance, and trading to the cuadrillas in exchange f or a percentage of the net value of their sales. However, in the gold cooperatives more primitive technologies that require the use of mercury are utilized. In addition, skilled labor, security/safety, or technical assistance are not provided. In all of the cooperatives, operation/ownership is controlled by former COMIBOL workers, their families, and even in some rare cases seasonal migrants who in a large part are the indigenous poor. These cooperatives have a total disregard for the safety and well bei ng of its workers as well as the environment. The methods of exploitation do not have proper environmental impact assessments, protocols for waste management (e.g. tailings dams or ponds, water treatment prior to discharge), or closure plans in place. In the gold cooperatives, the structure of organization is more complex and contains many laws of regulation established by the chief gold cooperative.

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100 These cooperative types contain both formal and informal miners (barranquilleros). For example, the barr They reprocess the tailings of the cooperatives in search of gold that was mistakenly lost during extraction by the formal miners. All of their practices can immense amount of damag e to the people and their environment. 5.4 The Mining Culture and the Exploitation of the Poor and I ndigenous P opulations The culture of mining is complex and oftentimes with no real alternatives. Miners working to produce generous earnings for their families join the profession with a clear understanding of the daily risks associated with their profession. In fact, before entering into the mines the miners believe that one must exclude the outside world from the mines including God known as Pachamam a to the indigenous Andean communities. Then as the miner enters into the mine one must close the door and submit to the mining devil, El To, by providing an offering before beginning work. Miners usually provide offerings of tobacco, liquor, and coca l eaves to simultaneously ask for protection and high mineral recovery. Traditionally, El To (The Uncle), lord of the underworld resembles the shape of a goat and is similar to Legba in the Voodoo religion 240 However, it is unconfirmed whether the use of mercury for ritualistic practices is performed among inner mine offerings or community sacrificial ceremonies which involve slaughtering a llama and smearing its blood on the outside of the mine doors in hopes that El Tio will grant refuge to the miners 241 In Bolivia, mining has caused extensive soil erosion and pollution of freshwater systems 242 It has stimulated the economy but continuous ly exploits the indigenous popula tion women, and children who play an integral part in the mining process. Some 90% of all mining children begin working in the mines at age six or seven to earn a salary of Bs. 4 (approximately, US$0.50 per day ), and work seven days a week between seven to eight hours or until a palo, 0.10 g, of gold is obtained with only one thirty minute break 243, 244 According to the Bolivian Code for Boys, Girls and Adolescents General Labor Law, fourteen years of age is the legal minimum age for employment In addition, minors are

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101 prohibited from conducting dangerous, unhealthy and phys ically exhausting work especially in underground mines. Wome n and children under 18 years of age are only allowed to work during the day 244 Furthermore, t he Ministry of Planning and Sustainable Development in Bolivia estimate s that 60% of children employed in mining and other practices do not attend school 244 Often grouped as informal miners or barranquilleros, they are exposed dai ly to deplorable and deadly conditions. These conditions warrant the use of special apparatuses and personal protective equipment which are not supplied by the co op officials. Due to financial hardships, miners often do not use them or improvise (e.g. u sing several layers of clothes to cover their nose and mouth to act as a breathing apparatus). The cooperatives do provide cost based medic services or sanitation posts at the mine sites. Due to financial reasons the informal miners prefer to use home re medies and/or chew on coca leaves to relieve any pain and exhaustion experienced from the deplorable working conditions.

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102 5.5 Sampling Area 5.5 .1 Lago Titicaca, Bolivia (S.A.) Figure 5.3. Lago Titicaca ( Lake Titicaca ) a nd Its Two Southeasterly Qua rters Known t o t he Indigenous, Quechua a s Lago Huinaymarca (2) a nd Lago Chucito (3). Lake Titicaca, also known in Spanish as Lago Tititaca, is an ancient nearly closed, basin altitude Alti plano basin (>3,800 meters above sea level) of the Andes Mountains. Jointly controlled and bordered by Peru, it occupies a total surface area of 8,400 sq. km 245, 246 which is shrinking due to increasing evaporation rates suspected t o be caused by increasing humidity and lack of rain 236 amplifiers to regional climate change 235 247, 248 It is divided into three main areas (Figure 5.3) known as (1) Lago Mayor (6,500 km 2 ), (2) Lago Menor (1,400 km 2 ), and (3) Bahia de Puno (500 km 2 ). The maximum depth of the lake is 288 m which is in the Lago Mayor division 246 whilst the shallower areas are Lago Menor (20 30 m) and Bahia de Puno 246 Bahia de Puno and Lago Mayor reside mainly on the Pe ruvian side of the lake 1 2 3

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103 where as Lago M enor is on the Bolivian side. Bahia de Puno is the most contaminated and Lago Menor is the most understudied. Precipitation accounts for 55% of the inflowing water to Lago Titicaca whilst 45% of its inflowing water comes from rivers and streams 246 The major rivers flowing in to the lake include the Ro Ramis (74 m 3 / s ), Ro Coata (47 m 3 /s ), Ro llave (38 m 3 / s ), Ro Huancan (19 m 3 / s), Ro Suches (11 m 3 / s ), Ro Keka, and Ro Tiwanaku 246 On the other hand, evaporation as well as the Ro only means fo r naturally releasing water flow or overflow. During the summer months of December to March, the lake is subjected to the influence of the intertropical convergence zone (ITCZ) and experiences monsoon weather events as North East and South East trade wi nd s converge to form large bands of clouds or thunderstorms. Average temperatures for the areas surrounding the lake are between 3 12C (37 54F) but can go lower. In addition, it is characterized by its unique flora and fauna. The lake spans a distance of 190 km in length and 80 km in width. It has been characterized to contain over 30 native fish species that represent 28 genus Orestia and 2 benthic catfish species of Trichomyceterus dispar and Trichomyseterus rivulatus 249 Exogenous species of pejerrey ( Basilichthyes bonariensis ) and trucha ( Salmo gaidneri ) were intentionally introduced into the lake in 1939 to help with issues of declining fish stocks. Such phenomenons have been frequently seen to occur globally in many freshwater systems. The lake is essential to many Bolivians and Peruvians. Serving as the primary water supply for over 1,000,000 people living in the lake region in both Bolivia and Peru, it is the capital city of LaPaz and the communities in the LaPaz department princ ipally receive their fish from this area. Residents have also described ice melts and rain waters as additional sources of water. It is managed by the Proyecto Especial del Lago Titicaca (PELT) and the Autoridad Autonoma Binacional del Lago Titicaca (ALT ) which formed as a result of the severe drought experienced in 1982 1983 246 PELT is a Peruvian management program for water resources, fisheries, and farming in Peru where as ALT is

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104 a binational master plan for water resource management and protection prevention of floods in Bolivia and Peru 246 5.5.2 Site Description Figure 5.4. Digital Mapping of Sample Points of the Tributaries of Lago Titicaca with Enlargements of the Tin (Sn) and Lead (Pb) Mining C oncessions and Lago Titicaca (from Google Earth). In July 2009, over a period of three days, water and sediment samples were collected from twelve locations in La go Titicaca and its rivers and streams ( Ro Suches, Ro Alcamarini, and mountain streams). Sample collection was done in collaboration with ACDI/VOCA, Universidad Tecnologica Boliviana, and the University of South Florida. This area was highly populated b y Quechua and Ayamar who do not speak fluent Spanish. The refore, the ACDI/VOCA representative acted as the translator for Quechua and the Unversidad Tecnologica Boliviana researcher was the Spanish translator. The sites have been denoted in Figure 5.4 a s LT1 LT7 for streams and rivers whilst LT9 12 T6 T7 T5 T 2 T1 T3 T4 T9 12

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105 represent samples collected directly from the lake. F ish samples of known origin, genera and habitat were bought at a popular outdoor m arket in the Lago Titicaca area. The area around the lake can be classi fied as arid containing several hills with mature slopes rising to over 800 meters above the lake. The lands directly surrounding the lake (T1 T4) ar e poor for rearing livestock (e. g sheep, llamas, and alpacas). Potatoes are grown close to the lake at E scoma (T2) and sampling areas T6 T7 contain several agricultural plots for the production of potatoes and quinoa, a staple product, as well as livestock (mainly llamas). Canton Humanata (T6 7) is fed by river water from the Ro Alcamarani and Ro Suches. It is also interesting to note that sampling areas T6 and T7 had an intricate system of piping and raised fields, an ancient farming practice. River levels along the lower reaches of the Ro Suches were low and residents were subjected to extreme water r estrictions. During sampling, the average daily temperatures were between 20 23F where as night temperatures fell below freezing. In addition, s ince ambient temperatures ranged between 5 23F and refrigeration systems were limited in the area, sample s were transported in a cooler to the Laboratorio de Calidad Ambiental of the Instituto de Ecologa of the facultad de Ciencias Puras of the Universidad Mayor de San Andrs for drying prior to shipping to the US for analysis by CVAAS.

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106 5.6 M aterials and Methods 5.6.1 Glassware and Field Supplies I Chem certified pre cleaned glassware ( 2 50 mL) was used for surface and depth water samples. Sediment samples were collected using a stainless steel scoop and bowl. Geographic data points were collecte d using a handheld Garmin eTrek using the Universal Transverse Mercator (UTM) World Geodetic System (WGS) 1984. 5.6.2 Reagents A bulk solution of potassium bromide/potassium bromate was prepared from reagent grade solids dissolved in water. KBr/KBrO 3 was comb ined with concentrated Fisherbrand hydrochloric acid in situ to preserve all water samples. 5.6.3 Water and Sediment Sampling Water and sediment sampling points have been shown in Figure 5.4 Samples were collected from a zinc and lead mine, Minera Potos (T4), a mountain stream in the town of Matilda Aqua Calientes (T4 b) in the town of Canton Humanata (T7) along the Ro Alcamarini which drains into the RioSuches, along the Ro Suches (T1 Tajani, T2 Escoma, and T3 Ullachapi), just before it drai ns into the Lago Tititca, and Lago Titicaca (LT9 LT12). Only unfiltered surface and depth water s amples were collected directly into certified 15 0 mL pre cleaned I CHEM glass bottles. Due to limited access and timing conflicts, depth and surface sediment and water samples were not collected at every sampling point. Water samples from rivers and stre ams entering into Lago Titicaca were collected along shore where as lake samples were collected from onboard a wooden makeshift row boat. All handling operatio ns were performed using ultra clean techniques employed by the US EPA Prior to sample collection at each site, the equipment was rinsed three times with water from the sampling point. Samples were then acidified with bromine monochloride prepared in sit u. All acidified samples were stored in a dark lined

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107 cooler for laboratory shipment Water quality measurements of pH, specific conductivity (SpC), temperature, dissolved oxygen (DO), saturated dissolved oxygen percent (DO sat %), salinity, total dissolve d solids (TDS), turbidity, and depth were collected in the field using a Hydrolab Quanta multiprobe. GPS meas urements were taken at each sampling point along with a corresponding sediment sample. As for surface sediment samples, the top 2 cm were discard ed while the remaining sample was placed in doubly sealed plastic bag and stored in a dark lined cooler separate from water samples. No water samples were collected at Mina Matilda (T4 b) due to concerns with health and safety. All sediments and tailin gs were dried and water samples were analyzed by the Laboratorio de Calidad Ambiental del Instituto de Ecologa de la facultad de Ciencias Puras del Universidad Mayor de San Andrs in LaPaz following the US EPA Method 1631 and for Trace Metal Analysis of Mercury in Water. Sediments and tailings were transported to the University of South Florida and analyzed using a Varian 240FS coupled with a VGA77 following Method 7471. 5.6.4 Fish Sampling Bolivian fish samples of trucha ( Salmo gaidneri ) and pejerr e y ( Basilichthyes bonariensi ) were obtained at the largest local market in the Alto Plano region. Based on fisherm e n accounts these samples came directly from Lago Titicaca where fishermen mainly use nets and traps. In Lago Titicaca, trucha and pejerrey are the dominate species and non native to Bolivia. These species were introduced into the lake in the 1940s and 1950s as a means to help with fish management issues 66 ; however, over fishing is still an issue as the principle source of protein in the region is fish. Samples were weighed, measured, identified for gender and filleted in the field then transported to the Laboratorio de Calidad Ambiental del Institu to de Ecologa de la facultad de Ciencias Puras del Universidad Mayor de San Andrs in LaPaz To ensure similar digestion procedures as

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108 Hillsborough River samples, the laboratory was provided a copy of the FDEP digestion and analytical procedures Otolith s for age identification were not collected. 5.7 General Results and Discussion 5.7.1 Total Mercury Loadings in Water and Sediment Twelve locations in the Lago Titicaca, Bolivia area were sampled. Water chemistry (pH, Temp, SpC, DO, and TURB) and unfi ltered water THg (uwTHg) concentrations were investigated to gain a general understanding of the possible influences water chemistry have on water mercury loadings. Table 5.1 (u wTHg Lago Tititcaca) and Table 5.2 (uwTHg rivers and streams) summarizes the w ater chemistry me asurements Data results were grouped into two categories (1) Lago Titicaca and (2) Rivers and Streams of Lago Titicaca. Due to previous mine closures and hostile relations among miners and government officials only sediment was collecte d for site T4b, Minera Potos Table 5. 1 Depth (DUF) Unfiltered Water Quality Parameters (pH, Temperature (Temp.), Speceific Conductivity (SpC ), Dissolved Oxygen (DO), and Turbidity (TURB) for Sample Sites Access by Rowboat in Lago Titicaca. Samplin g Was Conducted June 2009. Site uwTHg (ng/l) sTHg (ng/g) pH Temp. (C) SpC. (mS/cm) DO (mg/L) TURB (NTU) Depth (m) T9 DUF 0.3 919 7.0 9.9 3.5 3.7 17 7.0 T10 DUF 37.0 854 8.0 9.9 2.0 2.0 15 14.7 T11 DUF 0.3 878 8.0 10.3 2.0 2.4 6 10.8 T12 DUF 20 ND 8. 1 12.7 1.3 5.5 7 8.0 Titicaca Average 14 883 7.8 10.7 1.9 3.4 11 10.1 Titicaca Stdev 17 33 0.5 1.3 1.4 1.6 6 3.4 Lake pH ranged from 7.0 8.1 with an average of 7.80.5 where as rivers and streams of Lago Titicaca averaged 6.1 1.0 (5.1 7.6). Lake a verages were similar to natural and manmade lakes studied in Brazil 250 The lowest pH value was seen in sample T6 which was collecte d from Canton Humanata, a potato and quinoa farming and llama rearing community just downstream from a suspected gold mining area along the Ro Alcamarani (just before the river entererd into the Ro Suches ) Samples T1 (Tajani) and T2

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109 (Escoma) located on the Ro Suches about 5 10 miles from entering into the Lago Titicaca, also displayed low pH values (5.40 and 5.70, respectively) which may have be the reason for the small size potatoes grown in the a r ea. The low pH also may be attributed to the river se rving as a disposal site for municipal and industrial/electrical waste products. At Tajani (T1), the river is used for irrigation of potatoes and onions. Optimal growth for potatoes is in slightly acidic soils; however, if too acidic smaller potatoes are produced. In addition, low water levels were exhibited along this segment of the river; therefore, residents only received water every 3 4 days. Matilda Aqua Calientes (T4 a), located just downstream from Minera Potos or Mina Matilda (T4 b), a zinc and tin mine had a pH value of 6.27 but exhibited the highest temperature out of all of the means Average temperatures in the lake were slightly lower than those observed by Gilson at simila r depths (11.61 12.31C) 247 The overall sample pH ranges (5.1 to 8.1) in this study when in comparison to the Ro Ramis watershed that e nters into Lago Titicaca on the Peruvian side are within the exhibited ranges of 3.17 8.60 (lowest levels were in mining areas) 66 Additionally, average r iver and stream waters represented the lowest temperatures compared to lake temperatures Turbidity (TURB) averaged 116 NTU in Lago Titicaca and ranged from 6 to 17 NTU. The results also revealed that Matilda Agua Calientes had the highest levels of specif ic conductivity and salinity, 1.64 mS/cm and 0.82 ppt, respectivel y, Conductivity in lake samples ranged from 1.3 3.5mS/cm which is expected since salt concentrations in the lake have been seen to be considerably higher than fresh waters 247

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110 Table 5.2 Surface Unfiltered Water Quality Parameters (pH, Temperature (Temp.), Speceific Conductivity (SpC.), Dissolved Oxygen (DO), Turbidity (TU RB), and Salintiy for Sample Sites Access the B anks of R ivers and S tream s (RS). Sampling Was Conducted June 2009. Rivers and streams (RS) of Lago Titicaca(T) Area uwTHg sTHg pH TEMP (C) SpC (mS/cm) DO (mg/L) TURB (NTU) Salinity (ppt) (ng/L) (ng/g) Tajani T1 63.0 170 5.70 5.70 0.2 2 10.55 14.9 0.10 Escoma T2 67.0 132 5.40 10.75 0.22 9.82 15.6 0.10 Ullachapi T3 44.0 358 7.60 9.43 0.22 11.36 19.1 0.10 Matilda Agua Calientes T4 a 114.0 1568 6.27 15.47 1.64 7.31 16.2 0.82 Minera Potosi T4 b -28 91 ------Canton Humanata T6 63.0 757 5.05 5.56 0.2 7 10.67 15.2 0.20 C H Irrigation T7 45.0 24 6.86 5.57 0.23 11.61 18.1 0.11 RS Average 66.0 843 6.1 8.7 0 0.5 0 10.2 1 16.5 0.2 0 RS Minimum 44.0 24 5.1 5. 5 6 0.2 0 7.3 2 14.9 0.1 0 RS Stdev 25 .5 1048 1.0 4. 0 0 0.6 0 1.6 1 1.7 0.3 0 Given the small sampling size, m ercury loadings in the unfiltered water s within the rivers and streams of Lago Titicaca ranged from 0.3 114 ng/L and sediment loa dings ranged from 24 2891 ng/g. Mercury loadings from thi s site have been compared with water quality parameters in Table 5.2 whilst comparison to other areas is shown in Table 5. 3 and Pearson correlations in Table 5.4

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111 Table 5 .3. Mercury Concentrations in Sediment and Water Samples from Lago Titicaca and Oth er Studies. Location Sediment Unfiltered Surface Water Hg (ng/g) Methyl Hg (ng/g) Hg (ng/L) Methyl Hg (ng/L) Lago Titicaca and rivers and streams that flow into it (this study) 9.3 2891 0.3 114 Ro Ramis, Lake Tititcaca (Peru) 30 259 Antarcti ca streams and lakes 147 0.27 1.9* Amazon basin 144 146 streams a ffected by mining upstream from mining 24 406 67 93 0.07 1.9 2.9 33 2.2 2.6 0.2 0.6 Ro Pilcomayo Basin, Bolivia (agricultural area located near mines) 251 339 4270 75 260 Upper Madeira Rivers of Bolivian Amazon Basin 238 rivers affected by mining Andean piedmont upstream from mining outlet of Andean basin 7.22 8.22 2.25 6.99 Beni Basin (Bolivan Amazon Basin) 238 2.24 10.86* Mato Grosso, Brazil ( Pocon mines area) 252 23 198 18 160 US Streams 142 0.84 4520 0.01 15.6 0.27 446 <0.01 4.11 Florida Bays 149 1 219 3 7.4* Filtered samples (0.45um filters used). W ater parameters were compared against total mercury loadings u sing the Pearson correla tion coefficient assuming a one tailed distribution for two samples of unequal variance to determine if a linear relationship exists Strong positive correlation s were exhibited between s THg loadings and dissolved oxygen as well as salinity, total dissol ved solids and conductivity concentrations for rivers and streams of Lago Titicaca. This may be indicative of the presence of anaerobic bacteria such as sulfate reducing bacteria which are principal mercury meth y lators. Compeau and Bartha 253 determined that in the presence of high salt concentrations typically mercury levels in sediments increased. Weak associations between unfiltered water total mercury levels and most water parameters existed. W eak association s existed for unfiltered water total mercury and conductivity were consistent with studies by Lange et al. 159 Temperature showed a positive linear relationship with sTHg concentrations.

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112 Table 5.4 Pearson C orrelation C oefficients B etween T otal M ercury in S ediment and U nfiltered S urface W ater and W ater Q uality P arameters for A ll S ites in Bo livia and p V alues A ssuming a O ne T ailed D istribution for T wo S amples of U nequal V ariance. Parameter THg Unfiltered Surface Water (ng/L) THg Sediment (ng/g dry weight) r s p value r s p value Conductivity (mS/cm) 0.306 0.4233 0.8372 0.0049** pH 0. 7441 0.0215* 0.2227 0.5647 Turbidity (NTU) 0.5464 0.1279 0.1979 0.6098 DO (mg/L) 0.9618 0 0.1724 0.6574 TDS (g/L) 0.3046 0.4255 0.848 0.0039** Salinity (ppt) 0.2925 0.4449 0.8623 0.0028** Temperature (C) 0.2378 0.5377 0.705 0.0339* sTHg (ng/g d ry weight) 0.1154 0.7674 Significance tests for correlations: *p< 0.05; **p<0.01. Total mercury loadings in waters were similar to those found in areas considered to be impaired by mercury. High levels may be likely from suspension of particulate matte r from stream beds and the natural weathering of soils and sediments According to study findings by Zehetner and Miller 254 climatic gradient changes in Andean soil ecosystems can contribute to various soil leaching regimes. H igh elevations exhibiting cool and humid conditions similar to the Alti Plano can lead to the accumulation of organic matter that has been shown to increase mercury loadings in soils and sediments 255 High levels at Minera Potosi (2891 ng/g) may be due to the mineral processing of tin which is usually associated with sulfides and these can form s trong bonds with mercury as well. During the tin extraction process the crushed ore is roasted by heating to remove any impuriti es such as arsenic and sulfides. I f mercury is present it can be released in to the atmosphere Despite the relative small sa mple size (n=4) average Lake Tit i caca sediment mercury loadings were 888 33 ng/L which were within similar values found by Miller in the Ro Pilco mayo Basin in Bolivia (located in Southeast section of country flowing through

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113 Paraguay northward toward Suc re) 251 However, loadings were higher than those found in the Pocone mine areas in the Brazilian Amazon 252 5.7.2 Total Mercury Loadings in Fish Figure 5.5. Fish Species (a) Trucha ( Salmo Gaidneri ) and (b) Pejerrey ( Basilichthyes boariensis ) Collected from Lago Titicaca Area. Total mercury in fish (f T Hg) in units of mg of mercury per kg of wet fish weight along with average fish characteristics (sex, length, fish condition, and weight) have been summarized in Table 5.5 The average mercury concentrations in trucha ( Sa lmo gaidneri ) and pejerrey ( Basilichthyes boariensis ) collected from Lago Titicaca were 0. 06 1 respectively (depicted in Figure 5.5) Average mercury loadings for pejerry were three times higher than trucha. Gammons et al. 66 examined mercury fish loadings on the Peruvian side of the lake which showed that pejerrey, the most popular fish of Lago Titcaca, represented more than 27% of the fish spec ies that exceeded fish mercury tissue based water quality criterion levels of 0.3 mg/kg In the Tapajs river basin in the Brazilian Amazon, large predatory fish species showed average total mercury concentrations of 0.69 mg/kg, wet wt. (n=43) 256 This average is about two times greater than the average values exhibited in this study which may be a result of the intense mining activities; however, it does suggest that there may be possible inputs of mercury from the local mines.

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114 Table 5.5. Summary of Fish Characteristics ( L ength, W eight, S ex, and F ish B ody Condition (fbC)) and T otal Hg (fTHg) C oncentrations S ampled on 06/2009 from the Lago Titicaca A area in Bolivia. Spec ies N L range L avg W range W avg Sex fbC range fbC avg fTHg range fTHg avg ( mm ) ( mm ) ( g ) (g) ( M: F ) -( mg/kg wet wt ) ( mg/kg wet wt ) Pejerry 10 292 415 336 185 522 298.1 7:3 1.4 1.8 1.9 0.20 0.76 0.38 Trucha 10 225 375 299 203 946 496.1 5:5 0.7 0.9 0.8 0 .03 0.1 0.06 There are multiple drivers or conditions that can lead to increased mercury levels in larger predatory and omnivorous fish. Both trucha and pejerrey have similar feeding behaviors but their body shapes are different. These driving forces ca n be grouped into consumption behavior and water biogeochemical processes which can ultimately affect fish growth and spawning. In fishery studies, researchers use weight, length, and body condition as an index to assess fish nutritional well being, fitnes s as well as the relative suitability of its habitat 164 which has the ability to potentially reflect seasonal and longer term nutritional trends. Equation 1 from Chapter 3 best explains the calculation for body condition (K) 165 I f K is greater than or close to 1 it is assumed th at the fish is in good condition or receiving sufficient food and nutrition. F ish body cond itions can be comparable to stored fat as well as the incidence of disease 166, 167 In addition, various factors (e.g. s ex, body shape, sample collection method, environmental pollution, seasonal changes, disease, and parasites) can affect fish body conditions. The f ish body condition influences the levels of mercury 168 H igher mercury levels tend to decrease enzyme protein synthesis which reduces stored fat in fish 257 Fish body conditions and total mercury concen tra tions for pejerrey and t rucha have been determined in Table 5.5; however, ontogenetics, changes in body shape, seasonal, and sex differences were not taken into consideration. Despite the small sampling size, the K avg for perrrey and trucha were 0.8 and 1 .9, respectively. Fish species were considered to be in good condition and free of whirling disease, a fish disease that causes skeletal deformations and neurological damage, as well as white spot disease (mostly seen in trout species that once affected t he area in the 1980s). The body condition for trucha is about two times that of p ejerrey which suggests that the two exogenous species may be in competition; thus trucha maybe outcompeting pejerrey for food. During the 2002 United

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115 Nations Intern ational Year of the Mountains, the Food and Agriculture Organization (FAO) found that trucha introduced into five Andean water bodies represented 48% of the species of fish present and had rapidly adapted to the food organisms; therefore, out consuming its compet itors such as pejerrey 258 Figure 5.6a b illustrates the relationship of mercury loadings to fish body conditions for pejerrey and t rucha. There appeared to be a strong correlation between fTHg and fish body condition (fbC) in trucha and not pejerrey. The Pearson equation was applied to fish data results determine whether a linear relationship between fish characteristics and total fish mercury loadings exist. When examining weight and length independently, Berzas Nevado et al. 259 and Cizdiel et al. 170 determined that fish Hg levels increase when fish species undergo starvation. Therefore, thinner fish (in relation to weight and height) have hig h er mer c ury levels than robust fish which have been shown by Nicholls et al. to have fewer protein synthesis enzymes 260 Figure 5.6c f, show that there is a positive relationship that exist between fish lengt h and weight; therefore, as the length of the fish increases so does the concentration of mercury in the fish. Similar observations were seen by dos Santos et al. 261 in the examination of six carnivorous fish species Pimelodidae family ( Brachyplatystoma filamentosum filhote), ( Brachyplatystoma flavicans dourada) and ( Pseudoplatystoma sp., surubim); the Sciaenidae family ( Plagisocion squamosissimus pescada branca); the Cichlidae family ( Cichla sp., tucunar); and the Clupeidae family ( Pellona sp., sarda).

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116 Figure 5.6 (a f) Scatterplots of Total Mercury Loadings (fthg) in mg/kg Wet Weight As a Function of Length, Weight, and Age, f o r Each Fish Species. Pearson Correlation Coefficients, R s a nd p Values Are Shown. p Values Were Calculated Assu ming A Two Tailed Distribution for Two Samples o f Unequal Variance. 0 0.02 0.04 0.06 0.08 0.1 0.12 0 1 2 fTHg (mg THg/kg wet fish) Fish Body Condition (fbC) Trucha (a) r s = 0.58; p > 0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 0.5 1 fTHg (mg THg/kg wet fish) Fish Body Condition (fbC) Pejerrey (b) r s = 0.46; p < 0.5 0 0.02 0.04 0.06 0.08 0.1 0.12 0 200 400 fTHg (mg THg/kg wet fish) Length (mm) (c) r s = 0.40; p < 0.5 Trucha 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 200 400 600 fTHg (mg THg/kg wet fish) Length (mm) (d) r s = 0.61; p > 0.5 Pejerrey 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0 200 400 600 800 1000 fTHg (mg THg/kg wet fish) Weight (g) Trucha (e) r s = 0.51, p > 0.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 200 400 600 fTHg (mg THg/kg wet fish) Weight (g) Pejerrey (f) r s = 0.53; p > 0.5

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117 5.7.3 Health Implications Associated with Fish Consumption The haza rd index (H), which is commonly used to assess the potential implications of noncancerous adverse health effects that are expected to occur, have been applied here. A hazard index value of greater than 1.0 indicates that an adverse human health effect will occur whilst values less than 1.0 assume no adverse effects. H can be calculated using Equation 2 from Chapter 3.5.1. Although the consumptive behavior was not obtained in this study, a general assumption that aboriginals or natives from similar ethnic groups of Peru and Bolivia had similar body mass and consumption rates was applied. St udies have revealed that there is genetic relationship between the Quechua and Aymara 262, 263 They undergo similar environmental stress factors which include low partial pressure of oxygen, poor nutrition, cold weather, socioeconomic problems, and geographic isolation 264 Average body mass values of 22 kg for chil dren 265, 266 and 66 kg 264 for adults was used in this study. These values were based on research findings on the average body mass of Peruvian Quechua who have migrated to the cities as well as live in rura l areas. Consumption rates of 3.4 t o 4.8 kg of fish per week (486 and 686 g/day of fish, respectively) were assumed and based on rates of consumption determined by McClain and Llerena 234 for highland and lowland indigenous populations in Peru. Moreover, lower level ingestion rates were based on a daily serving of two fish fillets weighing 112 g (4 oz.) and 227 g of fish be ing consumed on a monthly single daily serving basis and. Fish concentrations (C) in Table 6 were derived from the total mercury analysis values of fish samples collected in this study. Low and high fish total mercury concentrations for all samples (C= 0 .03 mg/kg, trucha, and C=0.76 mg/kg, pejerrey) were used as well as the average total mercury concentration for pejerrey (C=0.38 mg/kg). The hazard index values have been reported in Table 5. 6 and 5. 7 for indigenous children and adults, respectively Giv en the current high concentrations of total mercury in trucha at the assumed consumption rate between 486 and 466 g fish/day have a hazard index consumption behavior places t hem at a higher risk of experiencing adverse health affects associated with the consumption of fish. However, this may be a high estimate for

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118 Bolivian Amerindians living in the Lago Titicaca area as the Quechua and Ayamara residents also consume other pro tein sources such as alpaca and llama 266 Although Wantanabe et al. 267 exhibit high mean levels of urinary mercury, wome n were seen to have the highest levels and dietary consumption behaviors were responsi ble for variations in concentrations. A fish mercury concentration less than 0.003 mg/kg would be needed in order for no adverse health effect to be exhibited. Adverse health effects associated with mercury intoxication may be difficult to identify as stu dies have showed that the Amerindians are faced with several health issues such as obesity 268 cardiovascular disease 269 and dyslipidemia (high blood cholesterol and triglcerides) 270 which all have been seen to exacerbate mercury levels in the human body 87 There were no observed postings of informational signage and/or warnings. However, residents have indicated in informal communications that they believed that upstream mining activities along the Rio Suches and the streams from the mount ain areas were possibly affecting the fish. Table 5.6 Child Hazard Index (H) and Critical fish concentration (C) for Lago Titicaca, Bolivia A ssuming H = 1. Calculations A ssumed a RfD = 1 x 10 4 mg/kg per day for D ifferent Ingestion R ates (I, g/day), F i sh M ercury C oncentrations (C, mg/kg wet weight) and B ody W eight (22 kg for a C hild). Ingestion Rate H H H C (mg/kg) (g fish/day) C=0.02 mg/kg C=0.38 mg/kg C=0.76 mg/kg H=1 child Child child child 8 0.11 1.38 2.76 0.28 227 3.10 39.21 78.42 0.01 486 6. 63 83.95 167.89 0.005 686 9.35 118.49 236.98 0.003

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119 Table 5.7 Adult Hazard Index (H) and Critical Fish C oncentration (C) for Lago Titicaca, Bolivia A ssuming H = 1. Calculations A ssumed a RfD = 1 x 10 4 mg/kg per day for D ifferent I ngestion Rates (I g/day), F ish M ercury C oncentrations (C, mg/kg wet weight) and B ody W eight of 66 kg for a T ypical I ndigenous Adult. Ingestion Rate H H H C (mg/kg) (g fish/day) C=0.02 mg/kg C=0.38 mg/kg C=0.76 mg/kg H=1 child adult Child adult child adult child Adult 8 0.11 0.04 1.38 0.46 2.76 0.91 0.28 0.83 227 3.10 1.02 39.21 12.95 78.42 25.90 0.01 0.03 486 6.63 2.19 83.95 27.73 167.89 55.46 0.005 0.014 686 9.35 3.09 118.49 39.14 236.98 78.28 0.003 0.010 5.8 Summary W ater and sediment samples were colle cted from twelve locations in Lago Titicaca and its rivers and streams ( Ro Suches, Ro Alcamarini, and mountain streams). Average mercury loadings in the unfiltered water s within the rivers and streams of Lago Titicaca were 6622.5 ng/L and sediment loa d ings ranged from 24 2891 ng/g. P ositive correlation s were exhibited between s THg loadings and dissolved oxygen as well as salinity, total dissolved solids and conductivity concentrations for rivers and streams of Lago Titicaca. This may be indicative of the presence of anaerobic bacteria such as sulfate reducing bacteria which are principal mercury me th y lators. However, weak associations between unfiltered water total mercury levels and most water parameters existed. Sediments were mainly composed of qu artz, aluminum, and iron; however, in agricultural and mining areas mercury complexes were seen in the XRD an alysis This was further confirmed by total mercury analysis showing that these areas were the most impacted.

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120 Mercury concentrations for trucha ( Salmo gaidneri ) and pejerrey ( Basilichthyes boariensis ) collected from Lago Titicaca fish market were 0.03 0.76 mg/kg, wet weight with highest levels exhibited in pejerrey. Fish body weight and legnth showed a linear correlation with total mercury concen trations. Although, total mean values do not exceed permissible limits set forth by the WHO and US EPA, special attention, monitoring, and communication may be needed to address any possible health effects or concerns.

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121 CHAPTER 6: BUILDING COMMUNIT Y PARTNERSHIPS FOR SUSTAINABILITY AND SCIENCE EDUCATION 6.1. Introduction Studies have revealed that communities and vulnerable populations with increased exposures to environmental pollutants are not appropriately receiving the necessary information 15, 72, 91, 177, 271 Despite governmental, federal, and international agency concerns regarding the impacts of mercury on water, soil, biota, and human health, regulations and recommendations provide contradictory information Moreover, there is an insufficient means of disseminating vital information which can potentially lessen the ability of 14 15 However, evidence has shown that community based participatory research programs are effective in b ridgin g gaps in knowledge, improving well being, and increasing effo rts of sustainability 272 Water Awareness Research and Education (WARE) is a Community Based Participatory Research (CBPR) program aimed to increase environmental/environmental health/sustainability awareness through the use of local stormwater ponds in Tampa, Florida. Over t he course of time spent doing the graduate research presented in chapters 3 implementation and constant expansion and improvement efforts. It became evident that educa tion has a significant role to play in fostering sustainable healthy communities and I merged my mercury research with many WARE activities. This c hapter discusses the important role of education in furthering sustainability concepts, including mechanisms for broadening participation like CBPR and Informal Science Education (ISE). It details the WARE project and uses personal reflective journaling to assess its effectiveness and applicability to promoting sustainability concepts as they relate to mercury exposures.

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122 6.1.1. Objectives and Tasks The objective of this chapter was to provide an initial evaluation of an existing CBPR project, WARE, for its ability to increase awareness of environmental, environmental health and sustainability concepts as they r elate to mercury exposure. The tasks include: Task 3a: Review educational literature and describe the WARE project. Task 3b: Assess project activities through reflective journaling in terms of their ability to increase awareness of environmental, enviro nmental health and sustainability concepts. Task 3c: Recommend focal areas for improving and expanding the project to reach larger populations. Chapter 6 is limited to a project already being implemented mainly in East Tampa, a community that is a part of the Hillsborough R iver watershed presented in Chapter 3. The extension of educational components to sites in Bolivia and Guyana is discussed in Chapter 7.

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123 6 .2. Background 6.2.1. Sustainability and Education Figure 6.1 Pillars of S ustainabilit y W ith E ducation B eing the P rinciple F orce J oining A ll S ectors Tra ditionally, 3 P illars H ave B een used ( E nvironment, E conomy, and S ociety), B ut R esearchers H ave E xtended it to 5 P illars ( E nvironment, E conomy, S ociety, C ulture and P olitics l ) 273 The United Nations has termed the years 2005 2014 as the Decade of Education for Sustainable Development. Their overall goal is to integrate the principles, values, and practices of sustainable development into a ll aspects of education and learning. Several definitions of sustainability exist and probably the most popular definition, and the one adopted by this work, comes from the 1987 Brundtland Report commonly known as Our Common Future. The Brundtland Report which the needs of the present are met without compromising the ability of future five areas, referred to as pill ars environment, economy, society, culture and politics with traditional emphasis on the first three 273 as shown in Figure 6.1. Education plays a critical role in ensuring sustainability concepts are u nderstood, and applied and

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124 sustainability is achieved. Emphasis on environmental education, therefore, would address one of the five pillars identified above. Approaches that integrate all five pillars into educational material would eventually be necess ary to adequately address sustainability issues. From the report of the United Nations C onference on Human Environment, Stockholm Recommendation 96, it is critical that the development of environmental education be implemented globally and is strongly re lated to the basic principles outlined in the United Nations Declaration on the New International Economic Order, a set of proposals that promote increasing assistance in development 274 Given that high quality environmental education is seen as an important first step for sustainability, researchers have found it effe ctive to target youth to initiate change, especially when a participatory research approach is used 275 In assessing the results of the research on mercury conducted for this work and its relevance to local community health, the role of educ ation became important if one wanted to initiate change in local behavior. The next few sections describe the state of education, especially in the sciences, and the approaches that various groups are using to deliver high quality education. 6.2. 2 State of Science Education S cience education is important in developing critical thinking so that students and communities can make well informed decisions in everyday life (e.g. nutrition, consumption, and health practices ) Environmental education provide s a good mechanism for developing critical thinking that also teaches across the school curriculum 276 Figure 6.2 shows the total number of students enrolled by educati onal level for Bolivia, Guyana and the United States in 2008. These countries have adult literacy rates greater than the world average (Table 6.1) and from the data presented in Figure 6.2, there is a decrease in the number of students enrolled as a funct ion of level in the system. This justifies the targeting of primary and secondary students, although not to the exclusion of tertiary students.

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125 Figure 6.2 2008 D ata for the N umber of S tudents E nrolled P er E ducation L evel in Bolivia, Guyana and the United States. The D ata P resented was O btained from UNESCO ( www.uis.unesco.org ) W hich O btains Ra w D ata from UNESCO Member States. While general education is essential for all, demograph ics, ethnicity/race, and gend er systems. In rural areas in developing countries and inner cities or urban poor neighborhoods of the US, students receive education of lower quality 277, 278 The World 279 determined that s tudents from rural developing areas are often left out of education reforms and usually only receive primary level education if at all and have to relocate for higher level training. The schools or districts within these areas are usually faced with many issues such as poor quality infrastructure, transport, and availa bility of quality teachers Therefore, the funding for science education 280 as well as a focus on sustainability is limited to non existent. 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 pre primary primary secondary tertiary log (number of students) Educational Level Bolivia Guyana United States

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126 Table 6.1 Demographics f or t he United States, Bolivia a nd Guyana a nd t he World. Demographics and Economic Devel opment Comparison Country Total Pop. (2007) Urban Pop. (2010) GDP (2007) Poverty Index National Poverty Line (2000 2006) (millions) (% of total) (US$ billions) Rank (N=177) % below United States 308.7 82.30 13,751.40 --Bolivia 6.7 66.5 13.1 52 65.2 Guyana 0.7 28.5 1.1 48 35 World 5,290.50 2.60 54,583.90 --Country Health Education Public Expenditure on Health (2006) Life Expect ancy at birth Public Expenditure on Education (2000 2007) Educational Attainment Levels (2000 2007) Adult Literacy (1999 2007) (% of total government expenditure) (years) (% of total government expenditure) (% of the population % aged >15 L M H United States 19.1 79.1 13.7 14.8 49 36.2 99 # Bolivia 11.6 65.4 18.1 61.6 23 .8 14 90.7 Guyana 8.3 66.5 15.5 ---98.8 # World -67.5 ----83.9 Educational levels are defined according to the UNDP HDI Report. L less than upper secondary; M upper seco n dary or post secondary non tert i ary; and H tertiary. # da t a obtained from the CIA 6. 2.3 Broadening Participation in Science Education in the US The American Competitiveness Initiative (ACI) and the America Competes Act reflect the concerns that the US is in danger of losing its position of world leadership in science and technology. If one were to look at worldwide patent filings over the past two decades, the United States still ranks number one in terms of patents granted and patents still in force (Figure 6.3 ). Since 1995, however, China has significantly increased both the number of patents filed worldwide and the number of patents filed in the U.S. (Table 6.2 ). If growth rates of patents filed in the U.S. is a reflection of advancement in STEMs research it is not difficult to imagine that in another 20 years, the patents filed by China will surpas s those of the U.S

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127 Figure 6.3. Comparisons of P atents (A) A pplied for, (B) Granted and (C) in F orce for the United States, Japan, Germany, the United Kingdom and China from 1984 to 2001. Figures W ere C eat ed U sing Gap Minder World on 3/4/10 and the S ize of the C ircle is R epresentative of P opulation S ize. ( www.g apminder.org ).

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128 Table 6.2 Patents Filed In t he U.S In 1995 a nd 2008. Data Taken From T he USPTO Technology All Patent Types. Granted: 01/01/1977 12/31/2008. Http://www .uspto.gov/web/offices/ac/ido/oeip/taf/cst_all.htm Accessed 3/4/10. Country Year % increase 1995 2008 Japan 22871 36679 60 U.S. 64510 92000 43 China 63 1874 2875 Germany 6874 10086 47 UK 2685 3843 43 In addition to low spending o n education an d focus on standardize testing reforms, science education in the US lags in the participation of young girls one of the most vulnerable populations 281, 282 This translates into serious underrepresentation at faculty levels, positions that are important for bei ng role models. Table 6.3 and Figure 6.4 show demographics for faculty in the Civil Engineering discipline, which includes environmental engineering, at the top 50 programs in the U.S. The percentage of female faculty is only 12.7% whereas that for mino rity female faculty is almost non existent (e.g. 0.4 % for Black women). Table 6.3 De mographics Of Civil Engineering Fac ulty At The Top 50 Departments i n The US f or The Year 2007. Taken from http://chem.ou.edu/~djn/diversity/Faculty_Tables_FY07/CivilEngTable2007.pdf

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129 Figure 6.4. Demographics of Civil Engineering F aculty at the T op 50 D epartments in the US for the Y ear 2007 by (A) E hn icity and (B) E thnicity of F emale F aculty. Total N umber of Fa culty was 1369. Taken from http://chem.ou.edu/~djn/diversity/Faculty_Tables_FY07/CivilEngTable2007.pdf Federal agencies, including the National Science Foundation (NSF) recognize that retaining world leadership requires Broader Participation (BP) in STEMs fields to take advantage of rapidly changing demographics. NSF defines broadening participation in te rms of individuals from underrepresented groups as well as institutions and geographic areas that do not participate in NSF research programs at rates comparable to others 283 Proposals are generally assessed according to the following criteria 283 : How well does the activity advance discovery and understanding while promoting teaching, training, and learning? How well does the proposed activity broaden the participation of underrepresented groups (e.g., gender, ethnicity, disability, geogr aphic, etc.)? To what extent will it enhance the infrastructure for research and education, such as facilities, instrumentation, networks, and partnerships? Will the results be disseminated broadly to enhance scientific and technological understanding? W hat may be the benefits of the proposed activity to society?

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130 opportunities to learn and develop in the U.S. society. Being born into a racial majority group with h igh levels of economic and social resources or into a group that has historically been marginalized with low levels of economic and social resources results in very different lived experiences that include unequal learning opportunities, challenges, and po tential risks to learning and development 284 9 Some of the challenges identified by the National Research Council 285 in engaging nond ominant groups in the sciences include: I nadequ ate science instruction in most elementary schools, especially those serving children from low income and rural areas G irls often do not identify strongly with science or science careers S tudents from nond ominant groups perform lower on standardized measures of scien ce achievement than their peers A lthough the number of individuals with disabilities pursuing post secondary education has increased, few pursue academic career s in science or engineering L ear ning science can be especially challenging for all learners because of th e specialized language involved According to the National Science Foundation (NSF) 282 not all students are actively engaged and new a pproaches to learning in the classroom o r in informal education settings (e.g. clubs, summer camps, and after school programs) is needed in order to spark interest and increase science and engineering participation. Despite low district 286 on education in the 21 st century in the United States determined that federal and state educational boards have focused on standards based reforms and choice as a result of low scores on standardized tests and unacceptable performance levels of low in come and minority groups 286 The National science education standards established by the National Research Council (NRC) 287 state that it is essential that adequate district and state funding be provided to create environments in which students of all grade levels and teachers can be

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131 active learners. Informal science is a burgeoning field that operates across a broad range of venues and envisages learning outcomes for individuals, schools, families, and society. Environmental education is central to effective community involvement in participatory re search 288 The NSF portfolio includes 23 BP focus programs (e.g. Scholarships in Science, Technology, Engineering and Mathematics), 18 BP emphasis programs (e.g. Research Expereinces for Undergraduates; Informal Science Educati on), and 18 BP potential programs (e.g. Graduate Teaching Fellows in K 12 Education). Based on research and experiences with BP, NSF 283 recommends that: Partnerships between science rich institutions and local communities show great promise for structuring inclusive science learning across settings, especially when partnerships are rooted in ongoing input from community partners that inform the entire process, beginning with setting goals. Learners thrive in environments that acknowledge their needs and experiences, which vary across the life span. Adult caregivers, peers, teachers, facilitators, and mentors play a cr itical role in supporting science learning. The means they use to do this range from simple, discrete acts of assistance to long term, sustained relationships, collaborations, and apprenticeships. Informal settings provide space for all learners to engage with ideas, bringing their prior knowledge and experience to bear. Learning experiences should reflect a view of science as influenced by individual experience as well as social and historical contexts. They should highlight forms of participation in sci ence that are also familiar to nonscientist learners question asking, various modes of communication, drawing analogies, etc.

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132 Programs, especially during out of school time, afford a special opportunity to expand science learning experiences for millions of children. These programs, many of which are based in schools, are increasingly folding in disciplinary and subject matter content, but by means of informal education. Banks et al. 284 propose s 4 principles of formal and informal education delivery to broaden participation. These are: Learning is situated in broad socio economic and historical contexts and is mediated by local cultural practices and perspectives. Learning takes place not only in school but also in the multiple contexts and valued practices of everyday lives across the life span. All lear ners need multiple sources of support from a variety of institutions to promote their personal and intellectual development. Learning is facilitated when learners are encouraged to use their home and community language resources as a basis for expanding t heir linguistic repertoires. The discussion thus far emphasizes the importance of broadening participation in STEMs fields, identifies barriers to broadening participation, and summarizes approaches needed to increase broader participation. The next sect ion discusses an overarching approach, 6.2. 4 Community Based Participatory Research According to Finn 289 participatory research has three key elements: people, power and praxis and Table 6.4 summarizes their meaning.

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133 Table 6.4. Elements of Community Based Participatory Research. Element Dictionary Definition Research Interpretations People (noun): persons indefinitely or collectively; persons in general (verb): to furnish with people; populate. The process of critical inquiry is informed by and responds to the experiences and needs of people involved 290 Power (noun): ability to do or act; capability of doing or accomplishing something. (verb): to give power to; make powerful. Power is knowledge and knowledge creates truth and therefore power 291 Praxis (noun): practice, as distinguished from theory; application or use, as of knowledge or skills. The inseparability of theory and practice and critical awareness of t he personal political dialectic. Community based participatory research (CBPR) is becoming more popular with support and funding from various foundations and national agencies 292 Some CBPR definitions used by the natio nal agencies include: National Institute for Environmental Health Sciences (niehs.gov) methodology that promotes active community involvement in the processes that shape research and intervention strategies, as well as in the conduct of resea rch studies" 293 Office of Behavioral and Social Sciences Research (OBSSR) based participatory research (CBPR) is an applied collaborative approach that enables community residents to more actively participate in the full spectrum of research (from conception design conduct analysis interpretation conclusi ons communication of results) with a goal of influencing change in community health, systems, programs or policies. Community members and researchers partner to combine knowledge and action for social change to improve community health and often reduce h ealth disparities. Academic/research and community partners join to develop models and approaches to building communication, trust and capacity, with the final goal of increasing community participation in the research process. It is an orientation to rese arch which equitably involves all partners in the research process and recognizes the unique strengths that 294

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134 The Agency for Healthcare Research and Quality (ahrq.gov) process of research involving researchers and community representatives; it engages community members, employs local knowledge in the understanding of health problems and the design of i nterventions, and invests community members in the processes and products of research. In addition, community members are invested in the dissemination 295 Centers for Disease Control and Prevention (cdc.gov) involves researchers and community representatives in all phases of the research process. The joint effort engages community members, em ploys local knowledge in the understanding of health problems and the design of interventions, and invests community members in the processes and products of research. In addition, the collaborative is invested in the dissemination and use of research find ings to improve community health and reduce health disparities 296 Table 6.5 summarizes some of the publications on CBPR that relate to environmental studies, many of which have linkages to c ommunity health. The studies highlighted involve multiple participants, some who belong to the community under study and use various tools to implement the research (surveys, monitoring, disseminating, assessing). Eight guiding principles have been ident ified for environmental health CBPR and these are summarized in Table 6.6. These guiding principles are and can be used to guide the development and execution of CBPR projects in areas not directly related to public health.

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135 Table 6.5 Examples of CBPR S tudies with E nvironmental L inkages. Study summary Reference Water/natural resource management Local Responses to Participatory Conservation in Annapurna Conservation Area, Nepal. Participants: Non governmental organization, community groups in Non Tour ist and Tourist villages. Tools: Surveys. Conclusion: The Conservation agency must devise strategies and initiatives appropriate to specific social groups so as to optimize their input in participatory conservation. Khadka, D.; Nepal S. K. (2010) 297 Assessing water use and quality through youth participatory research in a rural Andean watershed. Participants: Youth from schools in the Andean region in Colombia, NGO, university research center, technician at municipal telecenter. Tools: Surveys, Monit oring, Assessment, Youth led community workshops. Conclusions: The approach involving youth in research stimulated improved management of both land and water resources for small rural watersheds. Garcia C. E. R.; Brown S. (2009) 275 Scien tific perceptions and community responses in a participatory water management endeavor. Participants: a team of multidisciplinary scientist representing ICAR Participatory water management endeavor Research Complex for Eastern Region (ICAR RCER), Patna, Bi har, India, (b) group of scientists/consultants mainly based in different Universities of U.K led by Rothemsted, U.K., and (c) an Indian NGO and its apex bodies. Tools: Surveys, Feedback Conclusions: A more differentiated communication and a conceptual fra mework, can help researchers and practitioners to make better choices and more informed decisions when designing their research, communication and dissemination approaches. Flexibility in participatory approaches are very important which comprises of a ble nd of top to down and bottom to up approaches with scope for innovation. Singh, A. K. et al. (2008) 298 Air Combining community based research and local knowledge to confront asthma and subsistence fishing hazards in Greenpoint/Williamsburg, Brooklyn, New York. P articipants: Community based organizations: El Puente and The Watchperson Project in the Greenpoint/Williamsburg neighborhood in Brooklyn, New York, Scientists Tools: S eries of asthma health surveys and tapped into local knowledge of the Latino populatio n to understand potential asthma triggers and to devise culturally relevant health interventions. Conclusion: Problem definition, information collection, and data analysis all geared toward locally relevant action for social change. U.S. EPA Cumulative Exp osure Project in the neighborhood. Corburn, J. (2002) 299 Airborne concentrations of PM(2.5) and diesel exhaust particles on Harlem sidewalks: a community based pilot study. Participants: Residents of the dense urban core neighborhoods of New York City (NYC), Columbia University in New York (the Center for Environmental Health in Northern Manhattan; Harlem Center for Health Promotion and Disease Prevention; a community based organization, West Harlem Environmental Action (WE ACT) Tools: Surveys, traffic surveys, portable monitors worn by study staff. Conclusions: A new paradigm for community based research involving full and active partnership between academic scientists and community based organiz ations is feasible. Kinney P. L. et al. (2000) 300 Diesel exhaust exposure among adolescents in Harlem: a community driven study. Participants: High school students from WE ACT's Earth Crew Youth Leadership Program, seventh grade students from Thurgood Marshall Academy, researchers at Columbia University, and health care providers at Harlem Hospital Center and Columbia Presbyterian Medical Center. Tools: In person surveys, Urine sample analysis, Statistical Analyses. Conclusions: Community driven research initiatives are important for empowering communities to make needed changes to improve their environments and health. Northridge, M. E. et al. (1999) 301

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136 Table 6.6. Guiding Principles for Community Based Participatory Research. Based on the W ork of Israel et al., 302 CBPR Guiding Principles Explanation 1. Recognizes community as a unit of identity A community may be a geographic area, a shared ethnic/racial or other identity. 2. Builds on st rengths and resource within the community CBPR supports and expands existing social processes (community skills, assets, existing structures like community boards) to address community needs. 3. Facilitates collaborative partnerships in all phases of the research Investigators and communities work together to define the problem, collect data, and interpret results. It is truly an empowering process for all involved. 4. Integrates knowledge and action for mutual benefit of all partners All involved need to determine the mutual benefit of the process and develop an intervention or guide policy. 5. Promotes a co learning and empowering process that attends to social inequalities Researchers need to enhance their capacity and learn from the process. 6. Involves a cyclical and iterative process Research goals develop over time through many iterative processes used to reflect and evaluate and redefine. 7. Addresses health from both positive and ecological perspectives Builds on problems identified by the community, which are often linked by additional sources of data (e.g., epidemiological surveys, environmental stressors). 8. Disseminates findings and knowledge gained to all partners Community members co author reports, publications, and other forms of media that reach and are useful to the community

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137 6. 2.5 Water Awareness, Research and Education project (WARE) The Water Awar eness, Research and Education project (W ARE), is a pilot project funded ty, Planet (P3) program from 2008 participation in STEMs fields, improves community awareness of environmental health issues, and delivers K 20 education that integrates sustainability c oncepts The model of the collaborative partnerships required to sustainably manage an environmental system with an example of a stomwater pond in East Tampa has been described in Figure 6.5. It is based in Hillsborough County, Florida and involves stake holders from the K 12 educational system, community groups, the University of South F lorida, and government agencies. Hillsborough County Public S chools (HCPS) is the eighth largest public school district in the country. The demographics of the city and it s counties are given in Table 6. 7. Figure 6.5 Collaborative Partnerships Required to Sustainably Manage Environmental Systems With an Example of Stormwater Ponds in East Tampa Used as An Example

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138 Table 6. 7 Summary o f Demographic Data f or Florida, The City Of Tampa, a nd Counties That Make Up The Tampa Metropolitan Statistical Area. Data Taken f rom The U.S. Census Bureau 303 WARE initially focused on storm water ponds in East Tampa, a seven square mile economically disadvantaged urban area in Florida with a majority African American population Florida established a system t o reinvigorate communities in which 50% of the property is in disrepair, which requires that any additional increase in tax revenue collected by the city or county go into a kitty that is used to reinvest in the community. The East Tampa Community Revital ization Partnernship (ETCRP) serves as an organizational medium for the area's 13 different neighborhood groups. Although the city has fiduciary responsibility for how money is used, the partnership has a lot to say about how funds are invested. The storm water beautification project was one of the first funded and involved the redesign of 3 stormwater pond areas so that they became community friendly open green spaces as opposed to "eyesores where rubbish was dumped". Though not explicitly conceived as a CBPR project, it fits in well with the

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139 principles outlined in Table 6. 7 Moreover, it also addresses all four principles for delivering education that broadens education as listed by Banks et al 284 Prof. Trent Green from USF's department of architecture was contracted to redesign the areas and to date (M arch 2010), two ponds have been completed (Fair Oaks Lake and Robert L. Cole Sr., Community Lake). The close proximity of the ponds to local schools provided a natural fit for building curriculum around the ponds that provided a field site location for stu dents to not only learn about science and engineering, but to also provide a "service" to the community through monitoring and interventions to maintain pond health. Additionally, through community education and awareness, local pollutant inputs to storm water will be reduced; an activity that not only impacts local pond water quality, but also water quality in the Tampa Bay. Figure 6. 6 shows East Tampa with details on the flow of stormwater through the various pond systems and the pilot schools. Young M iddle Magnet for Math and Science (highlighted) is located opposite to the Robert L. Cole Sr., Community Lake on Martin Luther King Boulevard between 17 th and 19 th streets. Through local community input, the project grew to include Lockhart Elementary, a Academy, a private elementary school. These three schools fall within East Tampa and hence the City of Tampa. By August 2009, the project expanded to a new suburban area of Tampa, New Tampa owing to the fact that the science resource teacher changed schools from Lockhart Elementary to Chiles Elementary. Though not considered a part of the City of Tampa, New Tampa is a part of Hillsborough County. Chiles has a stormwater pond on its propert y.

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140 Figure 6. 6. Maps o f East Tampa Showing The Proximity of Schools in East Tampa t o ( A) Stormwater Ponds With Stormwater Drainage System (Obtained From The City Of Tampa Stormwater Department) a nd ( B ) Stormwater Ponds Without Drainage Pipe Overlays ( Mapped Using Google Earth. Pond C odes Correspond to City of Tampa Codes a nd Represent Sites That Exist in Google Earth With Pictures o f The Ponds).

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141 Figure 6. 7. 2008 2009 Demographics of (A) Young Middle Magnet, (B) Lockhart Elementary and (C) Lawton Ch iles Elementary. Figure 6. 8 Organizational Chart f or WARE, I ndicating Areas of Interaction of The Members of Each o f The Three Participatory Groups (Community, USF, Schools). Arrows Indicate Mutually Beneficial Interactions Between Various Members. Tables 6.8 and 6.9 summarize the roles of each of the partners and their method of d issemination as of March 2010 w hilst Figure s 6.7 and 6.8 describe the demographics of the various participating schools and the organizational flow resppectively organizational flow uses two way arrows to indicate the mutually beneficial interactions

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142 between each partnering member Furthermore, t he funds provided by the EPA allows for a stipend for four K5 hours of out of school time on WARE activities. It also funds some community participation (e.g. to lead bus tours of the neighborhood) and equipment purchases. WARE is a long term project with multiple feedback loops for improvement. With time there w ill likely be changes to the participatory groups, member roles and the dissemination activities. To date, this is already occurring. For example, when conceived in 2007 WAR E involved one school and as of 2009 it involves three, one of which is not in Ea st Tamp so it has also expanded to another community. In 2007 WARE involved one class at USF and during the 2010/11 academic year a new undergraduate class will be added that was developed by faculty and a community member with specific requirements for se rvice learning in East Tampa.

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143 Table 6.8 WARE Participants As o f March 2010, Their Roles and Ways i n Which They Disseminate WARE Generated Materials. Participatory Group Type Participatory Group Member Role Dissemination Community ETCRP ETCRP Chair Li nk between community, U S and schools; Provide guided tours of community; Assess and improve WARE. Share WARE with others; Support funding for WARE. ETCRP community meetings & meeting minutes (monthly); speeches; newsletter; workshop; publication with team. ETCRP HESS Committee Provide opportunities to interface with the community. Community Survival Day (August of each year) City of Tampa City of Tampa Share data and resources of area and stormwater infrastructure; Implement projects supported by the ETCRP (educational kiosk). Email to members of East Tampa Community and communicate to members of city government. Community Teachers Community teacher Develop curriculum & educational material; Communicate with community members Radio, communi ty interactions USF Faculty Engineering Architecture Design pond structures including kiosks and public outreach learning modules. Radio; newspaper articles; Ware easttampa.com & ESW website; booths at EPA EXPO, USF Engineering EXPO, Going Green Tampa B ay, Community Survival Day, School events; Workshops, Class material development; Teaching & training; Educational community Kiosk, K5 7 class activity ; Journal publications, conference presentations. Graduate Students Graduate student (ESW) and graduate directed research Develop and participate in all WARE activities; Assist teachers during school times; Mentor K5 12 students; Graduate (directed research) Develop and participate in WARE activities; Assist teachers during school times. Undergradu ate Students Undergraduate laboratory student Conduct stormwater pond water quality analyses, present data to class and as a report; Share project information with K5 12 Great America Teach In (K5 12) class activity; Class presentations. Undergraduat e researcher Conduct stormwater pond analyses and understand water flows in area; prepare materials for K 12 students and for outreach activities; contribute to design of educational kiosks. Newspaper articles; WARE & ESW website; booths at EPA EXPO, USF Engineering EXPO, Going Green Tampa Bay, Community Survival Day, School events; Educational community Kiosk; K5 7 class activity; Journal publications, conference presentations. 143

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144 Table 6. f March 2010, Their Roles and Way s i n Which They Disseminate WARE Generated Materials. Schools Teachers Middle school science teachers Develop curriculum; Teach; Develop publication/educational materials; Participate in various activities like science fairs, community EXPOs etc.. Newsl etters; Ware easttampa.com; booths at School events & science fairs; Educational community Kiosk; class activities; Publications. Elementary school science teachers Develop curriculum; Teach; Develop publication/educational materials; Participate in var ious activities like science fairs, community EXPOs etc.. Newsletters; Ware easttampa.com; booths at School events & science fairs; Educational community Kiosk; class activities; Publications. Students Middle school students Participate in class time act ivities, field trips, and special programs. Newsletters; Radio; booths at USF Engineering EXPO & School events; Science Fairs; Educational community Kiosk. Elementary school students Participate in class time activities, field trips, and special progra ms. Newsletters; Radio; booths at USF Engineering EXPO & School events; Science Fairs; Educational community Kiosk. Parents Parents Participate in various activities like science fairs, community EXPOs etc.. 144

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145 6.2.6 WARE Activities The National Scien ce Foundation supports constructivism as a promising new learning technique for science and engineering education 281 Constructivism purports that learners actively construct new concepts based on past and present experiences. It r elies on a cognitive structure or mental model in which the l earner can transform information to facilitate the construction of hypotheses to make well informed decisions 304 Active participation that involves all sensory functions and understanding of the eight different types of i ntelligences (naturalist, musical, logical, interpersonal, linguistic, intrapersonal, spatial and kinesthetic) has been used to create better ways of teaching complex subjects like science. M rning ability by using the Figure 6.9 Maximized Constructivist Learning Approach for the Water Curriculum Principles. (Adopted from Christie 305 ) st learning approach adopted by Christie 305

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146 This approach can best be described in Figure 6.9 which uses a ste p up and step down approach works to increase engagement, information exchange between the student and his/her instructor, peers, and parents, followed by a step up to empowerment. Zimmerman 306 explains that empowerment is considered the highest point of learning and occurs when i ndividuals, communities, or organizations gain mastery over their lives. Thus at this peak, students have gained an understanding and now modify their actions or seek other opportunities. Unlike the curriculum, the learning process uses a step down appro ach. In other words, a big question is explored then explained in a simplified manner using various media types that finally allows the student to draw a conclusion to make well informed decisions as well as feel a sense of influence on others which helps to create a sense of community 307 The objectives of the water curriculum can be best described according to the UN Tibilisi 308 which include helping to increase Knowledge, Awareness, Attitude, Participation, and Skills (KAAPS). KAAPS represents: K nowledge : obtaining basic understanding of the total environment, its associated A wareness : about the environment and environmental issues. A ttitude : students and groups become socially, politically, and environmentally conscious and are motivated to protect and improve our environment P articipation : develop a sense of responsibility and urgency regarding environmental problems to ensure appropriate action to solve those problems. S kills : acquire skill s for monitoring, identifying, and possibly solving environmental problems. An overview of the WARE curriculum for the schools is given in Table 6. 10 This material is continually being improved and adapted as the project progresses. Teachers and USF fac ulty and graduate students are the main persons in charge of this activity. The curriculum is divided into six sections. Section I of the curriculum explores the global and local perspectives of water

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147 followed by Sections II and III which highlight a low level understanding of water chemistry as well as the issues of quality, quantity, and sanitation/health. Sections IV and V, map the flow of water through natural and engineered treatment processes so that learners can draw a parallel understanding betwe en the two approaches. Each lesson within an individual section was designed to: Relate real world issues to activities in the classroom Focus on sustainable approaches to solving the real world problems Stress conceptual interrelatedness Provide a ppropriate tools and environments to assist learners interpretation of the perspectives of the world and Guide student investigative learning if necessary. Table 6. 10 Water Awareness Research and Education Classroom Curriculum Overview. 1. Section I: Water Matters (A brief introduction of global and local perspectives) a. Define water its uses b. Conservation and Sustainability 2. Section II: The Chemistry of Water a. Phases of water b. Water as a universal solvent 3. Section III: Water Quality, Quantity, and Public Health a. Point source vs. non point source contamination b. pH, DO, turbidity, biological indicators, temperature, nitrates, phosphates c. Typical usage values and crisis in the world d. Water related illnesses 4. Section IV: Water Cycle (natura l system) a. Emphasis placed on aquifer and surface water storage 5. Section V: Water Treatment (engineered systems student makes connection to water cycle) a. Drinking water b. Wastewater (i.e. stormwater and reclaim water concepts introduced) 6. Section VI: Water M onitoring a. Retention pond emphasis b. Rotation schedule development for the following subgroups: Lead engineer, field assessor, field sampler, lab analyst, and data analyst Student programs and lessons were designed as a series of activities which include d an introductory presentation followed by actively engaging hands on exercises. Each lesson was modified appropriately for each grade level and designed to meet at least one of the Florida Sunshine State Standards and Grade Level Expectations (SGLEs) lis ted in Table 6.1 1

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148 Table 6.1 1. Sunshine State Standards Grade Level Expectations a nd Benchmarks f or Grades 3 8 That Were U sed i n Curriculum Design Sunshine State Standard Grade Level Expectation and Benchmarks Description SC.D.1.2.2 3 Knows that 75% of the surface of the Earth is covered by water and knows that the water cycle is influenced by temperature, pressure, and topography. SC.G.2.2 The student understand s the consequences of using limited resources. SC.3.N.1.3: SC.H.1.2 Keep s records as appr opriate, such as pictorial, written, or simple charts and graphs, of investigations conducted. SC.7.E.6.6 Identif ies the impact that humans have had on Earth, such as deforestation, urbanization, desertification, erosion, air and water quality, changing the flow of water SC.7.E.6.In.e Recognize s that humans have had an impact on Earth, such as polluting the air and water and expanding urban areas and road systems SC.7.E.6.Su.e: Recognize s that polluting the air and water can harm Earth. SC.7.E.6.Pa. c: Recognize s time. 6.3 Methodology There are several challenges involved in evaluating environmental education programs 309, 310 Heimlich 310 argues that environmental education programs aimed at behavior al change are complex and that there behav ior More importantly the broader good should be of students and teachers were carried out for most of the WARE activit ies by the student organization, Engineers for a Sustainable World The surveys were used to assess whether the targeted concepts were successfully conveyed by the specific activity. Given that WARE is a CB P R project, evaluation of the impacts on all inv olved requires long term evaluation tools. Reflective journaling according to education theorist John Dewey 311 fosters a meaningful learning environment that actively engages students with co ntent in an interpersonal manner. It is a learning strategy that provides opportunities for internal and structural analysis, thus creating

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149 an environment for significant learning. Rogers 312 found that the use of reflective journaling is a good tool for learning, fostering personal growth, and professional development. Gil Garcia and Cintron 275 contend that reflective educators are aware that taking time and energy to reflect on and improve itself. Reflective journaling was used to assess WARE activities in which I was involved for their effectiveness and applicability to promoting sustainability concepts as t hey relate to mercury exposures Each of the main activities contained a set of reflections that were best grouped into student, teacher learning and the effectiveness of the technology used. A series of questions and free responses were developed to ide ntify partnership weaknesses and teaching effectiveness, and modifications required for enhanced understanding. Table 6.1 2 provides an example of the questions of the reflective journal This reflective tool was used for the in class activities and the o ther WARE activities described next. Note that while Table 6.10 refers to many different activities, the only ones assessed during the reflective exercise are those in which I was involved as a graduate researcher and member of ESW. Table 6.1 2 Example o f The Reflective Journal Assessment Tool. In class time activities included both classroom lectures and field sampling exercises. Students received various styles of lectures (i.e. group discussions, think tank subgroups, pow er points, Personal Perceptions What were your expectations before activity? Where you prepared, if not why not and how can you plan better in the future? Did you convey concepts using appropriate language? Perceived Student perspectives (free response) Did students appear confused? How did they respond to lecture? Where they able to recall this exercise and what they learned in the subsequent week? Perceived Teacher perspectives Were teachers actively involved? Did teachers want to learn more? Were teachers able to aid in learning based on your presentation before the activity?

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150 music, movies) that were to build concepts before applying to infield analys e s or classroom experiments. As part of the classroom discussions student interests and strengths were assessed via a questionnaire in order to break them into appropri ate teams for the design competition. The teams include d : field assessment team; analytical wet chemists; audio/visual engineers and graphic design artist s ; data reporters or scientific journalist s Each team had a specific set of tasks; however, all team s had to work with one another to produce a 3 5 minute video and final report that would be showcased at the EPA P3 Design Competition in Washington, D.C (Spring 2011). S tudents applied knowledge obtained from discussions and training sessions to field analysis skills to address the environmental and social issues associated with the stormwater retention pond located directly across from the school. The students learned how to utilize the Quanta Hydrolab probe to assess water samples for various paramet ers (temperature, pH, conductivity, dissolved oxygen, turbidity, etc.). Using these skills, the students were able to regularly monitor the status and progress/decline of the stormwater pond water quality Spatial and temporal changes for the ir own collected data were used to discuss pond mechanisms. In addition to the field activities, the students had an opportunity to create and design a website to post their research findings and conclusions, along with the chance to build a small scale model of the storm water pond following completion of the beautification. Community Outreach and Active Engagement activities refers to activities that engaged the community (East Tampa and beyond) through face to face interaction with WARE members. A five hour booth exhib it at the East Tampa Community Survival Day delivered environmental awarenes s information through handouts fro m local environmental agencies and various activities related to water. For example, a hands on activity using various materials (sand, wood chip s etc.) was used to demonstrate wha t happens to water when it falls to the earth. The booth was visited by approximately 700 community members in August 2008 and 2009. This was a partnership between the ESW and HESS committee to help to raise awareness o n environmental issues in the community. In addition to developing the booth content and activities, USF faculty, graduate and undergraduates manned the booth each year, directly connecting with community tivities. Similar activities were

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151 performed during the University of South Florida Engineering EXPO in February 2009 and 2010, and the Lockhart Elementary Night of Ecology in February 2009. Engineering EXPO is open to all schools in the area, so the comm unity reached is much wider than East Tampa. Middle school students from WARE helped to manage the booth at USF. The Lockhart Elementary Night of Ecology was visited by approximately two hundred people, mainly parents of students from the school. Field trips were set up to enhance student lectures by showing them real world applications of concepts covered in the classroom. Field trips included: Bus Tours historical narrative of the East Tampa community done by the chair of the ETCRP and a visual pre sentation of the stormwater ponds in the area with time allotted for sampling exercises. Howard Curren Advanced Wastewater Treatment plant students toured the Howard Curren Advanced water treatment plant to see how other engineered systems clean water b efore being discharged into the Bay Florida Aquarium Tours tours were divided into age appropriate activities which included mangrove in house planting (G3 G4), behind the scenes water quality monitoring (G5 8), and an aquarium exhibition scavenger hunt. Special programs refer to video productions, community kiosks/informational signage, competitions, and summer exploration projects. Videos were produced by the Young Middle Magnet students and the graduate researcher. This was used for the EPA P3 Design Competition in April 2009 and is now shown during community outreach activities. Graduate researchers also produced a laboratory video intended for prim ary level audiences that showcases the preparation and analytical tools required to determine the leve ls of environmental contamina nt s in various media samples (e.g. water, sediment, and fish) For example, one video was related to an in class sampling exercise in which Chiles Elementary students prepared fish samples (fish were collected from their sto rmwater pond by a caretaker who normally fishes there and a local market ) following the beginning steps of an actual laboratory standard operating procedures manual for preparing fish samples for digestion to determine the amount of mercury present. After viewing the video segment, students are given the analytical data results to determine the

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152 total mercury loading in their fish sample. Using previous information as well as guidelines from the state of Florida students draw their own conclusions on whether they should eat the fish as well as the frequency C urrently, c ommunity kiosks are under development as informal science education centers at the stormwater ponds. Figure 6.1 0 highlights the mercury informational signage developed from a part nership with the Southwest Florida Water Management District (SWFWMD) as well as the schematic of the first kiosk, designed by the USF architecture department. The City of Tampa has agreed to finance this project and it will be installed in March 2010. I n addition to conceptualizing the kiosk, the WARE members (community members, teachers, students, university faculty/students, and a graphic designer) worked on the content to be displayed on the four separate panels, the door and the rain barrel This first kiosk will be located at the Robert S. Cole Jr. Community Lake opposite Young Middle Magnet. Figure 6.1 0 Sketch of E ducational K iosk to be L ocated at the Robert S. Cole Community Lake in East Tampa. Prepared by Prof. Trent Gree n of the USF Architecture Department and Mercury Informational Signage as Joint Collaboration with the Southwest Florida Water Management District (SWFWMD)

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153 After students we re introduced to several WARE curriculum topics and sustainability concepts a co mpetition was held at each school in Spring 2010 to assess their ability to describe what they had learned. The competition requested that the students turn themselves into reporters and convey the importance of the WARE program or discuss an environmenta l topic they learnt and felt comfortable with conveying (the empowerment phase). Two to three students from each of the schools were selected to discuss the WARE project live on the WMNF radio station on Sunday February 14th, an activity arranged and coor dinated by the graduate researcher and a community member their parent/s and one of the teachers from Chiles Elementary. Some of the students from Young were selected based on their p revious and extended engagement with the class and WARE program Each student was asked a question on the air and presented along with USF faculty and the graduate researcher. WMNF (88.5 FM) is a community radio broadcasting and internet streaming statio n located four blocks away fro m Young Middle Magnet. Its Sunday morning program has a listenership of about 15,000 persons In addition to projects that incorporate the media, a two week summer apprenticeship program was implemented by the graduate rese archer in 2009. It involved four middle school African American girls, two of whom were from Young and participated in WARE the previous spring, and two from Lockhart Elementa ry who participated as well. Students were first reintroduced to concepts of me rcury more in depth than what was given in lessons during the academic year. Presentations were open to parents, teachers, and community members followed by lab tours. Students received USF laboratory safety training certificat ion and additional briefing s such as field safety Students then performed field preparation protocols and spent 3 day s in the field collecting water and sediment samples. While in the field each student assumed ownership of a specific role after being clearly informed of each tas k involved for the particular role. This was done to ensure team effectiveness. Though not directly involved in the analysis, students prepared sediment samples (e.g. appropriately labeling containers and data sheets, collecting wet and dry mass, drying, and cooling samples) for analytical analyses using a CVAAS. Students were also allowed to label all glassware and insert sample identification information into the analytical computer systems but were not allowed to come in contact with chemical reagent s or carry out analyses.

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154 6 4 Results and Discussion In 2009, regular classroom visits were made once a week to each of the schools for the first six months then biweekly for the remaining academic year. Partnership based progress and update meetings and educational sessions were held once a month for one hour. Classroom activities were designed to be completed within 45 minutes. The sections below summarize the findings f rom each reflective journal used to assess the in class activities as well as the evaluation of the progression of the WARE program 6.4.1 In Class Activities Section I: Water Matters (A brief introduction of global and local perspectives) Lesson Overview (Building on A wareness and A ttitude) During L esson 1, Water M atters students were shown a video documentary presentation on my travels throughout the world. The intent of the documentary was to bring about environmental awareness issues dealing with water as well as encourage positive attitudes and perception s. Reflection: Middle School Instructors and ESW members co taught about the global and local perceptions of water. Students were able to understand the hardships associated with water access, rights, quality, and quantity. However, there wa s still a negative perception about people who were not able to obtain water and had to get the resources from contaminated lakes. The children thought that it was easy for people to move to obtain better resources and that it was available to everyone at all ti mes except if you did not pay your bill on time. Teachers had to step in to use age appropriate language to conclude the lesson. Elementary School Students were extremely captivated and more compassionate than the middle school students. The think tan k discussion involved in this lesson was a little too much for the students to handle and their behavior became a little disruptive. Teachers then had to redirect the students focus to

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155 behavior. Despite minor behavioral issues t he video production was well perceived Students and teachers also inquired about other issues relating to health, sanitation, and food. Section II: The Chemistry of Water Lesson Overview (Building on Knowledge) The phases of water were discussed on the chalk board and using an interactive computer model. Students were then as ked to develop a model of a water molecule using marshmallows, toothpicks and balloons as well as perform various tests to charac terize its properties Middle s chool students were taught from a college textbook and assigned a homework assignment to review the periodic table of elements, learn abbreviations for important elements (carbon, oxygen, hydrogen, sulfur, nitrogen, phosphor ous, mercury, lead, zinc, and cadmium), molecular weight, atomic mass, and atomic number. Reflection: Middle School ESW affiliates were well prepared and had handouts for students. It was assumed that the students understood that there was a periodic t able of elements; therefore, the first lesson dealt with how to appropriately read the table of elements followed by how to write the electron configuration for the important elements we were to focus on. Students were asked to review the table of elements and based on their handouts answer three questions ready for the next meeting date. Unfortunately, not all students returned the assignment and there was little teacher assistance. In the next lesson, students explored the components of water and the bon ding structure using toothpicks and marshmallows. ESW members identified quickly that there was an extreme need to make modifications to this lesson for the following year. The lesson took over the allotted 45 minutes, clean up was not smooth, and students were eating the marshmallows while in the classroom laboratory which is strongly prohibited. Elementary School ESW members were extremely shocked that students identified immediately that water was 2 d; therefore, an explanation was given by using balloons to construct a water molecule Students were separated into teams of

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156 three to create their molecule. After spending too much time on blowing up the balloons, students were spatially arranged with their water molecule to represent the different phases of water (solid, liquid, and gas) and bonding orientations Section III: Water Quality, Quantity, and Public Health Overview (Building on K nowledge, A wareness, A ttitude, and P articipation) Students were to understand the differences in point source vs. non point source contamination; the importance of various water parameters (pH, DO, turbidity, biological indicators, temperature, nitrates, phosphates, heavy metals), typical values seen in the world and water related illnesses. Reflection: Elementary and Middle Schools This lesson was quite interactive and the lesson surpassed the allotted design time. All students were actively engaged and participated in the lesson. Teacher assistance was needed to help students setup various tests. Students worked well with each other and with educators. Students performed different water quality tests and then collectively drew a large illustration of the effects. Although studen ts understood the big picture, the experimental setup had students puzzled. Section IV: Water Cycle (natural system) & Water Treatment (engineered systems student makes connection to water cycle) Overview ( Building on K nowledge, A wareness, A ttitude, an d P articipation) Student emphasis was placed on aquifer and surface water storage and drinking/wastewater (i.e. stormwater and reclaim water concepts were introduced). Reflection: Elementary and Middle School Each year students are taught about the water cycle; therefore, middle school students were not enthusiastic about the lesson. On the other hand, elementary students enjoyed the water cycle song

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157 The lessons and activities in this section were all well received Students were given an age appropriate PowerPoint presentation that they were to read aloud, examine the figures, and discuss natural and engineered systems. Then based on the reading students were to put together a filtration system using a media of th eir choice that they believed wo ul d work best. Some teachers and students were intrigued by the filtration process and even identified this exercise with home water purification systems. Section VI: Water Monitoring Overview This section serve d as a lesson that would be taught the entire second semester. Students were to focus on the retention pond and rotate work schedules based on the following subgroups: Lead engineer, field assessor, field sampler, lab analyst, and data analyst. Each gr oup had a specific task and a team lead er The team lead er was responsible for getting information from all the other teams. Lead er s would remain the same for a week and students would rotate based on their likes analysis conducted in the beginning of th e semester. Lead field sampler s had to package samples using a chain of custody form that would be sent to USF for further metals analysis. Reflection: Elementary and Middle School Memory recall from the previous lessons was good; however, students were not focused on their specific tasks within their groups and equipment malfunctions were an issue Teacher and students took the initiative to construct a water sampler and tested samples using water a nalysis test kits on a more frequent basis. Table 6.1 3 describe s the r eflections on WAREs incorporation of the Guiding Principles for CBPR Research as l isted in Table 6.6

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158 Table 6.1 3 Reflections on WAREs incorporation of the Guiding Principles for CBPR Research L isted in Table 6.6. CBPR Guiding Princip les 302 ( Taken from Israel et al ) Reflections on WARE 1. Recognizes community as a unit of identity I nitially and cor e focus: P artnership with East Tampa, a seven square mile community with 13 different neighborhood associations and a strong governi ng community group, the ETCRP. Expansion: O ther locations in Tampa due to movement of WARE members out of East Tampa or East Tampa schools. Future: R edefine the communities involved with WARE, and link communities via website which would eliminate geograp hic boundaries and extend WARE to other cities, states and countries (e.g. the sites in Guyana and Bolivia that were discussed in Chapters 4 and 5). 2. Builds on strengths and resource within the community Development of t eacher and student training and c ommunity aw areness of environmental issues; b ackground material for larger grants that build on the partnerships developed with WARE and that involve other faculty from USF from education and health; working with engineering faculty and the chair o f the ET CRP to develop a future USF class based on community engagement and know that workshop attendance enhanced both faculty and community member understanding of community engagement opportunities. 3. Facilitates collaborative partnerships in all phases of th e research Investigators and communities work together to define the problem, collect data, and interpret results. It is truly an empowering process for all involved. 4. Integrates knowledge and action for mutual benefit of all partners All involved need t o determine the mutual benefit of the process and develop an intervention or guide policy. 5. Promotes a co learning and empowering process that attends to social inequalities Researchers need to enhance their capacity and learn from the process. 6. Involves a cyclical and iterative process As descrbied earlier WARE has grown and continues to evolve since its inception. Improving outcomes (e.g. learning of students and engagement of community) is a constant process and there are multiple places where review and repackaging is implemented. 7. Addresses health from both positive and ecological perspectives WARE was conceived by members of the ETCRP, the City of Tampa, USF faculty, faculty from Young Middle Magnet, and initially b uilds on problems identified by the community, which are often linked by additional sources of data (e.g., epidemiological surveys and environmental stressors). 8. Disseminates findings and knowledge gained to all partners Table 6.8 lists the various dissemination activities in which each WARE member played a role. The monthly meetings were the most accessible place for sharing all of the information on the project to date even though the material is posted to the website, including pictures o f all activities.

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159 Although, the metrics used to collect empirical data are a short term outcome for individual program achievements with partners, it does not address the long term impacts of effectivel y promoting change in behaviors. T herefore, the tot al success of the project is highly unknown at this time S tudents are able to discuss and address environmental concepts especially in smaller participant sizes and with the community (e.g. summer apprenticeship s and community outreach programs), and the best overall responses were seen within the special programs. This may be due to personal mentoring relationships that developed and additional team building exercises that were not a part of the main curriculum (e.g. canoeing, ropes course, student guided horseback riding, concerts in the performing arts museum exhibitions, and botanical garden and state park field trips). Sullivan et al. 313 found similar results for high school girls who explored careers in engineering and technology during a summer internship program. Additionaly, i n a week 314 found that after one week girls in grades 9 and 10 havin g developed a strong bond with university student mentors were more interested in science and wanted to take computer science course electives. Chickering and Gamson 315 all levels of education that learning is enhanced in a team setting. Additionally, community outreach and engagement were also tools that all members enjoyed which gave each student as well as teachers a sense of ownership in tackling a real world proble m and helping to build self confidence. Seifer ascertained that service learning or active community outreach programs benefit students, faculty, communities, higher education institutions, as well as other relationships among all stakeholders 316 This is suggestive that the iple design of active engagement leading to information exchange and empowerment can be achieved. Students who participated in the summer field exploration program were se lf motivated to participate in science fair competitions as well as student presentation on their roles in environmental sampling. One student who entered into the state science fair won first place in her school and has since moved on to compete in the d istrict fair. Studies by Feldman argue that people learn through taking part in apprenticeship experiences and that assigning different roles to different participants effective ly develops proficient researcher skills 317 Moreover, studies

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160 have shown that strong links exist between high quality programs that go beyond core literacy and numeracy skills often found in in school programs. In addition, there was seen to be a greate r impact factor on girl participation. This may be attributed to program coordinators being females who did not resemble the perceived normal scientist or engineer thereby inspiring and empowering participation. 6.4.2 Partnership Progression and Evaluat ion Figure 6.1 1 Schematic o f Growth i n Partnerships a nd The Need f or Curriculum Development Gathered f rom Reflective Journal Entries. Since it is difficult to determine the measure of success based on student knowledge, the progression and evaluation in partnerships has been examined. Figure 6.1 1 highlights the progression of the program and the changes needed to be made to each of the lessons based on reflective journals and teacher input.

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161 The program has expanded from its inception in 200 8 from one school to three schools (with ~ 60 student participants and four teachers), a university based student organization, radio and TV personalities, university professors, local government officials, and active east Tampa social and civil engagement community members. Although, the program has grown and students have become actively involved there is a need for internal restructuring and strengthened communication amongst all vital partners. Some of the program downfalls include conflicts in partic ipation or project sustainability, scheduling, administration, and effective communication amongst all partners. However, the expertise of each partner has been effective at developing new activities and engaging the students. Stakeholder feedback althou gh discussed informally in meetings is needs to be in a formal and uniform manner. 6.5 Conclusion A six step curriculum developed with the assistance of teachers and community members was designed and incorporated into the classroom to serve as a tool for teaching sustainability concepts with an initial focus on water quality of stormwater ponds. The study revealed some key findings from researcher reflective journals. Partnerships from all areas of society (GK 12 schools/students, un iversity professors/students, community members, and governmental agencies) are critically important in educating and addressing issues of sustainability. T he collaborations established in the WARE Program ha ve led to a heightened awareness of the importance of partnerships in teaching on sustainability with a focus on stormwat er ponds with respect to their function water quality issues and an overall understanding of heavy metal pollutants such as mercury. Student s teacher s and community increased awareness has resulted from the direct involvement in a formal capacity (presentations inside and outside of school) as well as an informal capacity (East Tampa Community Survival Day, USF Engineering Expo, field trips, field training, team building exercises, and mentoring). Moreover, this may be used as an effective teaching tool for the required graduate course hours in instructed methods to to different audiences and therefore engaging them in decision making processes related that can improve environmental quality and community health

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162 CHAPTER 7: INTEGRATED EXAMINATION OF MERCURY 7.1 Introduction Mercury cycles through the environment in a complex global network depicted in Figure 7.1. As m ercury is introduced to the atmospheric environment from natural and anthropogenic sources, it is transported around the world via patterns of wind dispersion, atmospheric deposition, volatilization, and suspension which ultimately leads to bioaccumulation and biomagnifcation up the food chain. Figure 7.2 presents pathways for mercury in commerce. Human activities like coal combustion, ore refining, manufacturing processes, small scale gold mining, religious practices as well as the chemical characteristi cs of mercury facilitate the transport of mercury throughout the world. Laws, regulations, technologies and informed human decisions and actions can all minimize the negative impacts of mercury and vary both spatially and temporally. The traditional (eco nomic, social, environmental) and non traditional (economic, political, socicultural, community participation, environmental) pillars of sustainability capture the critical areas to address in producing a sustainable outcome 273 In this chapter the five pillars of sustainability are used to compare the field sites which vary geographically, politically, economically, socioculturally, demographically and geologically. Chapter six presented education as es sential for ensuring sustainable outcomes and included a program being developed for an area within the Tampa, Fl field site. This discussion on education is expanded to the Guyana and Bolivia field sites. 7.1.1. Objectives Task s and Approach The obje ctive of this chapter is to compare mercury occurrence, use and exposure associated with field sites in Bolivia, Guyana and the USA using the pillars of sustainability as critical areas for consideration. These three countries differ in terms of demograph ics, geography, geology, politics, economics, commerce, history and culture. The tasks and approaches are:

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163 Summarize major characteristics of each study site/country through literature review. Compare mercury occurrence, use and exposure associated wi th the different field sites using the pillars of sustainability as critical areas for consideration. Literature reviews, data analysis (from Chapters 3 6), and personal observations were used to assess mercury as it relates to: Economic Sustainability Are the drivers for mercury use sustainable for the different levels of participants? Political Cohesion Is there political support, commitment and processes to attain sustainable outcomes? Community Participation How do the principles of Community Based Participatory Research (CMBR) guide activities at local sites? Environmental Sustainability Are there negative impacts on environmental compartments thereby impacting ecosystem and human health? Socio Cultural Impacts How is socio cultural behav ior influenced by current practices and how can the sustainable outcome respect those customs? Propose potential partnerships for Guyana and Bolivia that can contribute to reaching sustainable outcomes for reducing mercury impacts on the local and global environment. 7.2 Results and Discussion Environmental, social and economic conditions have geospatial and temporal variability. The concept of sustainability addressed in the context of this work has been derived from the Brundtland Report and McConville and Mihelcic 273 and pays particular attention to human needs. A need is a socially constructed term that depends on the specific society/community. The definition of need in this study is on e including food, clothing, shelter, a healthy environment and economic stability. These needs are limited by the carrying capacity of society, the economy, and the environment.

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164 Table 7.1 compares the characteristics of the different study sites presented in Chapters three to five, located in Florida, Bolivia and Guyana. The following sections discuss their similarities/differences as they impact mercury presence and potential exposure for the given areas.

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165 Figure 7.1 The P resence of M ercury in the G lobal E nvironment 165

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166 Figure 7.2. Pathways of M ercury T ransport in the E nvironment ( M odified from Swain et. al 318 ) 166

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167 Table 7. 1 Site Comparison of S ocial, E nvironmental, and E conomic F actors in Florida, Bolivia and Guyana. Factor Tampa, FL Bolivia Guyana Population State 17, 019,068 Tampa 303,000 9,775,246 (July 2009 est.) 752, 940 Geography Located in US Coastal (1926 km) Land Area 140,512 sq km Water Area 11,157 sq km 22 nd largest state in US Located in Central South America Landlocked Land Area 1,083,301 sq km Water Area 15, 280 sq. km 28 th largest country in world Located in Northeast region of South America Coastal (459 km) Land Area: 196,849 sq km Water Area: 18,120 sq km Language English Spanish, Quechua, Ayamara English, Amerindian dialects, Creole Hindi Climate Semi tropic Three seasons Varies with elevation Arid Altiplano Two Seasons (rainy and dry) Tropic, hot humid Two Seasons (rainy and dry; rainy: May to August and November to January) Natural Resources/Major Commodity Oranges Phosphat e Sn, Zn, Pb, Fe, Au, natural gas, petroleum, Li Sugar, gold and diamonds, bauxite, shrimp, timber and rice (60% of GDP) Major Weather Events Hurricanes Flooding Droughts (Altiplano) Volcanic eruptions Flooding (North East) Flooding Environmental Issues Water availability Water quality and Total Maximum Daily Loads Everglades restoration Mercury Soil Erosion Water pollution/privatization Mercury Water pollution Deforestation Food Source of Concern wrt Hg Loadings Fish Fish, potato, llama, alpaca, qu inoa, coca Fish, rice, cassava Economy HDI 13 (very high development) 40% of all US Exports to Latin and South America 75% of US orange production Tourism CPI 7.5 # HDI 113 (medium development) Export commodities: natural gas, soybeans, crude oil, Zn, Sn, Au (low) CPI 2.6 # HDI 1 14 (medium development) 60% of GDP from sugar, gold, bauxite, shrimp, timber, and rice CPI 2.7 # Political Society Major Laws Affecting Mercury Democracy 1 st Arican American President The Clean Air Act, The Florida Management of Mercury Containing L amps and Devices Destined for Recycling The Clean Water Act, Impaired Waters Rule Mercury Export Ban Act; EPA Clean Air Mercury Rule Republic (new constitution state 1 st Indigenous President (Ayamara) Social Unitarian State) Environment Regulation on Mi ning Activities 1995; Mining Code 1997; General Environmental Law, 1992; International Labor Organization, 1991 239 Republic Forest Bill 2009, Mining Law, Amerindian Act 2006, and the Environmental Protection Act 2006. Additionally the Land Law, the Iwokrama Act, National Infrastructure Policy Principle Sources of Mercur y Exposure Coal fired power plants Municipal/Medical Waste Incinerators Gold and tin mining Volcanic Eruptions Gold mining activities Deforestation or Land Degradation. *Information collected from State of Florida ( www.stateofflorida.com ). Obtained from CIA World Factbook. Obtained from UN 2009 Human Development Report ( http://hdr.undp.org/en/statistics/ ) where the closer the Human Development Index (HD # Obtained from Transparency International for 2009 where the closer the Corruption Perceptions Index (CPI) is to 10 (on a scale of 0 to 10), the least corrupt it is (http://www.transparency.org/policy_research/surve ys_indices/cpi/2009).

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168 7.2.1 Economic Sustainability, Political Cohesion and Community Participation Mercury is used to extract several precious metals and is found in various household products It is also used in ritualistic practices in Afro Caribbean and Amerindian religions and for obtaining gold (e.g. jewelry). Human consumption and consumerism can inadvertently cause destruction to the environment. Currently, consumption of resources and capital in developed countries are being utilized at a faste r rate than they are being replenished by natural geological and biological processes. On the other hand, developing countries allow developed nations to establish in Development Index (HDI), an indicator that measures development and human progress based on health, education, and purchasing power, ranks Bolivia and Guy ana as 113 th and 114 th out of 182 countries, respectively. These two countries are classified as being medium development whereas the United States is classified as having a high HDI. The GDP for Guyana, Bolivia, and the US is $13, $11, and $13 751 billi on US dollars respectively. Compared with the US, Guyana and Bolivia are at a severe market disadvantage. the growth of the economy results in a degradation of the environment until the desired economic development is obtained 319, 320 This was further supported by Beckerman 321 who environmental degradation in the early stages of development, in the end the best and probably the only way to attain a decent environment in most countries is Bank, one of the main lenders to developing countries for infrastructure improvements, argues that the EKC is based on a static assumption that economic development hurts the environment 322 Mechanisms like the Clean De velopment Mechanism (CDM) created under the technological development. Through binding agreements with developed country industries they can acquire the newest, most efficient and clean technologies since their lack of infrastructure makes it more cost effective to implement them and get the carbon credits versus making improvemen ts in existing developed world infrastructure. With the absence of any binding

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169 agreement at the 15 th Conference of Parties, mechanisms like the CDM remain under utilized. The Human Development Report presented by the United Nations Development Programme 233 has stated that: It is exacerbating inequalities. And the dynamics of the consumption poverty inequality environment nexus are accelerating. If the trends continue without change not re distributing from high income to low income consumers, not shifting from polluting to cleaner goods and production technologies, not promoting goods that empower poor producers, not shifting priority from consumption for conspicuous display to meeting basi c needs and human development will worsen. \ The real issue is not consumption itself but its patterns and effects According to the World Bank 323 20% of the United States) account for 76.6% of the total consu mptive expenditures whilst the middle (e.g. Guyana and Bolivia) and lowest countries (e.g. Haiti) contribute to 2 1.9 % and 1.5% of consumer expenditures respectively (Figure 7. 3 ) Globally, the historic production of mercury dates back to fourth century B C during Egyptian times and increase d as the Spanish silver mining expeditions evolved in the 1600s and further climax ed during World War II in the 1900s 324 Also d uring World War II, tin production in Bolvia and export to the US increased 325 Cinnabar (HgS), the product mined to obtain mercury, has been produced in Idirija (present day Slovenia) and other locations (e.g. as well as Kyrgyzstan, Russia, and Ukraine ) for 500 years Al maden for 2000 years, and us ed in Guyana for over 500 years and China for over 2000 years Gold and silver were mined in Bolivia by the Tiwanacu and Incan peoples long before Spanish arrival in 1545 326 R ecent reports indicate that Bolivia has at least 3 million troy ounces of gold worth in claims t hat have been untouched 327 The historic use of mercury has been shown to be devast at ing to h umans, animals, and the environment.

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170 Figure 7. 3 World Consumption Behavior (a) Total Consumption 323 and (b) Mercury Consumption from (1500 2000 T aken from Hylander 324 ). Figure 7.4 highlights the reported current consumption, production, price, and legislation of mercury from 1970 1997 in the United States. In 1970, when mercury consumption and prices were at a peak, mercury was identified as a hazardous pollutant under the Clean Air Act. Following this legislation, the production rate decreased but consumption continued to soar until 1992 when the EPA banned land disposal of high mercury content wastes and the National Defense Stockpile (NDS) suspended mercury sales 328 The World Mercury Ban established by the European Union passed a regulation banning the export of elemental mercury in 2007. Sena tor Barack Obama (D IL) and Senator Lisa Murkowski (R AK) introduced the Mercury Export Ban Act (MEBA) of 2008 (S.906) that prohibits the sale of federal stockpiles of elemental mercury and prohibits the export of elemental mercury from the US, effective J anuary 1, 2013 329 The provision s of the MEBA call for : Al l Federal agencies to immediately cease conveying, selling or distributing elemental mercury under Federal control or jurisdiction to any other f ederal agency, any s tate or local government agency, or any private individual or entity except for transfers t o facilitate storage or transfers of coal. The prohibition of elemental mercury from the United States starting on January 1, 2013. term management and storage of any elemental mercury generated within the United States.

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171 Balistreri and Worley 329 argue that payment for seq uestration of mercury in the US offers less drawbacks than the export ban which will encourage local mercury use, discourage mercury recovery from byproduct and waste sources and result in a surplus of mercury in the domestic market, even at a zero price. The impact of a mercury ban on artisanal gold mining can be dramatic given the number of people employed and dependent on this way of life, and their already poor economic situation. In the absence of capacity building efforts that provide either alterna tive mining methods or alternative livelihoods one can imagine the destruction of these communities if mercury becomes scarce as well as the destruction due to current mining activities. Ironically, the US provision never called for an export ban of m ercury compounds commonly found in the waste stream T able 7.2 summarizes the report s from Congress that describe the possibilities of mercury compounds being extracted for mercury from waste products such as electronic components. Figure 7. 5 shows an i ncrease in mercury exports which may be due to the large cost associated with storing toxic waste which is a part of the provisions for the MEBA. Additionally, the European Union o n October 22, 2008, expanded the mercury export ban to include certain merc ury compounds and mixtures (e.g. met allic mercury (Hg 0 ), mercury (I) chloride (HgCl) ; mercury(II) oxide (HgO) ; cinnabar ore (HgS) ; and mixtures of metallic mercury with other substances, i ncluding alloys of mercury having a mercury conce ntration of at leas t 95% by weight. This new ban will be effective on all exports from the European Union after March 15, 2011.

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172 Figure 7. 4. Legislation, C onsumption, and P roduction of M ercury in the US from 1970 1997. A FL ASK is E quivalent to 1 216 ozs (34.5 kg) of M ercury. 172

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173 Table 7 .2. Summary of Info rmation on Mercury Compounds Req uired in the Mercury Export Ban Act of 2008. Produced in US Imported Purposes and Uses Quantity used annually in US Quantity used 2010 and aft er Sources and quantities exported i n last three years (2006, 2007, 2008 ) Potential for export for regeneration of elemental merc ury Compound Name Source Sector kg in 2004 S o u r c e Quantity (annual) Mercury (I) Chloride Air pollution by product at mines, 25 000 Hg Data for individual compounds not currently available Data for individual compounds not currently available 1. Processed for elemental regeneration Data for individual compounds not currently available Data for individual compounds not currently avail able Data for individual compounds not currently available Likely, unlikely chemical manufacturing 1.3 2. Calomel (mercury (I) chloride) electrodes Mercu ry(II) nitrate Chemical Manufacturing 88.7 1. Preparation of other mercuric products 2 Analytic reagent (test kits) Somewhat likely Mercury (II) oxide Chemical manufacturing; Battery recycling 32.5 1. Batteries 2. Synthesis of other compounds 3. Analytical reagent Somewhat likely Mercury (II) sulfate Chemical manufacturing; Wa ste Treatment 260.8 (amount from waste treatment unknown) 1. Gold and silver extraction 2. Reagent Somewhat likely Mercury (II) Sulfide Naturally occurring; chemical manufacturing; waste treatment 0.6 (amount from waste treatment unknown) 1. Ex traction of elemental mercury 2. Pigment Somewhat Unlikely Mercury (II) acetate chemical manufacturing 41.3 1. Manufacturing of organomercuric compounds 2. Catalyst or reagent Unlikely 173

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174 Figure 7. 5 1998 2008 US Commodities Imports and Ex ports Report for Mercury (Data Collected from USGS Minerals Database 330 332 ) Aside from the direct extraction of mercury, the use of mercury in the mining industry helps to drive the economies of Guyana and Bolivia where mining and timber and oil account for 60% of the GDP. The US economy was once backed by gold and contains one of the largest reserve holdings of gold alongside Germany, the Internat ional Monetary Fund, France, Switzerland, and Italy. In a global economy that has been on edge due to the wake of financial collapses, gold prices have soared to alarmingly historical high rates above $1200/oz (Figure 7. 6 ) and mining activities in develo ping countries (e.g. Guyana) have increased (Figure 7. 7 ). The amount of wealth remaining in the developing country and the sectors of the societies which benefit remains questionable. Many environmentalists argue that this is due to consumer wants rath er than needs 107 as this the health of many inhabitants which include miners, non miners (both local and global ) as well as animals. According to the World Summit on Sustainable Development in Johannesburg, many stakeholders in the mining sector as well as consumers should be held responsible for their consumptive behaviors and not blame the corporations. 0 150 300 450 600 750 900 1050 1996 1998 2000 2002 2004 2006 2008 2010 Import/Export Gross wt. (metric tons) Year Hg Import Hg Export

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175 Figure 7. 6. 10 Year Gold Price in USD per O unce Last Closing Price was $1,134.80 on 03/05/2010. Figure 7. 7. Declared G old Production for (A) Guyana: 1979 2008 from L arge S cale OMAI M ine and S mall to M edium S cale M ines (non Omai) (GGMC, 2009) and (B) Bolivia: 199 6 2007 D ata O The Min eral Industry of Bolivia in 2007 (2002, 1997, and 1996) T aken from http://minerals.usgs.gov/minerals/pubs/country/sa.html A Some g overnments are taking measures to reduce mercury usage by developing legislation that requires th Many of the clean technologies can be classified as gravity based 333 and can also lead to additional des truction to the environment In addition,

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176 require the removal of forest cove r. In Guyana, WWF Guianas with the assistance of the Guyana Geology Mines Commission Guyana Environmental Capacity Development (GENCAPD) program established training on gravity based mercury free technologies that promise similar yields 108 Without incentives in Guyana for using these technologies, no miners currently use them even though the GENCAPD (funded by the Canadian International Development Agency (CIDA)) project is over ten years old. Interesting to note is that the largest claims in mining concessions held in Guyana are registered to Canadian mining companies. These larger concessions normally utilize cyanide leaching techniques, a process whereby mercu ry forms a complex with cyanide that is recovered in a chemical plant. A 1995 tailings dam spill from the OMAI gold mine released 3 million m 3 of cyanide slurries into freshwater systems 326 It remains the largest such catastrophe in Guyana that affected water supply and fish consumption of downstream communities. The Environmental Protection Agency was formed more or less as a result of this spill. Hence, international aid from CIDA is assisting with improving sustainability practices amongst small to medium scale miners whilst large scale Canadian registere d mining operations failed to institute sustainable practices in Guyana. 334 the government of Guyana is trying to enforce more stringent regulations that would better manage mining site activities, make mercury use in mining illegal and institute better management of developed in conjunction with the consulting firm McKin sey & Company with financial backing Climate Initiative. The LCDS was developed to take advantage Emissions from Deforestation and Forest De gradation in Developing Countries; and conservation, sustainable management of forests and enhancement of forest carbon stocks in ecosystem services, mainly their abil ity to reduce CO 2 emissions from avoided deforestation activities 335, 336 An estimated 20% of global annual CO 2 emissions comes from deforestation with power plant emissions being the largest at 24% 336 One of the few substantial outcomes of

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177 COP 15 held in Coppenhagen in December 2009 was the commitment of funding from the most develope d nations for REDD+ which would be managed by the Forest Carbon Partnership Facility (FCPF) of the World Bank. An estimated $175 million is currently pledged for the various funds to support REDD+ 337 website, the first set of proposals for initial REDD + funding (Readiness Plans, R PLANS) of approximately $300,000 US are now in their second phase of review (as of March 2010) and will be used as pilot studies for various aspects of REDD+, including fina ncing and monitoring exercises. Guyana will be one of the first, if not the first country to receive funding from the FCPF. The government of Guyana also entered into a bilateral agreement with Norway for REDD+ like initiatives under the LCDS in Novemb er 2009. Norway has pledged $250 million US over five years with an initial installment of $30 million 334, 338 The LCDS estimates annual payments greater than $580 million US under the REDD+ program in a tiered approach that would reach this value after 2020 338 To put this amount of money in perspective, a recent application by a Canadian company for a gold mining permit in the Marudi Mountain area estimates mining of 1 using mobile screen and conc generated in one year would equal the entire 5 year Norwegian pledge. Many other new mining applications are in the pipeline for Guyana. Mahdia, one of the sites presented in Chapter 4, wa s once to be mined by large scale mining operations. The grade of the ore and gold prices at the time (around 2000) converted the concessions into small to medium scale mines all of which use mercury recovery techniques. Now that gold prices have more t han tripled since the larger mining interests left, it remains to be seen if the medium to small scale local miners will be action since closure in 2005, it is unknown whether the larger scale, international mining operations would be any more sustainable than the small to medium scale miners. In January 2010, the government of Guyana proposed regulations that would require gold miners to obtain approval from the Guya na Forestry Commission for new mining activity. Gold miners would have to identify their intentions six months prior to mining activity, something that has raised major concerns amongst the mining community and resulted in well organized protests in

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178 Barti ca and Mahdia in January a nd February 2010. Miners believed that the LCDS would force at least 80% of the local miners out of a job. Some of the regulations being enforced all of a sudden have actually been part of Guyanese law for over a decade. Lack o f interest or provision of proper resources by the government to the agencies in charge of regulation like the Guyana Geol ogy and Mines Commission (GGMC) ha s resulted in little to no action being taken to ensure proper mining practices. There has been ver y little government investment in technical capacity building that could improve the small to medium scale gold mining sector through partnerships with the local university and technical training institutes. The NGO WWF Guianas has supplied equipment to both the GGMC and the University of Guyana over the past five years that is being used to monitor mercury levels of miners whenever they declare their gold. The last equipment purchase capable of mercury detection by a governmental institution (Institue of Applied Science and Technology) was over twenty years ago in the form of a Cold Vapor Atomic Absorption Spectromter. The very recent move to enforce standards, institute new mining regulations, and commit to capacity building is very interesting in ass essing sustainability as it really shows the impact of political will and political engagement. Given this sudden and almost immediate change in governmental strategy towards mining, a more in depth discussion of the LCDS process follows with linkages to sustainability issues raised in Chapter 6 through the Community Based Participatory Research (CBPR) process. Chapter six described the principle guidelines required for successful CBPR projects and Table 7.3 summarizes the relationship between those princ iples and LCDS activities based on published material, reviews of publicly accessible material posted on the official LCDS website, newspapers, blogs, website postings and personal communications.

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179 Table 7.3 Linking P rinciples of Community Based Parti cipatory R esearch CBPR Guiding Principles ( Israel et al. 302 ) P rocess Recognizes community as a unit of identity Based on the impact of the LCDS on livelihoods of all Guyanese, the community represents the entire country. The main participants are the President and Office of the President, the LCDS appointed steering committee, Guyana Office of Climate Change, Indigenous groups, Forestry Commission, Non Governmental Organizations (especially Conservation International and WWF Guianas). Partnering members also include the international financing community (e.g. FCPF and Norway), members of the Guyanese diaspora, and foreign research institutions. Builds on strength s and resources within the community CBPR supports and expands existing social processes (community skills, assets, existing structures like community boards) to address community needs. Facilitates collaborative partnerships in all phases of the resear ch The LCDS has potential for engagement and empowerment for all involved (Conservation International 335 ) Organized civil protests by mining gold communities in 2010 suggest that collaborative partnerships are not yet in place for all members of the communities that will be affected by the LC DS. Integrates knowledge and action for mutual benefit of all partners The initial development of the LCDS took a very top down approach that is politicized in a country sensitive to these associations. The draft LCDS was shared with the Guyanese publ ic after it had been drafted by members of the government and McKinsey & Company. Promotes a co learning and empowering process that attends to social inequalities The LCDS has the potential to do this if communities are truly allowed to participate in the decision making and implementation processes. Involves a cyclical and iterative process The LCDS was released to the Guyanese population in June 2009. Listening sessions throughout the country were held between June 2009 and September 2009. The dr aft LCDS proposal stated that the website would be used to collect comments from the public that would be considered by the LCDS steering committee. This was never made available. An updated draft document was published in December 2009 and it did not ad dress many issues raised in the consultations and this has resulted in non support from the indigenous groups. Addresses sustainability from all five pillars* The LCDS is a binding mechanism that affects all Guyanese. It should build on problems ident ified by the citizens of Guyana, but for the most part in its current state it has not adequately engaged all Guyanese so that they can meaningfully contribute to its design. Disseminates findings and knowledge gained to all partners A large publicity campaign followed the release of the draft LCDS in June 2009. All media types were used, consultation sessions were held throughout Guyana, and the LCDS website hosts many of the documents and meeting minutes. The accessibility of these materials is quest ionable as the consultation sessions revealed that indigenous communities wanted the information translated into their own language and others stated that the material was difficult to understand. *modified Principle 7 that is better suited to Guyana a nd the LCDS. 179

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180 especially those who depend on the forest for livelihoods must be active participants in framing a solution. In the same way as there is no solution to climate change without forestry, there is no solutio n to deforestation ( Parker et al. 336 ) and implementation and argued for developing countries to be equally involved in the framing of REDD+. His insistence on developing country pa rticipation at the international level fails to transfer to local affairs on the ground with respect to the LCDS PLAN under review by the FCPF. The official Government of Guyana LCDS website (http://www.lcds.gov.gy/) has provided meeting min utes from the and September 2009, reaching an estimated 7,000 persons 339 These consultation sessions were organized by the Guyana Office of Climate Change in the Office of the President and included a steering committee of various representatives of Guyanese society, though key representatives were missing like members of the opposition parties and members from the educational sector. Dow et al. 339 provide a thorough summary of the consultation process in their report, includin g commentaries raised through local newspapers. They discuss areas for improvement that would better engage and benefit Guyanese and make note of the fact that the government developed the LCDS prior to widespread local consultations, an action that could 339 document was published in September 2009 and therefore missed newspaper headlines in which citizens responded to new mining guidelines needed to meet LCDS protest mining proposals 340 Forest Measures Anger Miners 341 The second draft of the LCDS was released in December 2009 and does not address many of the limitations identified by Dow et al., 1990. In fact, it states that the

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181 the reader to the original report by Dow et.al 342 to learn about the stressed limitations. In addition to the January and February protests organized by gold miners, some indigenous groups have called for a halt to implementation of the LCDS and REDD+ projects as leaders call for hold on LCDS September consultations were inadequately administered to the indigenous groups and land rights issues need to be resolved prior to their support for LCDS and REDD+ related projects. The second d raft of the LCDS published in December 2009 338 government has been working with the mining sectors to identify ways to embark on wide ranging reform of the mining regulations and their enforcement to en sure that mining operations promote higher standards of environmental sustainability alongside economic development. Further information will be outlined in the REDD+ Governance in the second draft and not more than one month later, mining protests are occurring around the R PLAN submitted to the FCPF and concluded that since mining is the maj or cause of deforestation and forest degradation a functional working relationship that addresses integrated land use assessment is urgently needed between the GGMC and Forestry Commission and other related parties. The second R PLAN is currently under re view by the FCPF and the protests of miners and attitude of the President of Guyana to proceed with or without the consent of miners implies that more work needs to be done to forge a meaningful partnership. tation of the LCDS consultation process in news releases displayed on the LCDS website. However, on reading the posted recorded videos it becomes quite evident that commun ities were not involved in

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182 the creation of the LCDS and were merely being consulted/informed after it was developed by a multinational company in collaboration with the local Guyanese government. These criticisms have been raised in Guyana and abroad thro ugh various media outlets like newspapers, websites/blogs (globalwitness.org; lcdsguyana.com; ht tp://guyanaforests.blogspot.com), especially since there is widespread concern that lack of transparency in developing countries will prevent the funding from r eaching the communities that inhabit and depend on the forested lands or for even reaching the local population exclusive of the government. Guyana scores 2.7 on the Corruption Perceptions Index which has been developed by Transparency International with a value of 0 being the most corrupt and a value of 10 being the most corrupt 343 The LCDS is the governing document that includes REDD+ projects which are managed through the FCPF. Four institutions will manage the LCDS, all of them government associated. FCPF funding would go directly to an office within the Guyana Ministry of Finance, which raises questions on accountability on what specific investments (how contracts would be awarded etc..) will be made to improve livelih oods of the wider population, especially those directly dependent on forested lands. The potential is there for meeting the CBPR principles, however to date the LCDS has failed to satisfy these in their entirety. The LCDS is in its early stages of devel opment and the entire REDD+ funding mechanism is also new. Using the CBPR principles as a guide would actually enhance the LCDS and its prope r development. The TAP review 344 PLAN does suggest that there needs to be a clearer understanding by GoG [Government of Guyana] that this kind of information sharing is only the beginning of a process that has much larger aims. The purpose of full consu ltations is to involve the various sectors of society in discussing, identifying, and understanding in an interactive way, their level of knowledge about climate change and sustainable development linked to REDD. p a strategy for moving

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183 Like Guyana, Bolivia is also a potential site for REDD+ funding. In 2008 the Bolivian government filed a Readiness Plan Idea Note (R PIN) and are further behind Guyana in being a REDD+ pilot site. The review of their R PIN highlighted issues of engagement n the two main areas, Amazon forest and the dry Chiquita no, forest indigenous peoples are the main players, and their participation needs to be secured through better stakeholder consultation during the whole readiness The potential influence of REDD + on gold mining practices in Bolivia remains to be seen, but the widespread adoption of new ways of doing things is possible. Mining has always been a major driver in the Bolivian economy and in 1952, when the sector represented 97% of foreign exchange earned, the government nationalized mining and placed it under the management of CA MIBOL Low world market prices and 20,000 workers from the industry and by 1990, foreign inv estment was once again encouraged in Bolivia through int ernational monetary mechanisms 345 The mines are o wned by the state with some mining concessions to private Bolivian cooperatives and foreign mining companies In 2006 President Evo Morales of Bolivia nationalized the hydrocarbon industry with mining next on the agenda. Figure 7.6 compared go ld exports from Guyana and Bolivia W hilst the Guyanese exports correlated with the rise in gold prices, this was not necessarily seen in the Bolivian case which is likely influenced by political changes. As exports from a large foreign investor, OM AI, decreased, the small to medium scale mining declarations increased significantly as did the number of permits and people involved in the industry. Whilst OMAI used cyanide, the small to medium scale miners use mercury for gold recovery. Table 7.4 lists the companies registered as large scale gold mines in Guyana and Bolivia, where the former is much more open to private and foreign investment. Ineffective efforts at water privatization in Bolivia are cited throughout the world (famous examples inc lude documentaries Flow & Blue Gold) as an example of engaged and active citizenry

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184 that fights and wins over multination al enterprise s The same actively engaged and organized citizenry in the form of mining cooperatives have delayed nationalization effor ts of the Bolivian mining sector. Many of the cooperatives began during Medium Scale Miners, The National Association of Small Scale Miners and the National Federation of Mining Cooperatives are the three m ain groups representing the Bolivian mining sector 239 The most co mmon types of small scale mining operations in Bolivia are cooperatives working in alluvial gold deposits (dwindling resources), cooperatives working in primary gold deposits and informal mining (gravel scratchers, individual miners, tailings re treatment, 239 This informal sector uses the least technicall y advanced methods of mining, unwarranted amounts of unrecovered mercury, and with no safet y precautions for human health 239 Civic engagement/activism in Guyana pales in comparison to Bolivia. The recent protests by members of the Guyana Gold Miners Association against the LCDS suggest that the association is becoming more engaged; however, their initial intent is to continue their regular modes of operation. Non g overnmental o rganizations like the MEDMIN Foundation in Bolivia have focused on the development and application of technologies for the reduction of enviro nmental impacts caused by mining operations especially in a rtisan and s mall s cale m ining 239 An example project was the construction of a collective dam to receive tailings from 40 separate flotation plants which serviced approximately 8 000 miners who were producing approximately 1 500 t/day (almost 100 times the amo unt of gold produced annually) 333 In Guyana, WWF Guianas is the organization that has been leading the charge in terms of impr oving the practices of small to medium scale gold mining.

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185 Table 7.4 Gold Companies in Guyana and Bolivia Gold Companies in Guyana Gold Companies in Bolivia Argus Metals Corp. Caerus Resource Corporation Gold Port Resources Lt d. Goldstone Resources Ltd Guyana Goldfields Inc. Iamgold Corporation Infinito Gold Ltd. Newmont Mining Corp Sacre Coeur Minerals, Ltd. Shoreham Resources Ltd. Takara Resources Inc. Uramet Minerals Limi ted Valgold Resources Ltd. Victoria Gold Corp. Vista Continental Corp Eaglecrest Exploration Bolivia S.A. Empresa Minera Inti Raymi S.A. Empresa Minera Paititi S.A. Gold production employs over 10 million individuals and could c economic development, but there is great debate over the need to mine for gold. According to Lehman Brothers and Ali 107 the total amount of gold above ground is far larger than the known u nmined reserves. Figure 7. 8 shows that unmined reserves only account for 50,000 tons of the total gold reserves. Non governmental agencies such as Oxfam This campaign encourages con sumers to be cognizant of their behaviors and proactive in market rate for gold increases the rate of mercury use will increase; however, resources are indeed finite so additional measures will need to be taken to address the needs of small scale miners and their families. Fair trade historically applied to agricultural miners with jewe lers 346 The illegality of practices at many small to medium scale operations complic ates support for fair trade Gold and Hilson 346 argue that rather than directly link miners with jewelers, emphasis should be placed on strengthening the small scale mining sector to meet regulations and practices that better benefit them and the environment.

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186 Figure 7. 8 Gold Reserves Above and Below Ground ( M odified from Lehman Br others and Ali 107 ) The field sites in Guyana and Bolivia were mainly in the remote parts of the country, many times close to or in mining areas. In the case of Guyana, the gold mining sites used mercury amalgamat ion methods. Phosphate, titanium and zirconium are the two main mined commodities in Florida, none of them using mercury in the process 330 The Hillsborough R iver, the field site in Tampa, Florida was an urban river with mercury inputs coming mainly from atmospheric deposition (incineration of medical waste and burning of fossil fuels), either directly or through stormwater runoff. The closest mining related activity to the Hillsborough R iver would be phosphate and vermiculite mining, a cement plant and a gypsum plant. Like mines in Guyana and Bolivia, the Floridian mines result in removal of forest cover, chang es in hydrological processes, degradation of river water quality, and release of hazardous materials (e.g. radon and uranium) as a result of tailings exposure. The pollutants released are not considered global pollutants of concern because they are neithe r transported like mercury no r are they as toxic. Proximity of urban communities to these locations, existence of enforceable environmental regulation, and activism of environmental watchdog groups continuously work to ensure more Total Above + Below Ground = 201,000 tons Breakdown of 115,00 0 tons 151 ,000 tons 50 ,000 tons

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187 sustainable practices b y these mines. The mining of phosphate used for agriculture and food production is also probably perceived differently by the public than the mining of gold used to fill the vaults of banks or for individual glorification. Mercury emissions regulations have been established for power plants using a cap and trade design under the 2005 EPA Clean Air Mercury Rule (CAMR). The CAMR takes effect in 2010 and establishes that a 69% overall reduction in emissions be achieved by 2017 347 Legislative processes in the US are strongly influenced by special i nterest s like the utilities. In addition, the laws passed in Florida depend heavily on the political party in power. For Florida, emissions from utilities and incinerators are the main contributors to mercury pollution. This poses a concern for local citizens like those living in East Tampa, some of whom fish in the Hillsborough R iver. In framing the concept of political cohesion, economic sustainability, and community participation as it relates to mercury use and exposure in the Tampa, Florida, one must ask who makes decisions on acceptable pollutant levels, who has access to and can access information to make informed decisions for health protection (e.g. each year the Florida Department of Health posts fish advisory levels for water bodies in Florida on its website, but many minority communities lack access to computers and internet connections) and who is engaged in the development of research agendas to study these phenomena.

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188 Figure 7. 9 V arious P layers W ho I nfluence S ustainability as it is R elated to M ercury U se and E xposure

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189 Figure 7. 9 depicts the various players at the different field sites who influe nce sustainability as it relates to mercury use and exposure. The previous section discussed actions across the gamut of players as they related to po litical cohesion, economic sustainability and community participation. In Section 7.3 the last two sustainability pillars, environmental sustainability and socio cultural impacts, are discussed mainly within the smallest sphere the local community, in Fi gure 7.9 7.3 Environmental Sustainability and Socio Cultural Impacts In this study, environmental sampling and analyses were done to determine mercury loadings and potential exposures to humans. Table 7.5 describes the analytical tests performed in th e various sites described in greater detail in Chapters 3 5. Table 7.5 Environmental A nalysis P erformed a t F ield S ites in the USA, Bolivia and Guyana. Tampa, FL Bolivia Guyana Waterbody Analyzed Hillsborough River Lake Titicaca Essequibo River an d tributaries Media Collected Sediment, water, fish Sediment, water, fish Sediment water Analytical Test CV AFS X R D CV AAS SEM /EDAX B E T CV AFS X R D CV AAS SEM/ EDAX B E T CV AFS XRD C V A A S SEM/ EDAX B E T CVAFS Cold Vapor Atomic Fluorescence Spectromtery; XRD Xray Diffraction; CVAAS Cold Vapor Atomic Absorption Spectrometry; SEM/EDAX Scanning Electron Microscopy/Elemental Analysis; BET Surface Area. Table 7.6 summarize s the results for total mercury in unfiltered water samples and total mercury in sediment samples. Guidelines for mercury to consider are: 1 000 ng/ L for drinking water 348 and 77 0 ng /L for the protection of aquatic life through chronic exposure 190 The unfiltered water samples for the Hillsborough River (0.9 7.8 ng/L) and for Lake Titicaca (44 114 ng/L) measured total mercury concentrations below b oth of these regulatory guidelines Most uncontaminated surface waters usually have total

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190 mercury concentrations below 4 ng/L so the Lake Titicaca samples are high relative to Hillsborough River and high relative to uncontaminated baselines. River water is not drunk directly from the Hillsborough River, but in the communities around Lake Titicaca, untreated river water is a source of drinking water. Water samples were not analyzed for Guyana, but communities there also directly drink river water in addition to rain catchment and well water. Mercury loadings in sediment samples for the sites in Tampa, Guyana and Bolivia ranged from 50 119 ng/g, 29 1200 ng/g, and 132 2891 ng/g respectively. Unmined US basins had total mercury loadings between 0. 9 2480 ng/g 174 The total mercury loadings in the Hillsborough R iver were lower than the loadings observed in the Titicaca area and for most of the Guyana samples, even the remote, unmined, conservation areas li ke Kanashen. Cadwell et al. studied mercury in sediments from arid lands in New Mexico and found that mercury levels were temporal with higher loadings seen during the d ri er seasons 349 This may be a contributing factor to the higher levels of mercury seen in the Titicaca area when compared to Guyana. The higher loadings around Titicaca could also be due to greater use of mercury by miners and worse modes of disposal/r ecovery. According to Bocangel 239 some artisanal miners in Bolivia grind ore with mercury in flowering a greater amount of mercury and extensive dispersal of mercury in the environment with the spent ore. The mines visited in Guyana (1 in Arakaka, 5 in Mahdia) all used sluice boxes with mats for collecting heavy gold containing ore. Mercury application occurred either on the mat (illegal), or in m the amalgam was never observed by our team and questions remain on whether retorts were generally used. Compared to some of the mining practices highlighted by Bocangel 239 in Bolivia less mercury would be used and released from the Guyanese processes. Iwokrama and Konashen would be considered extremely remote, spars ely populated environmen ts with no industrial activity; however, there is a logging industry in Iwokrama Their sediment loadings for mercury range up to ~ 300 ng/g whereas the

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191 highest loading seen in the Hillsborough R iver was 119 ng/g. Samples from som e mining sites in Guyana were surprisingly low and could be due to the nature of the sediment materials or to the fact that mercury was used in such a way that it minimized contamination. Cohen et al. 350 found soil total mercury concentrations across the greater E verglades to range from 2 917 ng/g with the average being 162 ng/g 141 ng/g. Other studies of soils in Florida have found mercury loadings that range from 0.62 430 ng/g with the average being 12.6 34.4 ng/g 351 Sediment Quality Assessment Guidelines (SQAG) for coastal waters in Florida recommend a Threshold Effects Level (TEL) of 130 ng/g and a Probable Effects Level (PEL) of 696 ng/g 352 The TEL represents the upper limit of the range of sediment contaminant concentrations not considered to represent significant hazards to aquatic organisms and the PEL defines the lower limit of the range of contaminant concentrations associated with adverse biological effects. The Hillsborough R iver and Guyana samples, with the exception of a sample from the Phillips Tailings which was 1200 ng/g, would fall below the PEL guideline. There is actually no regulatory limit on sediment mercury loading s but given the complex biogeochemical mercury cycle higher loadings could result in increased availability for consumption by organisms. Drinking water is definitely a route of mercury exposure to animals and humans. Sediments on the other hand would be a route of exposure through absorption through the skin or ingestion (e.g. on improperly washed food). Samples from surface tailings would also be a source of mercury that could potentially contribute to a ir emissions. More important ly, mercury in sediments can be transform ed into mercury loadings in fish. Cohen et al. 350 has correlated total mercury sediment loadings with mercury concentrations in fish and has further justified measuring total mercur y loadings by citing the cost effectiveness of both (n = 600). The consumption of fish is the primary route of exposure to mercury in the world. Patterns of exposure vary by consumption pattern, market values, geographic location,

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192 method of preparatio n, and ethnicity/race whilst concentrations vary by fish species, fish size, and locale (polluted and unpolluted waters, fresh vs. marine, etc.). Fish harvesting in the developed world is composed of 92% marine fish, 5% freshwater, and 3% aquaculture 318 Swain et al. 318 estimated that over one third (85 x 10 6 t) of the global marine harvest enters international trade with fifty percent co ming from developing nations. High value tuna and piscivorous fish usually have higher mercury concentrations in the global markets. Table 7.6 Mercury Results f rom Sites in The USA, Guyana a nd Bolivia Reported for Unfiltered Water Total Mercury (uwthg) and Sediment Total Mercury (sT H g) Location uwTHg (ng/L) sTHg (ng/g) Tampa, Florida (US) Hillsborough River, Tampa, Florida 0.9 7.8 50 119 Guyana (SA) Arakaka Mathews Ridge Port Kaituma Mahdia mine wastes Konashen river and creek sediments Iwokrama river sediments 41 300 190 1200 142 364 29 601 92 301 53 298 Bolivia (SA) Lago Titicaca Rivers and Streams of Lago Titicaca Mine waste and stream (downstream of mine) 44 114 114 132 2891 1568 2891 US Stream 174 unmined bas ns mined basins 0.90 2480 0.84 4520 *No water sample was collected for mine site

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193 Table 7.7 Fish Length (L), Weight (W), and Total M ercury Loading (fTHg) from Tampa, Fl Guyana, and Bolivia. Area Species N L range L avg W range W avg fTHg range fTHg avg (mm) (mm) (g) (g) (mg/kg wet wt) (mg/kg wet wt) Bolivia Pejerrey 10 292 415 336 185 522 298.1 0.20 0.76 0.38 Trucha 10 225 375 299 203 946 496.1 0.03 0.1 0.06 Tampa LMB 20 249 495 347 307 1841 618.1 0.22 0.97 0.56 0.22 BLUE 10 163 209 184 59 183 105.3 0.12 0.24 0.17 0.4 RESU 8 126 243 168 30 262 88.7 0.02 0.21 0.10 0.07 Guyana* Zipfish ** 20 -----0.429 Sunfish ** 13 -----0.276 Various 168 ----0.02 1.034 0.439 *Taken from World Wildlife Fund Guianas and Guyana Institute of Applied Science of Technology Guyana Project Report 353 ** Zipfish is local name for Dora micropeus and Hemiodus unimaculatus *** Sunfish is local name for Crenic ichia lugubris and Cynodon gibbus Total mercury loadings in fish samples are summarized in Table 7.7 for sites in Bolivia, Tampa and Guyana. Fish mercury levels in Florida ranged from 0.02 0.97 mg/kg wet weight with highest levels exhibited in largemo uth bass whilst in Bolivian mercury concentrations were fro m 0.03 to 0.76 mg/kg wet weight with Pejerrey having the highest levels. Mercury loadings in fish usually correlate positively with fish weight, but this was not the case for the Trucha which had lower loadings than Pejerrey despite heavier weights. Using data results from the mining areas of Isseneru and Kurupung in Guyana mercury levels for various species were 0.02 1.034 mg/kg wet w eigh t 353 (average = 0.439 mg/kg wet wt). According to Singh et al 353 90% of the population surveyed in Isseneru can be considered at risk and may display adverse health effects. Section 3.6 discussed t he Hazard Index which relates the mercury loading in fish to the human consumption rate required to ensure there are non cancerous health effects to children and adults

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194 The study of hair mercury loadings amongst an indigenous riverine population close to a n amalgamated gold mining operations in the Bolivian Amazon revealed loadings lower than other Amazonian communities 354 Barbieri et al. 354 (2009) sampled hair from and interviewed 150 members of the area (population of 829) and found that on average they ate 10.5 meals of fish per week with that of childre n aged 1 5 being 12.52 meals per week. Average hair concentrations were 3.02 g/g with the highest found amongst the Garimperos (miners), but still for the most part below the 10 g/g unofficial level used by researchers (The WHO level is 50 g/g) 355 Unfortunately, Barbieri et al. 355 did not report mercury loadings in fish, water or sediment for the c ommunity surveyed. The number of fish meals consumed per week is significantly greater than that observed by the Guyana study discussed above which suggested 3 4 meals of fish per week. One meal per day, per week and per month were all found to represent consumption habits of fisherfolk along the Hillsborough River 177 Table s 7.8 and 7.9 compare the Hazard Index for a given fish mercury loading and also the fish mercury loading that would be required to obtain a Hazard Index of 1 (above 1 would be of concern) assuming a Reference Dose ( RfD ) value of 1 x 10 4 mg/kg day and that one serving of fish is 227 g Table 7.8 Hazard Index (H) and Critical Fish Co ncentration (C) for Children A ssuming H = 1. Calculati ons A ssumed a Rfd = 1 x 10 4 mg/kg d ay fo r D ifferent I ngestion R ates (I, g/day), F ish M ercury C oncentrations (C, mg/kg Wet Weight) and B ody W eight (16 kg for a C hild). Ingestion rates of 8, 32, and 227 g/day correspond to 1 meal per month, week, and day

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195 Table 7. 9. Hazard Index (H) and Critical Fish Co ncentration for Adults (C) A ssuming H = 1. Calculations A ssumed a Rfd = 1 x 10 4 mg/kg d ay fo r Different Ingestion Rates (I, g/day), Fish Mercury C oncentrations (C, mg/kg Wet W eight) and Body W eight (70 kg for an Adult). Ingestion rates of 8, 32, and 227 g/day correspond to 1 meal per month, week, and day. Assuming a consumption rate of 10.5 meals per week (341 g/day), the mercury loading in fish shou ld be 0 for children and 0.02 mg/kg for adults. This ingestion rate has been observed in Bolivia, though not necessarily at the sites tested for this study. Using the average Trucha and Perrejey loadings, the Trucha should be consumed by children at a ra te of ~ 1 meal per week and Perrejey less than once per month. The average weight of a Bolivian adult and child may be different than the values used above. Regardless, the high ingestion rates would raise concerns if common in the areas studied in this research. Using the average LMB loading seen for the Florida site, children should consume LMB less than once a month and adults once a month. For the mercury loadings in fish ranging from 0.1 to 0.56 mg/kg, H>1 for ingestion rates of once per week for bo th children and adults. Many of the fish mercu ry loadings reported in Tables 7.8 and 7.9 fall within this range, suggesting that ingestion rates should be adjusted accordingly to protect human health or fish selection should adjust to favor fish with low er loadings (e.g. trucha vs p errejey or b luefi sh vs LMB). It should also be noted that the serving size for children is probably different from that of adults and this was not considered here however th is can be easily adjusted in Table 7.8. Awareness of mercury in fish and the recommended ingestion rates was beyond the scope of this study. There was no information posted at any of the study sites that discussed fish mercury loadings and human consumption. For non mining indigenous populations like the Wai Wai at Kanashen or the villagers in Fairview, Iwokrama, fishing is part of

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196 the culture and cha nging that to other forms of protein would be complicat ed when compared to mining areas in Guyana where access to the cit y is easier This challenge is not unique to these populations as fishing communities around the world are grappling with chang the light of increased pollutant levels in fish. Other routes of human exposure to mercury do exist and differ according to geographic location and setting (urban or rural in a developed or developing cou ntry). Table 7.10 identifies the main routes of exposure for the different field sites. The environmental sampling conducted for this work is limited to the first row and were discussed above in terms of water and fish. The inhalation and absorption rou tes are based on direct observation and literature review. Figure 7. 10 shows images of mercury storage and use in retorts in a mining site in Guyana. The poster was from the GENCAPD project cosponsored by the Guyana EPA. The retort is placed in a fire a t various locations around the mining site, sometimes closer to where miners live and cook. The mercury is recovered by collecting the vapor under water. With the given retort set up, there are many opportunities for inhalation exposure as the system is not 100% closed. Figure 7. 11 sh ows the open torching of amalgam at a local shop in a Guyanese gold mining area. This would contribute to inhalation exposure for those in close proximity to the burning, including children. It also shows a gold miner hand ling pure mercury by hand at an eating establishment. The mercury is worn on his person for spiritual reasons and contributes to both inhalation and absorption exposure.

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197 Table 7. 10 List of A ctivities that C ontribute to V arious E xposure P athways in S t udy S ites in Bolivia, Guyana and Tampa. Exposure Route Lake Titicaca Bolivia Kanashen, Iwokrama Guyana Tampa, Fl USA Ingestion River water, Fish, Other food River water, Fish, Other food Fish, Other food Inhalation Soil & dumped wa ste emissions, Amalgam burning, Stored mercury Forest fires, Soil & dumped waste emissions, Amalgam burning, Stored mercury, Wood burning stoves in house (Kanashen) Incinerators, Coal Fired Power Plant, Cement manufacture, Landfill emissions, Soil emission s, Phosphate mines, Crematoriums, Religious practices Absorption Soil, Mercury for amalgamation, Handling of mercury containing materials/waste Soil, Mercury for amalgamation, Handling of mercury containing materials/waste Soil, Handling of mercury contai ning materials/waste Figure 7.10 Mercury Use at a M ine in Mahdia, Guyana with P osters D one by the GENCAPD Project in C onjunction with t he Guyana EPA. (A) Mercury is Stored in a Safe Place, (B) A R etort with the A malgam H eated Over a F ire in a C lose d C ontainer and the Vapors Collected Under Water, (C) Retort is Burned in a Fireplace in the Mining C amp.

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198 Figure 7. 11 Pictures from Guyana S howing D irect E xposure to M ercury T hrough (A) Using a B low T orch in an O pen Space to Clean Gold, and (B) Carrying M ercury on P erson for S piritual R easons. Gold mining occurs on almost 50% of indigenous lands 107 and a greater percent occurs on lands that impact the environment of indigenous populations. The technologies empl oyed by artisanal miners in Guyana and Bolivia use mercury to extract precious metals and result in environmental degradation with little effort at reclamation or remediation. Amerindians represent 9% of the population in Guyana and to date own ~14% of th e land in the country which are titled under the State Lands Act, however, criticisms remain on the failure of the government of Guyana to recognize Amerindian land rights in accordance to international provisions 178 In Bolivia, there have been similar sentiments with the Ayamara and Quechua populations though the dynamic s is probably different given indigenous leadership in the form of President Evo Morales. According to the 1999 National Emissions Inventory Database for Hazardous Air Pollutants, mercury emissions for Hillsborough C ounty were estimated to be 1 224.5 0 k g/yr. Advancement in technology has probably lowered this value as the most recent estimates for mercury emissions for the entire state of Florida are 7,500 kg 356 As CAMR takes effect, emissions from the main sources (coal powered fuel plants, incinerators, cement manufacturers) will drop significantly and sources like solid waste landfills which now only contribute 1% of emissions, will account for a larger percentage of emissions. In time, as less mercury is used in our products source emissions from landfills will also decrease. Compared to the Guyana and Bolivia sites, direct handling of mercury by individuals in Tampa is not common nor is inhalation ex posure, although

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199 breakage of mercury continaing bulbs or compact fluorescent lights (CFLs) is increasingly popular within the closed home environment as well as old storage in school science laboratories The levels of mercury found in fish are a health concern for all of the communities studied. Enforcing policy measures may affect the livelihoods of miners, subsistence fisherfolk, and their families. Health according to the World Health Organization is a state of complete physical, mental and socia l well being and not merely the absence of disease or infirmity 357 Mercury bans may not be practical measures of control if m iners are given no other alternatives to generate an income if not equal or greater to then what they receive while working in the mines. This is especially true if gold demand continues to increase as do gold prices. Bans on export s in the US can also c reate leakage A round the world the illegality of mercury use may lead to an increase in the use of time, energy, effort, and resources on criminaliz ing current practices rather than spurring innovation and capacity building. Instead of updating old techn has been the case in Guyana and Bolivia, truly green engineering should be used. Green engineering is defined by Mihelcic and Zimmerman 358 implantation of engineering solutions with an awareness of potential benefits and mining industry, the so ciocultural change needed to reduce the main driver, gold demand, cannot be ignored. 7. 4 Education For all of the sites studied monitoring data on environmental mercury loadings is sparse as is the awareness of local communities on their exposure to m ercury through various pathways. For example, in locations where the smartphone is available a new downloadable (Figure 7.1 2 ) indicates that there probably is an already aware and con cerned global population interested in monitoring and making informed decisions on things that affect

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200 their health and that are within their immediate control. The application collects the latest data on mercury loadings in 125 fish and provides consumpti on guidance based on the consumer characteristics. This application uses a GUI or graphical user interface and allows its users to switch between different guidelines (FDA, EPA, and WHO) and it e fish in question which would be useful for fisherfolk. In Figure 6.1 sustainability and education share the same sphere, the implication being that they are directly intertwined. The pillars of sustainability represent five different areas that must al l be considered in order to assess the most sustainable outcome. Education that addresses and integrates those five pillars plays an important role in reaching the most sustainable outcome. Chapter 6 presented an evolving model for raising environmental awareness in Tampa, increasing community and personal engagement on local issues and forging partnerships through a CBPR process. The model mainly focuses on East Tampa, a distressed urban community that has formally organized its resources to reinvest in and improve the community. The Water Awareness Research and Education (WARE) project is a long term commitment to a partnership that evolves as all participants grow and learn through the work. Based on the partnerships already established in the oth er study sites that enabled the research presented here, Figures 7.1 3 and 7.1 4 extend WARE to Guyanese and Bolivian sites. The figures list the various participants representing the local community, the university and the NGO community. The NGO community has been identified as key players for strengthening civic engagement in developing countries, especially places where actions are highly politicized (Trotz, 2008).

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201 Figure 7.12 A S martphone A Q uantifying M ercury Exposure from F ish. http://www.pcworld.com/appguide/app.html?id=289697&expand=false A ccessed 2/10/10. For immediate implementation, it would be best to work with agencies that have built trusting relationships with the indigenous populations and/or mining communities within each of the area s as well as integrates indigenous culture into the program design. In Guyana, agencies a lready actively involved in the community like the WWF Guianas Conservation International and Iwokrama Center for Biodiversity Research along with university and community officials in the indigenous and mining communities can form a joint collaboration. In Bolivia, ACDI/VOCA, the Universidad Tecnologica Boliviana, AARM, the University of South Florida, health care workers, and the indigenous community (Ayamara and Quecha) would be ideal partners in an effort to increase active participation in modernizing the ancient practices of mining and yet be benefi cial to the economy.

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202 Figure 7.1 3 Potential P artnershi p S tructures with Conservation International (CI) in Guyana Figure 7.1 4 Potential P artnership S tructures for G uyana and B olivia W here Bolivian P artnerships are F aded. COMMUNITY Kanashen/Fair view Leaders Forest Rangers Teachers Students USF/UG Faculty Graduate Students (USF only) Undergraduate Students NGO CI USA CI Guyana Iwokrama COMMUNITY Mine owner Miners Teachers Students Ayamara or Quechua USF/UG Faculty Graduate Students (USF only) Undergraduate Students Undergraduate Students (USF & UTB) Graduate Students (USF & UTB) ORGANIZATIONS WWF Guianas EPA Guyana ACDI VOCA

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203 7.5 Conclusion This c hapter discussed mercury in study sites in Bolivia, Guyana and Tampa, Fl orida three countries that differ in terms of demographics, geography, geology, politics, economics, commerce, and culture. Despite the many differences, mercury occurrence, use and exposure for the sites were discussed in terms of the five different pillars of sustainability and Table s 7.1 1 and 7.12 summarizes the main findings for the different study sites in terms of: (1) economic sustainability, (2) political cohesion, (3) communi ty participation, (4) environmental sustainability, and (5 and 6) socio cultural aspects. Education is a key to integrating the pillars of sustainability to create sustainable solutions and promote sustainable development. Community Based Participatory Research principles capture the sustainability pillars and if implemented correctly have the capacity to generate awareness and action around the issue of sustainability. Based on the experience from the WARE model in Tampa, partnerships for Guyana and Boliv ia were proposed that can implement similar capacity building programs to raise awareness on sustainability, including mercury use, occurrence and exposure.

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204 Table 7.1 1 (A) Summary of M ercury U se, O ccurrence and E xposure in Bolivia Guyana and Tampa, Flo rida as T hey Re late to the F ive P illars of S ustainability. Pillars of Sustainability Bolivia Guyana Tampa, Fl Economic Sustainability High gold prices increase mining activity and mercury use and many artisanal miners inefficiently use mercury and use it in such a way that environmental contamination results. The impact of mercury use on human health (women and children also mine in Bolivia) can decrease the profits made from mining which are few or non existent to begin with. Cooperatives and NGO collabo rations help to devise sustainable solutions for improved mining. High gold prices increase mining activity and mercury use since it is still the most readily available and cheapest way to produce gold for artisanal miners. New rules making mercury use in mining illegal may not stop artisanal miners from using mercury and may criminalize a larger portion of the Guyanese workforce in order to meet new international monitoring mechanisms for forest preservation. CAMR requires utilities and industry to reduc e emissions through implementation of new technology and a mercury export ban is underway. The cost versus effectiveness of these measures at reducing community exposure to mercury is unknown. Political Cohesion Mining cooperatives are engaged and activ e groups who are against mining nationalization and who form cohesive bargaining units. Bolivia has a history of community engagement and activism on unfairness as it relates to basic human needs (e.g. water). Highly politicized environment with minimal, b ut growing, community activism around environmental issues. Various governmental agencies make decisions on mercury, many times special interest lobbying plays a role in outcomes. Minimal engagement of local communities in these decision making processe s. Awareness of some communities on mercury impacts is non existent. East Tampa has a strong community group and serves as a good model for developing CBPR projects that raise awareness on mercury.

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205 Table 7.1 2 (B) Summary of M ercury U se, O ccurrence an d E xposure in Bolivia, Guyana and Tampa, Florida as T hey Relate to the F ive Pillars of S ustainability. Pillars of Sustainability Bolivia Guyana Tampa, Fl Community Participation Mining cooperatives represent a large group of miners though artisanal mine rs who are the most reckless with mercury are not a part of any of the legal ly recognized groups. NGO presence has tried to develop sustainable solutions for mining that require buy in and participation of large groups of individual miners. Top down de cisions clash with local communities and new international funding mechanisms have opened the door for the creation of truly engaged and participatory decision making processes. To date this has not been 100% implemented, especially as it related to fores t communities and miners. NGOs have been instrumental at forging better community participation in all aspects of projects. The WARE project is a model underway for increasing awareness of mercury related issues and in general creating a more engaged publ ic that critically incorporates sustainability concepts into decision making processes. Environmental Sustainability Mercury from mining activities impact ecological, animal and human health Mercury from mining activities and deforestation impact ecologi cal, animal and human health Mercury emissions from utilities account for most local loadings. Socio Cultural Impacts Local customs increase risk of exposure (fish consumption habits, spiritual use) and education through CBPR can potentially allow local communities to make better informed decisions. Local customs increase risk of exposure (fish consumption habits, spiritual use) and education through CBPR can potentially allow local communities to make better informed decisions. Local customs increase ris k of exposure (fish consumption habits) and education through CBPR can potentially allow local communities to make better informed decisions.

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206 CHAPTER 8: CONCLUSION 8.1 Introduction Mercury and concepts of sustainability are mainstream issues that require the active participation and engagement of all members of society to help improve current conditions for future generations. These relationships are quintessential in acquiring, assessing, and disseminating information required to reduce exp osure factors as well as make well informed decisions. This section provides a summary of the experimental results, conclusion, and recommendations for future work. 8.2. Summary of Results and Conclusions The main goal of this research was to improve our understanding of the factors contributing to mercury exposures in three geographically unique locations, Tampa, FL; Mahdia/Iwokrama, Guyana; and Lago Titicaca, Bolivia, and develop community oriented solutions that reduce exposure. The three objective s and summary of the findings for this work have been provided below: Characterize mercury loadings in three previously unmonitored freshwater bodies that represent different geologies, demographics, and regulatory frameworks. 86% of the total mercury loadings in fish collected from the Hillsborough River (Tampa, Florida), warrant an advisory warning if following the US EPA fish consumption guideline especially for largemouth bass Sediments (50 119 ng/g) contained levels highest in areas just after t he dam in the urban reaches but all values were similar to levels found in Florida Bays

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207 In Guyana, the conservation and actively mined areas along t he Essequibo R iver exhibited sediment and soil concentrations ranging from 29 to 1200 ng/g with lower ave rage levels seen in conservation areas. F rom twelve locations in Lago Titicaca and its rivers and streams ( Ro Suches, Ro Al camarini, and mountain streams) w ater and sediment samples were collected. Average mercury loadings in the unfiltered water s wit hin the rivers and streams of Lago Titicaca ranged from 0.3 114 ng/L and sediment loa dings ranged from 24 2891 ng/g. In comparison to other sites, it is suggestive that mercury is of concern for the area. For all sampling sites a positive linear correla tion existed between total mercury in sediment with pH, DO, and turbidity. Compare results and conditions at study sites to determine the role of socioeconomic factors in mercury loadings. The re are varying socioeconomic, regulatory and geopolitical fa ctors within Florida, Bolivia and Guyana ; however, limited to no informational signage exist and mercury hazard index data suggest that children are being under protected Critical adjustments are nee ded within internataional and domestic r egulatory framew ork s to include universal mercury and health guidelines that reduce loop holes in clauses Mercury loadings in fis h from both Bolivia and Florida may cause adverse health effects to residents if consumption rates remain the same and larger predatory fish are consumed Community partnerships and active participation is needed to address issues of sustainability Implement partnerships between education and local community sectors that focus on increasing an awareness of sustainability concepts in a mutuall y beneficial manner that informs on mercury contamination and reduces exposure.

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208 Education is a key to integrating the pillars of sustainability to create sustainable solutions and promote sustainable development. Community Based Participatory Research ( CBPR) principles capture the pillars of sustainability Florida represented the model location for CBPR Suitable local partnerships were identified and have since grown Current partnerships exist with 3 schools and 4 teachers from East and New Tampa (Hillsborough County Public Schools), the City of Tampa Economic and Urban Development, East Tampa Civic and Community leaders, University of South Florida professors and student organization (Engineers for a Sustainable World), 88.5 WMNF radio personaliti es, and the Southwest Florida Water Management District. An environmental c urriculum with a principle focus on stormwater ponds and various special programs were designed with the assistance of various partners The curriculum utilized constructivis m theory of learning and a teaching philosophy of inquiry based learning to p ro vide a broader impact and actively encourage active community participation All stakeholders or partners are quientessential in addressing various avenues of the project; however, there is room for growth and improvement and this is allowable in the design of WARE The WARE program can probably be modified appropriately and be used in Bolivia and Guyana with p otential partners being local non governmental organizations that have built a relationship with the indigenous (ACDI VOCA, Iwokrama, WWF Guianas,) 8.3 Reccomendations for Future W ork Table 8.1 summarizes recoomendations for future work using the five pillars of s ustainabili ty presented in Chapter 7.

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209 Table 8.1. Reccomendations for Future Work Using the Pillars of Sustainability This dissertation has presented several opportunities to conduct additiona l research and build partnerships with in each of the given areas. Table 8.1 summarizes some of the opportunities according to the pillars of sustainability A l ist of recommendations for future work within the context of the area s studied within this wor k are as follows: Tampa, Florida: A regular monitoring program can be established for the Hillsborough River as well as the upper Hillsborough Bay as a joint collaboration between the Florida Department of Environmental Protection and the United States G eological Survey to help expand the data in the South Florida Information Access Program Use regular monitoring programs as a means to educate and actively engage the community to promote sustainability Temporal sampling o f environmental media. Pillar Recommendations Societal (political cohension, sociocultural respect, and community participation) CBPRs be used to create sustainable s olutions and promote sustainable development Improve and expand existing partnerships Universal Health Guideline Develop cyber infrastructure for international and interdisciplinary linkages for CBPR type projects Use principles of cogeneration of knowledg e Environmental Analyze coca, potatoes, cassava (Yucca) and quinoa products for mercury and additional heavy metals to understand Additional sample collection and monitoring to capture temporal variation and more spatial coverage Fish consumption habit s and fish loadings relevant to immigrant communities in the US Economical Use CBPR to reduce mercury consumption Create alternative means of income to reduce Hg exposure Through sustainability education enhance self reflection on individual role (e.g. j ewelry preference) in outcomes and impacts around the world. Extend Life Cycle Analysis approaches to incorporate socio cultural, political and community empowerment indicators.

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210 Improv e existing partnerships within the Hillsborough County School District Develop a road map of mercury in the Tampa area by collecting air and flora samples along the Hillsborough River and Hillsborough Bay Partner with state agencies (e.g. Hillsborough County Environmental Protection Commission, Department of Health, FDEP), film/media specialist, schools, non profit organizations that represent the interest of the communities to promote knowledge and awareness of mercury and other environmental issues G uyana : Work with local agencies to gain access to interior regions and to analyze results in country instead of transporting to US for analysis Survey mining and pristine areas for mercury concentrations in air, water, sediment, and staple products produc ed in vicinity of area Collect and analyze fish for total mercury concentrations Obtain results on worker and community consumption behaviors and exposure to mercury to develop appropriate measures of exposure Bolivia : C ollect additional samples from th e Altiplano Region of Lago Titicaca ensuring that a larger sampling size is obtained Obtain fish samples and water samples from locations where river and streams entering into the lake as well as in the Desagudero. Analyze coca, potatoes, and quinoa pro ducts for mercury and additional heavy metals to understand human health risks Perform community surveys on consumption practices and knowledge of mercury and sustainability to begin to appropriately assess health hazards Develop stronger relationships with ACDI/VOCA and other agencies that work in indigenous communities to build a similar community based participatory program as in Tampa

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246 343. Transparency International, T. Transparency International for 2009 W here the C loser the CorruptionvPerceptions Index (CPI) is to 10 (on a S cale of 0 to 10), the L east C orrupt I t I s Periodical [Online], 2009. http://www.transparency.org/policy_research/surveys_indices/cpi/2009 (accessed March 2010). 344. Blaser et al., Guyana R Plan: Synthesis Review By FCPF Technical Advisory Panel (TAP) In June 8, 2009: 200 9. 345. Jordan, R. W., A. The Bolivian Mining Crisis. Resour Policy 1992, 18, (1) 9 20. 346. Hilson, G., Fair Trade Gold : Antecedents, Prospects and Challenge. Geoforum 2008, 39, (1) 386 400. 347. McCarthy, J. Mercury Emissions from Electric Power Plants: States Are Setting Stricter Limits ; Order Code RL33535; 2006. 348. WHO. Guidelines for Drinking water quality 3rd edition Periodical [Online], 2004. http: // www.who.int/wat er_sanitation_health/dwq/GDWQ2004web.pdf (accessed September 21, 2009 ). 349. Caldwell, C. A.; Canavan, C. M.; Bloom, N. S., Potential E ffects of F orest F ire and S torm F low on T otal M ercury and M ethylmercury in S ediments of an A rid L ands R eservoir. Sci Tot al Environ 2000, 260, (1 3) 125 133. 35 0. Cohen, M. L., S; Osborne, TZ Soil Total Mercury Concentrations Across the Greater Everglades. Soil Sci Soc Am J 2009, 73, (2) 675 685 351. Chen M. M., L.Q.; and Harris, W.G. Baseline Concentrations of 15 Ele ments In Florida Surface Soils. J Environ Qual 1999, 28, 1173 1181. 352. MacDonald, D. D.; Ingersoll, C. G.; Berger, T. A., Development and Evaluation of Consensus Based Sediment Quality Guidelines for Freshwater Ecosystems. Arch Environ Contam Toxicol 200 0, 39, (1) 20 31.

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247 353. Singh, D., Watson, C., Mangal, S. Identification of the S ources and A ssess ment of the L evels of M ercury C ontamination in the Mazaruni B asin in Guyana, I n O rder to R ecommend M itigation Measures ; Technical S ummary S ubmitted to WWF Gui anas. 1999. 354. Barbieri, F. L. G., J. Hair Mercury Levels in Amazonian Populations: Spatial Distribution and Trends. Int J Health Geogr 2009, 8, (71 ) 355. Barbieri, F. C., A; Gardon, J Mercury Exposure in a High Fish Eating Bolivian Amazonian Populati on with Intense Small Scale Gold Mining Activities. Int J Environ Health Res 2009, 19 (4 ) 267 277. 356. Lindberg, S. E.; Southworth, G.; Prestbo, E. M.; Wallschlager, D.; Bogle, M. A.; Price, J., Gaseous M ethyl and I norganic M ercury in L andfill G as fro m L andfills in Florida, Minnesota, Delaware, and California. Atmos Environ 2005 39, (2) 249 258. 357. WHO. Frequently asked questions: What is the WHO D enifition of H ealth? Periodical [Online], 2010. http://www.who.int/suggestions/faq/en/index.html (accessed January 2010). 358. Mihelcic, J. R., Crittenden, J.C., Small, M.J., Shonnard, D.R., Hokanson, D.R., Zhang, Q., Chen, H., Sorby, S.A., James, V.U., Sutherland, J.W., Schnoor, J.L. Sustai nability Science and Engineering: The Emergence of a New Metadiscipline Environ Sci Technol 2003, 37, 5314 5324.

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248 Appendices

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249 Appendix A: Equipment and Supplies List. Table A 1. Catalog and Price List for Sampling Supplies and Field Equ ipment Item Detail Company Qty Price Cat # Silicone Tubing Fisher 2 $39.70 ` Teflon Tubing (1/8 in x 3/16 in) (case of 2 $52.92) Fisher 2 39.70 8050 0187 Cole Parmer C Flex Tubing (3/8 in x 5/8 in) Fisher 2 76.96 NC 9781223 Whatman Polycap Filt ers (0.45m) (assuming 1 filter/sample) Gelman AquaPrep Filter Fisher Fisher 24 Or 24 19.35/ea 30.08/ea ($258.50/case of 10) 05 714 036 12176 (Gelman #); GWSC04510 (Fisher #) Plastic Storage Bags Fisher 1 1 110.18 45.96 01 816 1E (9x12) 01 816 1 D (5x8) 500 mL disposable glass bottles (case of 12) Fisher 2 25.86 (Alternate) 24.15 02 912 013 (Alternate) 05 719 171 Solinst Portable Peristaltic Pump Fisher Solinst 1 999.00 NC9611459 Model #410 Extra Battery Werker 12V 5AH AGM Battery W/ .187 Terminal WKA12 5F Batteries Plus 1 29.99 WKA12 5F LaMotte Water Sampler Model JT 1 (Vandorn water sampler) Fisher LaMotte 1 205.58 S45085J CODE1077 Ekman Bottom Grab Sampler Wildco 1 485.00 196 B12 Standard w/case Quanta Hydro lab Hach 1 45 00.00 Stainless Steel Bowl Wal Mart 1 9.96 Durapet: Stainless Steel Pet Bowl, 1ct Stainless Steel Scooper Wal Mart 1 4.96 Trimble Ranger Handheld GPS Garmin GPSMAP 76S Trimble Walmart 1 1 $5500 w/case $299.00 Includes warranty and base maps for SA,NA,CA Powder Free Nitrile gloves (1 pk = 100 gloves) Fisher 2 2 9.27 9.26 19 130 1597C (M) 19 130 1597B (S) Marking Pens Fisher 1 13.73 13 379 4 (black) Clipboard w/storage Wal Mart 1 18.99 Waterproof Field Notebook (alter native: Nalgene* PolyPaper* Pocket Data Books; 1 pk. = 4) Fisher 2 (1) 52.40 (70.04/pk) 6303 1000 (alt: 6306 0500) Potassium Bromate (ACS Reagent Grade) (5g) Fisher 1 13.47 AC424070050 Potassium Bromide (ACS R Grade) (500g) Fisher 1 70.15 AA4001336 Hydrochloric Acid (ACS Plus) (500 mL) Fisher 1 14.75 A144 212 Eppendorf Pipette 100 1000 uL Fisher 1 221.90 05 402 90 Eppendorf Pipette 500 5000 uL Fisher 1 222.19 05 402 91 Eppendorf pipette tips 100 1000 uL Fisher 1 49.85 05 403 68 Eppendorf pip ette tips 500 5000 uL Fisher 1 21.77 05 403 29 Turbidity Standard 40 NTU Hach 1 122.01 NC9943238 Conductivity/TDS Standard, 500S/cm Hach 1 13.18 224132 Conductivity Standard, 150 mS/cm Hach 1 26.29 22491532 Turbidity Standard, 10 NTU Hach 1 62.48 R8 8010004C

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250 Appendix B : SOP for CVAAS and Analytical Parameters CVAAS MERCURY ANALYS IS STANDARD OPERATING PROCEDURE (SOP) Safety Guidelines In compliance with the USF Division of Environmental Health and Safety Agreement soil/sediment and biological sam ples should be handled accordingly. All samples must be handled with care due to strict USDA and USF guidelines. In addition, mercury compounds are highly toxic if inhaled, swallowed, or absorbed through the skin; therefore laboratory safety and field sa fety measures must be adhered to at all times. Appropriate attire should be worn when handling mercury or potentially mercury contaminated samples from all matrices. Proper attire includes the following: Lab coat Gloves/Protective eye gear Closed toed s hoes Long pants Nasal/Mouth Mask While in the laboratory all samples should be handled under the ventilation/fume hood at all times. Work surfaces/areas must be cleaned. Note: Untreated samples should not be retained longer than 12 months from receipt un less proper authorization has been granted from PPQ .* According to the USDA Compliance Agreement (details are outlined in the Foreign and Domestic Soils SOP Manual ) all foreign and domestic soil samples must be stored and locked at all times in the secu rely locked freezer in ENB 227A

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251 Appendix B Continued Storage Regulations According to the United States Department of Agriculture Animal and Plant Health Inspection Services the following guidelines must be adhered to when shipping domestic and fore ign samples to the Civil and Environmental Engineering Department at the University of South Florida I n preparation for the shipment of foreign soil samples to the University of South Florida the following must be followed: 1. Individual soil samples must be stored in doubly bagged and sealed Ziploc or other tightly closed, doubly contained containers. The samples must then be contained in a sturdy, leak proof container (i.e. a cooler) to prohibit the possible spillage or escape of pest while in transit to the university. 2. Samples should be labeled and accompanied with a copy of the Soil Permit and have a PPQ Form 550 clearly displayed on it as follows: 3. All foreign and domestic soil shipments must be sent via a bonded carrier Samples from Guyana will be shipped by via Fedex in Guyana. The port of entry in the US will be Memphis or Miami. 4. Record Soil Shipments in binder kept in KOPP 227A. O nce samples are received and properly stored d econtaminate shipment containers. Mercury Stan dards and Reagents A ll standards and reagents have been outlined below: Reagent Water: Reagent Referenced as water in method. o 5%HCl or 5% HNO 3

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252 Appendix B Continued Aqua Regia: (soil digestion) *Prepare immediately before use.* Add volume of 3:1 concen trated HCl to concentrated HNO 3 Sulfuric acid, 0.5 N: Dilute 14.0 mL of concentrated H 2 SO 4 to 1L. Stannous sulfate: (CVAA) Add 25 g stannous sulfate to 250 mL of 0.5 N H 2 SO 4 This mixture is a suspension and should be stirred continuously during use. A 10% solution of stannous chloride can be substituted for stannous sulfate. Sodium chloride hydroxylamine sulfate solution: (soil digestion) Dissolve 12 g of sodium chloride and 12 g of hydroxylamine sulfate in reagent water and dilute to 100 mL. *Hydrox ylamine hydrochloride (NaCl/NH 2 OH) may be used in place of hydroxylamine sulfate.* Potassium permanganate, mercury free, 5% solution (w/v): (soil digestion) o Dissolve 5 g of potassium permanganate in 100 mL of ultra pure deionized water (DI water with resi Ultra Stock mercury standard NIST certified 10,000 ppb aqueous Hg solution (NIST 3133).

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253 Appendix B Continued Standards Preparation All standards should be taken through the digestion process even if using the EPA Method 6971 Modified by Environmental Express for use with there digestion bottles. Take the 10,000 ppb stock aqueous Hg solution (NIST 3133) and dilute it down to 500 ppb Hg using the reagent water (5% HCl or 5% HNO 3 ; however be consist ent) in a 100 mL flask Using the 500 ppb Hg working solution make dilutions to obtain 350 ppb, 250 ppb, 150 ppb, 100 ppb, 50 ppb, and 25 ppb. Follow the aforementioned method. However, a smaller flask size can be used (i.e. 10 mL; however, please be advi sed there is a higher error associated with smaller sizes and is not recommended). Interferences with CV AAS Analysis I nterferences and contamination of water samples may occur. The following list describes the potential hindrance to total mercury resul ts: Waters containing sulfide, chloride, copper and tellurium (concentration levels unknown) Copper Only concentrations as high as 10 mg/Kg have no effect on recovery of mercury from spiked samples. Chlorides high concentrations require additional pe rmanganate (as much as 25 mL) due to the oxidation steps conversion of chloride to free chlorine, which also absorbs radiation of 253 nm.

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254 Appendix B Continued Reduced by using excess hydroxylamine sulfate reagent (25 mL) or purging dead air space in th e digestion vessel before adding stannous sulfate (or stannous chloride) Organic compounds (broad band UV absorbance ~253.7 nm) Volatile materials (e.g., chlorine) that absorb at 253.7 nm will cause a positive interference. To remove any interfering vol atile materials, dead air space in the digestion vessel should be purged before addition of stannous chloride solution. Potassium permanganate is added to eliminate possible interference from sulfide. Concentrations as high as 20 mg/Kg of sulfide, as sodiu m sulfide, do not interfere with the recovery of added inorganic mercury in reagent water. Low level mercury sample preparation, digestion, and analysis may be subject to environmental contamination if preformed in areas with high ambient backgrounds (i.e locations where mercury was previously employed as an analytical reagent in analyses such as total Kjeldahl nitrogen (TKN) or chemical oxygen demand (COD)) Mercury Standard Methods T he following is a condensed version of the digestion procedure for me rcury using the plastic digestion tubes from Environmental Express. The procedure is based on EPA Methods 245.1 and 7470. EPA Method 245.1 is applicable for aqueous samples and TCLP extracts. The procedure for hair, soils, oils, and sediments are based on EPA Method 7471. Only sample preparation steps are outlined below:

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255 Appendix B Continued Oils, Hair, Soils, and Sediments : Add 30 mL of each standard solution or appropriate amount of standard spiking solution to give desired concentration when diluted to 30 mL to environmental express 100 mL digestion vessel. The standards should be made in 3% HNO 3 Weigh 0.60 0.05 g of homogenized sample into a tube. Add 30 mL of 3% HNO 3 solution T o each tube add 0.5 mL of concentrated HNO 3 and 2.0 mL of concentrate d HCl Lay cap on tube and digest at 95C for 10 minutes. Add 3 mL of 5% KmnO 4 and let stand for 15 minutes. If sample does not maintain purple or brown color, add an additional 3 mL of KMnO 4 solutions to all samples, blanks and standards. If the sample sti ll does not maintain color, discard set and dilute the sample prior to digestion. Heat samples at 95C for 30 minutes. Let samples cool to room temperature and add 3.0 mL of 12% NaCl/NH 2 OH solution. Cap tubes and shake. If color does not dissipate, inc rementally add 0.5 mL of 12% NaCl/NH 2 OH solution until color is gone. Analyze using the Varian 240FS/VGA77

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256 Appendix B Continued Table B 1. Analytical Parameters for Varian 240FS/VGAA7 7 CVAAS Parameters (Varian 240FS) Wavelength (nm) 253.7 Slit Width (nm) 0.5 Lamp Current 4 Integration time (s) 3 Vapor Generator (VGA 77) Acid uptake tube (mL/min) 1 Reductant uptake tube (mL/min) 1 Sample uptake tube (mL/min) 8 Argon* or Nitrogen Gas 99.99% pure Permissible pressure range*** 43 57 psi Reagents Usage 5% Hydrochloric Acid, (from concentrated) Acid Line, Reagent Water*, Preservation* 20% (w/v) Stannous Chloride Reductant Line 5% Nitric Acid, concentrated** Reagent water, preservation Notes: used in this study ** sug gested (Varian, 1985) *** recommended pressure is 50 psi

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257 Appendix C: SOP for CVAFS and Analytical Parameters CVAFS MERCURY ANALYS IS STANDARD OPERATING PROCEDURE (SOP) Water: Pour 100 mL aliquot of preserved sample into a 125 mL fluropolymer container. Add BrCl was not added as preservative add accordingly Clear water & filtered samples add 0.5mL of BrCl Brown water and turbid samples add 1.0 mL BrCl If yellow color disappears because of consumption of organic matter or sulfides add more Br Cl until permanent (12 h) yellow color is obtained Digest at room temperature for 2 hours in UV cabinet Please see Method 1631 or equipment guidelines for reduction and purging preparation procedures Analyze following FDEP Method 1631 Tissue, Sludge, Sedi ment, and Soil: Sediment and soil samples should be sieved through ASTM certified sieves Digestion by hot re fluxing HNO 3 /H2SO 4 followed by BrCl oxidation will be conducted for biota, wood, paper, tissue, municipal sludge, other primarily organic matrices (excluding coal) Weigh the required amount into a digestion vessel Table C 1 Mass of Sample Required for Analytical Testing for CVAFS Analysis. Matrix Required Mass Biota 0.2 0.4 g tissue (e.g. fish), plant material, or sludge 0.5 1.5 g Wood, paper, and CRMs 0.2 0.4 g Under fume hood, add 8.0 mL concentrated HCl and swirl

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258 Appendix C Continued Add 2.0 mL HNO 3 and cap the vessel. Allow to digest at room temperature for 4 hours or overnight Table C 2 Method Parameters for Tekran Model 2600 CVAFS Te kran Model 2600 Method Parameters # Start Cmd Command Value Duration End Time Note 0 4 12 MFC 100 ml/min 600 604 MFC: 100 ml 1 4 11 Pump 20% 600 604 Pump: 20% 2 4 8 V4: WashPmp ON 600 604 Wash Pump ON 3 5 5 V1:Vent ON 190 195 V1: Vent A 4 7 21 A/S Up 5Spd 0 7 A/S Up 5 8 22 A/S Move Sample Tube 2 10 A/S Move to 6 9 24 A/S Down 5Spd 0 9 A/S Down 7 125 6 V2:Load A ON 60 185 V2: Load ON 8 145 21 A/S Up 5Spd 0 145 A/S Up 9 146 22 A/S Move ON 3 149 A/S Move 10 147 24 A/S Down 5Spd 4 151 A/S Down 11 2 00 1 Heater A 85% 30 230 Heater A: 85% 12 205 21 A/S Up 5Spd 2 207 A/S Up 13 206 22 A/S Move Wash Stn 3 209 A/S Move 14 20 24 A/S Down 5Spd 4 211 A/S Down 15 7230 3 Fan A ON 35 265 Fan A ON 16 265 1 Heater A 0% 80 345 Heater A: 0% 17 265 2 Heater B 1 00% 30 295 Heater B: 100% 18 275 14 AD24 Start 100% 50 325 AD24 Start 19 340 4 Fan B ON 40 380 Fan B ON 20 355 20 Done Done 0 355 Done

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259 Appendix D: Analytical Parameters for Bruker D4 Endeavor XRD Table D 1 Analytical Parameters for Bruker D4 End eavor XRD Scans Operator Operator Setting Value Raw Data Origin BRUKER binary V3 (.RAW) Scan Axis Gonio Start Position [2Th.] 2.0000 End Position [2Th.] 120.0000 Step Size [2Th.] 0.0250 Scan Step Time [s] 2.0003 Scan Type CONTINUOUS Offset [2T h.] 0.0000 Divergence Slit Type Fixed Divergence Slit Size [] 0.2000 Specimen Length [mm] 10.00 Receiving Slit Size [mm] 0.1000 Measurement Temperature [C] 25.00 Anode Material Cu Generator Settings 40 kV, 40 mA Diffractometer Type Unknown Gonio meter Radius [mm] 200.50 Dist. Focus Diverg. Slit [mm] 91.00 Incident Beam Monochromator No Spinning No

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260 A ppendix E : Standards Preparation Procedure All standards were made on a weight basis in 100 mL PTFE (teflon) bottles and diluted with DI water The minimum concentration that can be analyzed was 0.5 ppt and the maximum 250 ppt. Table E 1 Standards Preparation Procedures for CVAAS Analysis Concentration (ppt) 1 ppb Hg Stock Required (uL) DI required (mL) 0.5 50 100 2 200 99.8 3 300 99.7 5 500 99.5 10 1000 99 15 1500 98.5 20 2000 98 30 3000 97 50 5000 95 100 10 000 90 200 20 000 80 250 25 000 75 *Note: Samples should be diluted with DI only. Formula: C stock V stock = C desired *V flask Ex. 1: 0.5 ppt Hg desired 1 000 ppt V stock mL = 0.5 ppt 100 mL V stock mL = 50/ 1 000 = 0.05mL V stock uL = 0.05 mL 1000 uL/mL V stock = 50 uL therefore, 50 uL of 1 ppb Hg working stock is required. 1 ppb = 1 000 ppt*

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261 A ppendix F : Cleaning Procedures Containers used to store the reagents a re cleaned thoroughly with solutions of 5% Aqua Regia and distilled water before use. All containers are rinsed twice with this acid solution, followed by rinsing with de ionized water at least six times. All beakers, measuring cylinders, volumetric flasks glass pipettes and plastic pipette tips (Eppendorf) are also subject to the same cleaning procedure before use. Narrow mouth 60 and 125 mL Teflon (FEP) bottles with leak proof Tefzel caps are used to digest the preserved samples for digestion. The bottle s are cleaned with 5% Aqua Regia solution to the brim, capped, and stored under the UV cabinet for at least 24 hours prior to use. The bottles are emptied and rinsed thoroughly with distilled water, (at least six times) before use. The Tefzel caps are also treated with the same degree of cleaning.

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262 A ppendix G : Fish Data Results Table G 1 2008 Hillsborough River, Florida Total Fish Mercury Levels Extended Large Mouth Bass (Micropterus salmoides) Red Sunfish (Red Drum) # Age THg (mg/kg) Length (mm) *Fi sh Body Condition Weight (g) # Age THg Length (mm) *Fish Body Condition Weight (g) 1 2 0.27 249 1.19 184 31 -0.20 144 1.07 32 2 3 0.29 295 1.20 307 32 -0.04 143 1.20 35 3 3 0.28 309 1.20 353 33 -0.06 126 1.50 30 4 5 0.35 323 1.18 398 34 -0.13 1 30 1.50 33 5 6 0.39 356 1.28 577 35 -0.02 180 1.47 86 6 4 0.22 333 1.24 459 36 -0.03 175 1.40 75 7 4 0.42 337 1.33 509 37 -0.21 205 1.74 150 8 3 0.62 296 1.27 330 38 -0.09 243 1.83 262 9 3 0.55 291 1.34 331 Bluefish (Pomatomus saltatrix ) 10 3 0.65 310 1.15 342 # Age THg Length (mm) *Fish Body Condition Weight (g) 11 3 0.62 337 1.12 428 21 -0.15 168 1.24 59 12 3 0.67 315 1.23 386 22 -0.19 190 1.90 130 13 5 0.70 358 1.35 620 23 -0.13 191 1.71 119 14 3 0.75 313 1.09 335 24 -0.21 209 2 .00 183 15 4 0.65 358 1.33 610 25 -0.13 163 1.59 69 16 4 0.54 372 1.35 697 26 -0.15 195 1.42 105 17 4 0.53 410 1.28 879 27 -0.24 170 1.71 84 18 6 0.92 411 1.28 886 28 -0.15 188 1.58 105 19 6 0.88 469 1.41 1452.5 29 -0.20 185 1.64 104 20 6 0 .97 495 1.52 1841 30 -0.12 179 1.66 95

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263 Appendix G Continued Table G 2. 2003 Historical Fish Mercury Data for Hillsborough River, Florida. ( Collected and analyz ed by FFWCC and FDEP Da ta Re sults provided by Mr. Doug A dam s and Te d L ange ) 2003 Historical Fish Data Results LABID Dat e Sampled Species TL TW AGE SEX THg (DEP) 303047 3/26/2003 LMB 257 234 1 M 0.650 303048 3/26/2003 LMB 272 305 2 M 0.580 303049 3/26/2003 LMB 289 347 2 M 0.360 303050 3/26/2003 LMB 287 303 2 M 0.540 303051 3/26/2003 LMB 277 304 2 M 0.390 303052 3/26/2 003 LMB 316 415 2 M 0.430 303053 3/26/2003 LMB 332 528 2 M 0.360 303054 3/26/2003 LMB 292 397 2 M 0.470 303055 3/26/2003 LMB 338 626 3 F 0.520 303056 3/26/2003 LMB 327 501 3 M 0.590 303057 3/26/2003 LMB 334 543 4 M 0.500 303058 3/26/2003 LMB 353 663 3 M 0.520 303059 3/26/2003 LMB 376 771 6 M 0.690 303060 3/26/2003 LMB 364 668 6 M 0.680 303061 3/26/2003 LMB 402 949 5 F 0.700 303062 3/26/2003 LMB 388 904 6 M 0.650 303063 3/26/2003 LMB 396 838 8 M 0.740 303064 3/26/2003 LMB 458 1356 4 F 0.610 3030 65 3/26/2003 LMB 428 1272 5 F 0.530 303066 3/26/2003 LMB 487 1661 4 F 0.450

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264 Appendix G Continued Table G 3 200 4 Historical Fish Mercury Data for Hillsborough River, Florida. ( Collected and analyz ed by FFWCC and FDEP Da ta Re sults provided by Mr. Doug A dam s and Te d L ange ) 2004 Historical Fish Data Results LABID Date Sampl ed Species TL TW AGE SEX THg (DEP) 304084 3/24/2004 LMB 320 444 2 M 0.650 304085 3/24/2004 LMB 305 388 3 M 0.770 304086 3/24/2004 LMB 309 421 2 M 0.890 304087 3/24/2004 LMB 263 240 2 M 0.910 304088 3/24/2004 LMB 299 357 2 M 0.810 304089 3/24/2004 LMB 262 273 2 M 0.890 304090 3/24/2004 LMB 316 373 2 F 0.750 304091 3/24/2004 LMB 285 298 2 M 1.100 304092 3/24/2004 LMB 243 179 2 F 0.800 304093 3/24/2004 LMB 280 299 2 F 0.900 304094 3/24/2004 LMB 257 199 2 M 0.850 304095 3/24/2004 LMB 319 422 3 M 0.7 60 304096 3/24/2004 LMB 324 435 2 M 0.660 304097 3/24/2004 LMB 247 189 2 F 0.920 304098 3/24/2004 LMB 237 166 2 M 0.960 304099 3/24/2004 LMB 351 587 2 M 0.920 304100 3/24/2004 LMB 391 849 7 M 1.100 304101 3/24/2004 LMB 374 805 7 M 1.100 304102 3/24/ 2004 LMB 432 1205 7 M 1.300 304103 3/24/2004 LMB 489 1836 7 F 1.200

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265 Appendix G Continued Table G 4. 200 5 Historical Fish Mercury Data for Hillsborough River, Florida. ( Collected and analyz ed by FFWCC and FDEP Da ta Re sults provided by Mr. Doug A dam s and Te d L ange ) 2005 Historical Fish Data Results LABID Date Sampled Speci es TL TW AGE SEX THg (DEP) 105127 1/27/2005 LMB 473 1745 4 F 0.850 105128 1/27/2005 LMB 295 348 3 M 0.700 105129 1/27/2005 LMB 351 591 3 F 0.740 105130 1/27/2005 LMB 381 798 4 M 0.990 105131 1/27/2005 LMB 350 603 3 M 0.870 105132 1/27/2005 LMB 432 14 12 4 M 0.780 105133 1/27/2005 LMB 406 1240 4 M 0.820 105134 1/27/2005 LMB 408 1208 3 F 0.740 105135 1/27/2005 LMB 367 884 4 M 0.810 105136 1/27/2005 LMB 366 754 4 M 0.960 105137 1/27/2005 LMB 405 1046 3 F 0.740 105138 1/27/2005 LMB 335 530 3 M 0.820 105139 1/27/2005 LMB 331 558 3 M 0.810 105140 1/27/2005 LMB 323 544 3 M 0.520 105141 1/27/2005 LMB 357 723 3 M 0.890 105142 1/27/2005 LMB 375 737 3 M 0.880 105143 1/27/2005 LMB 293 337 3 F 0.610 105144 1/27/2005 LMB 287 309 3 M 0.850 105145 1/27/200 5 LMB 314 397 3 F 0.720 105146 1/27/2005 LMB 259 187 2 F 0.550

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266 Appendix G Continued Table G 5. 2006 Historical Fish Mercury Data for Hillsborough River, Florida. ( Collected and anal yz ed by FFWCC and FD EP. Results Provided by D A dams ) 2006 Historical Fish Data Results LABID Date Sampled Species TL TW AGE SEX THg (DEP) LAB ID Species TL TW AGE SEX THg (DEP) 306008 3/15/2006 LMB 315 401 4 M 0.990 306055 RBSU 168 73 --0.180 306009 3/15/2006 LMB 322 438 4 M 0.930 306056 RBSU 162 72 --0.160 306010 3/15/2006 LMB 329 527 4 M 0.900 306057 RBSU 165 79 --0.200 3060 11 3/15/2006 LMB 321 530 4 M 1.100 306058 RBSU 171 93 --0.320 306012 3/15/2006 LMB 375 729 4 F 0.770 306059 RBSU 176 94 --0.270 306013 3/15/2006 LMB 357 691 5 M 0.970 306060 RBSU 182 105 --0.180 306014 3/15/2006 LMB 272 271 3 F 0.690 306 061 RBSU 198 147 --0.190 306015 3/15/2006 LMB 343 612 4 M 1.200 306062 SPSU 145 71 --0.700 306016 3/15/2006 LMB 346 552 4 M 0.940 306063 SPSU 148 73 --0.360 306017 3/15/2006 LMB 327 450 4 F 0.830 306064 SPSU 152 86 --0.410 306018 3/1 5/2006 LMB 337 524 4 F 0.850 306065 SPSU 153 79 --0.670 306019 3/15/2006 LMB 251 230 3 F 0.810 306066 SPSU 152 91 --0.170 306020 3/15/2006 LMB 328 480 4 M 0.920 306067 SPSU 155 94 --0.230 306021 3/15/2006 LMB 221 135 2 M 0.640 306068 SPS U 161 102 --0.350 306022 3/15/2006 LMB 291 327 3 M 0.790 306069 SPSU 170 108 --0.550 306023 3/15/2006 LMB 281 257 3 M 0.890 306070 SPSU 163 97 --0.410 306024 3/15/2006 LMB 406 1062 4 F 0.870 306071 SPSU 164 100 --0.380 306025 3/15/20 06 LMB 395 848 4 F 0.840 306072 SPSU 167 125 --0.480 306026 3/15/2006 LMB 388 777 4 F 0.700 306073 SPSU 168 122 --0.290 306027 3/15/2006 LMB 411 1156 4 F 0.980 306074 WAR 172 128 --0.410 306038 3/15/2006 RESU 196 154 --0.230 306075 W AR 166 111 --0.410 306039 3/15/2006 RESU 189 127 --0.370 306076 WAR 165 104 --0.370 306040 3/15/2006 RESU 193 159 --0.270 306077 WAR 166 116 --0.520 306041 3/15/2006 RESU 225 246 --0.250 306078 WAR 178 142 --0.410 306042 3/15/2006 RESU 222 239 --0.500 306079 WAR 176 147 --0.630 306043 3/15/2006 RESU 212 223 --0.390 306080 WAR 178 149 --0.510 306044 3/15/2006 RESU 215 214 --0.320 306081 WAR 180 147 --0.600 306045 3/15/2006 RESU 231 295 --0. 430 306082 WAR 200 205 --0.540 306046 3/15/2006 RESU 273 525 --0.430 306083 WAR 175 146 --0.500 306047 3/15/2006 RESU 173 99 --0.240 306084 WAR 205 243 --0.700 306048 3/15/2006 RESU 182 120 --0.270 306085 WAR 211 240 --0. 570 306049 3/15/2006 RESU 161 83 --0.130 306086 BLUE 156 60 --0.370 306050 3/15/2006 RBSU 152 55 --0.120 306087 BLUE 181 114 --0.240 306051 3/15/2006 RBSU 152 65 --0.110 306088 BLUE 192 140 --0.440 306052 3/15/2006 RBSU 150 5 7 --0.110 306089 BLUE 187 125 --0.200 306053 3/15/2006 RBSU 146 58 --0.180 306090 BLUE 200 163 --0.290 306054 3/15/2006 RBSU 144 49 --0.140 306091 BLUE 206 209 --0.500 266

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267 Appendix G Continued Table G 6 Historical Fish Mercury Data for Hillsborough River, Florida. ( Collected and analyz ed by FFWCC and FDEP Da ta Re sults provided by Mr. Doug A dam s and Te d L ange ) 2007 Historical Data Results LABID Date Sampled Species TL TW AGE SEX THg (DEP) 507001 5/2/2007 LMB 242 176 3 M 0.5 507002 5/2/2007 LMB 283 269 3 F 0.73 507003 5/2/200 7 LMB 308 378 4 M 0.88 507004 5/2/2007 LMB 297 329 3 F 0.75 507005 5/2/2007 LMB 316 372 5 M 0.93 507006 5/2/2007 LMB 304 346 4 M 0.95 507007 5/2/2007 LMB 305 365 3 F 0.76 507008 5/2/2007 LMB 301 349 3 F 0.75 507009 5/2/2007 LMB 317 390 3 F 0.81 5070 10 5/2/2007 LMB 314 412 5 M 1.2 507011 5/2/2007 LMB 312 362 3 F 0.93 507012 5/2/2007 LMB 358 567 5 M 1.2 507013 5/2/2007 LMB 328 450 5 M 0.86 507014 5/2/2007 LMB 389 919 5 F 1 507015 5/2/2007 LMB 432 1080 5 F 1.2 507016 5/2/2007 LMB 297 330 3 M 0.64 507017 5/2/2007 LMB 224 141 2 F 0.7 507018 5/2/2007 LMB 389 931 5 F 0.64 507019 5/2/2007 LMB 438 1195 5 F 1.1 507020 5/2/2007 LMB 474 1519 6 F 1.4

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268 Appendix G Continued Table G 7. 2009 Historical Fish Mercury Data for Bolivia (Analyzed in Bolivia) 2009 Bolivia Fish Results LABID Sample ID Length Weight *Fish Body Condition Sex fTHg wet weight (mm) (g) (K) (M/F) (mg/kg) Trucha (Salmo gaidneri, n = 10) 26 1 1 TG 365 834 1.7 M 0.1 0 26 2 2 TG 355 731 1.6 F 0.04 26 3 3TG 375 946 1.8 M 0.09 26 4 4TG 334 654 1.8 F 0.05 26 5 5TG 346 680 1.6 F 0.04 26 6 6 TP 225 210 1.8 M 0.0 6 26 7 7 TP 232 203 1.6 M 0.0 7 26 8 8 TP 24 6 218 1.5 F 0.0 3 26 9 9 TP 250 247 1.6 M 0.0 4 26 10 10 TP 260 238 1.4 F 0.0 4 Average 29 9 496 1.9 M(5); F(5) Peje rrey (Basilichthyes bonariensi, n = 10) 26 11 1 PG 382 418 0.7 M 0.43 26 12 2 PG 356 295 0.7 F 0.63 26 13 3 PG 297 209 0.8 M 0.27 26 14 4 PG 362 423 0.9 F 0.23 26 15 5 PG 415 522 0.7 M 0.76 26 16 6 PP 300 219 0.8 F 0.58 26 17 7 PP 313 211 0.7 M 0 .22 26 18 8 PP 335 283 0.8 M 0.25 26 19 9 PP 305 185 0.7 M 0.23 26 20 10 PP 292 216 0. 9 M 0.2 0 Average 33 6 298 0.8 M(7); F(3) 0.38

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269 Appendix H : Field Notes and Water Quality Data Table H 1. Guyana (Mahdia) Water Quality, Total Mercury Concentr ations and Field Notes Sample Name [THg] (g/kg) Temperature (C) Conductivity (mS/cm) DO (mg/L) DO Sat (%) pH TDS (g/L) Turbidity (NTU) Salinity (ppt) ORP UTM Coordinates Elevation (m) Notes Mine 1 11 331 27.78 0.058 6.59 86 4.28 0 47.7 0.03 99 T ailings from hydraulic pump motor 12 127 27.78 0.058 6.59 86 4.28 0 47.7 0.03 99 N05.38023 W059.13596 90 Near sluice box 12B 143 27.78 0.058 6.59 86 4.28 0 47.7 0.03 99 12C 81 27.78 0.058 6.59 86 4.28 0 47.7 0.03 99 12D 134 27.78 0.058 6.59 86 4.28 0 47.7 0.03 99 Dio's Smp 114 27.78 0.058 6.59 86 4.28 0 47.7 0.03 99 At mine entrance Mine 2 Top Soil 253 Top soil of pit; close to land dredging Top Soil B 111 Topsoil of pit opposite Top so il A; close to land dredging 14 29 29.8 0.106 7.33 90.2 3.85 0 14.5 0.005 139 N05.29134 W059.13186 83 recirculation water 14B 150 29.06 0.104 7.25 93.4 4.07 0 12.3 0.5 142 N05.29117 W059.13206 79 15 222 28.49 0.288 3.87 3.51 3.51 0.2 178 0.14 290 N 05.28982 W059.13229 By tailings 16 49 29.62 0.06 5.95 73.7 4.25 0 14.6 0.03 113 N05.29007 W059.13061 80 Bottom of pit water going into pit from higher ground 17 66 31.44 0.025 7.05 94.2 4.99 0 34 0.04 109 N05.26475 W059.13805 81 Mine 2. Mine 3 18 40 9 34.05 0.03 7.31 84.9 5.66 0 116 0.03 75 N05.26437 W059.13745 83 Tailings 19 443 By hydraulic pump motor Mine 4 Tailings 601 31.07 0.024 7.21 85.2 5.45 0 104 0.03 69 N05.26443 W059.13791 82 Tailings 20 508 32.18 0.018 6.73 91. 3 5.5 0 80.2 0.02 63 N05.25819 W059.13311 88 Area where two mines meet 21 471 30.62 0.02 7.11 96.3 5.59 0 95 0.02 52 N05.25814 W059.13308 73 By hydraulic pump motor and adjacent to cooking area Mine 5 22 72 ---------N05.27391 W059.133 72 85 By hydraulic pump motor 22b 127 ---------Directly from sluice box 269

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270 Appendix H Continued Table H 2. Guyana (Iwokrama) Water Quality, Total Mercury Concentrations and Field Notes Iwokrama [THg] # (g/kg) Temp (C) Cond. (mS/cm) DO (mg/L) DO Sat (%) pH TDS (g/L) Turbidity (NTU) Salinity (ppt) ORP UTM Coordinates Elev. (m) Notes 1 53 26.63 0.022 6.91 81 5.42 18.5 19.1 0.02 104 N04.78912 W058.87139 56 Taken near brush 2 225 26.1 0.024 6.85 83 5.6 0 13 0.02 93 N04.7 3200 W058.85048 55 Water is visibly darker in this area; reported to have been an old mining camp area 3 298 27.4 0.022 7.62 87 5.7 0 32.2 0.02 89 N04.76645 W058.88126 42 Close to mining community. Water is bubbly & frothy. 4 120 27.1 0.022 10 98.4 5. 95 0 28.8 0.02 73 N04.74021 W058.92834 56 Abandoned mining area across from sampling location; 5 27.99 0.014 7.86 99.7 6.4 13.2 0.02 N04.67193 W058.68386 Iwokrama Field Station and housing 270

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271 Appendix I : XRD Minerological Profile s Table I 1. Hillsborough River XRD Mineralogical Profile. Sample ID Sample Name SemiQuant [%] Ref. Code Compound Name Chemical Formula HR1 Sargent Park 42 01 075 1072 Berlinite AlPO 4 58 01 081 0066 Quartz SiO 2 HR2 River Blvd 100 01 086 1562 Q uartz, low SiO 2 HR3 56 th Street 42 6 52 01 085 0930 01 075 0589 01 089 4201 Quartz Silicon Berlinite SiO 2 Si AlPO 4 HR4 HR State Park 40 58 1 00 033 1161 01 076 0232 01 089 4781 Silica Berlinite Tin Selenide SiO 2 AlPO 4 SnSe HR5 Rowlett Park* 100 01 08 3 3468 Quartz, syn SiO 2 HR6 Rivercrest 65 35 01 085 0930 01 076 0226 Quartz syn Berlinite Si O 2 AlP O 4 HR7 Lettuce Lake 41 45 15 00 005 0490 01 087 0086 01 087 0580 Quartz, low Berlinite, syn P AFH Si O 2 Al PO 4 K (As F 5 ( OH)) HR8 Rotary Park 50 50 03 065 0466 01 076 0228 Quartz low Berlinite, syn Si O 2 AlP O 4 HR9 Water Works 30 32 3 3 32 00 033 1161 00 046 1045 01 074 0154 01 084 0855 01 075 1072 Silica Quartz, syn SPF Aluminium Arsenate Berlinite, syn Si O 2 Si O 2 Na P F 6 Al AsO 4 AlPO 4 HR10 Curtis Hi xon 35 26 36 4 03 065 0466 00 033 1161 01 076 0227 01 075 0449 Quartz low, syn S ilica Berlinite, syn Magnetite Si O 2 Si O 2 AlP O 4 Fe 3 O 4 HR11 Trout Creek 59 41 03 065 0466 01 071 1041 Quartz low, syn Berlinite SiO 2 AlPO 4

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272 Appendix I Continued Table I 2 Hillsborough River XRD Mineralogical Profile (2) Sample ID Sample Name SemiQuant [%] Ref. Code Compound Name Chemical Formula HR12 Riverhills 40 27 2 1 31 01 085 0796 00 046 1045 01 081 1824 03 065 0928 01 085 0695 Quartz Quartz, syn Si lver Telluride Aluminium Uranium Silicon Oxide Si O 2 Si O 2 Ag 2 Te Al 3 U Si O 2 HR13 Riverfront 15 37 5 25 2 4 11 01 077 2064 01 085 0865 01 088 1431 00 036 0432 01 087 0095 01 087 0095 03 065 3257 00 046 1045 Sodium Chloride Quartz PHC Gypsum MCB Copper Oxide Platinum Zinc Quartz, syn Na Cl Si O 2 K 5 H (CN 2 ) 3 Ca(SO 4 ) 2 H 2 O Hg, Cr, Ba 2 Cu O 4.267 Pt 3 Zn Si O 2 HR14 Lowry Park 79 11 10 01 074 1784 00 046 1045 00 033 1161 Kaolinite Quartz, syn Silica Al 2 Si 2 O 5 (OH ) 4 Si O 2 Si O 2 HR15 Bullard Parkway 29 3 6 29 5 00 005 0490 01 079 1095 01 076 0225 01 086 0365 Quartz, low Aluminum Phosphate Berlinite, syn Lead Arsenate Si O 2 Al(PO 4 ) AlPO 4 Pb(As 2 O 6 ) HR16 Epps Park 64 13 19 4 01 085 0798 01 075 0278 01 076 0314 01 089 4088 Quartz Aluminum Oxide Aluminum Arsenate Manganese Sulfide Si O2 Al O Al As O4 Mn S *Unresolved peaks exist in lower sections of scan PAFH Potassium Arsenic Fluoride Hydroxide SPF Sodium Phosphorus Fluoride PHC Potassium Hydrogen Cyanamide MCB Mercury Chromium Barium

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273 Ap pendix I Continued Table I 3. Hillsborough Guyana (Iwokrama) River XRD Mineralogical Profile Sample ID Sample Name SemiQuant [%] Ref. Code Compound Name Chemical Formula IWO1 Iwokrama 1 -IWO2 Iwokrama 2 -01 083 2187 01 087 0082 01 072 1064 01 089 1362 01 070 1797 01 075 1700 Quartz Berlinite, syn Aluminium Phosphate Gallium Arsenic Oxide Mercury Hydrogen Phosphate Threadgoldite Si O 2 Al (PO 4 ) AlP O 4 Ga(AsO 4 ) Hg 2 (H 2 PO 4 ) 2 Al (UO 2 ) 2 ( P O 4 ) 2 (OH ) (H 2 O) 8 IWO3 Iwokrama 3 -----01 083 2187 01 072 1064 01 071 1041 01 083 2476 01 080 1255 01 082 2122 Quartz Aluminum Phosphate Berlinite Germanium Oxide Iron Arsenic Carbonyl Copper Bromide Si O 2 AlP O 4 AlP O 4 Ge O 2 (Fe 2 (CO) 8 As) 2 ( Fe 2 (C O) 6 ) Cu Br IWO4 Iwokrama 4 ------01 085 0796 01 074 0154 03 065 3271 01 071 1041 01 082 2455 01 078 0283 Quartz SPF* Aluminum Neptunium Berlinite Brucite, syn MGT Si O 2 Na P F 6 Al 3 Np Al P O 4 Mg (OH ) 2 Hg Ga 2 Te 4 *SPF Sodium Phosphorus Fluoride MGT Mercury Gallium Telluride

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274 Appendix I Continued Table I 4 Guyana (Konashen) River XRD Mineralogical Profile Sample Area Sample Name SemiQuant [%] Ref. Code Compound Name Chemical Formula Essequibo ER 11 25 75 01 085 0794 01 080 0886 Quartz Kaolinite Si O 2 Al 2 ( Si 2 O 5 )(OH ) 4 ER 12 ----------------------------------------------------ER 16 69 1 1 28 1 1 01 077 1060 01 086 0666 01 082 2122 01 072 1064 03 065 3492 03 065 0682 Silicon Oxide Potassium Manganese Copper Br omide Aluminum Phosphate Aluminum Chromium Zinc Oxide Si O 2 K O.27 MnO 2 ( H 2 O) Cu Br AlP O 4 AlCr 2 C Zn O Acari Creek AM 01 32 6 1 6 50 5 00 005 0490 00 052 0922 0 3 065 0022 01 087 0628 01 087 0084 01 089 0437 Quartz, low ACS Gold Indium Lutetium Osbornite Berlinite, syn MMS Si O 2 AlCr Cu 2 Au 2 In Lu Ti N Al(PO 4 ) (Hg 0.67 Mn 0.33 ) S AM 02 23 29 25 23 00 005 0490 01 087 0082 01 085 1123 00 033 1161 Quartz, low Berlinite, syn Mercury Peroxide S ilica Si O 2 Al(PO 4 ) Hg O 2 Si O 2

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275 Appendix I Continued Table I 5 Guyana (Konashen) XRD Mineralogical Profile (2) Sample ID Sample Name SemiQuant [%] Ref. Code Compound Name Chemical Formula Acari Creek AM 0 3 15 16 16 5 3 00 033 1161 00 046 1045 01 076 0225 01 077 1060 Silica Quartz, syn Berlinite syn Silicon Oxide SiO 2 Si O 2 AlP O 4 Si O 2 AM 04 ----Kamoa River KR 02 25 16 27 2 27 4 00 046 1045 01 086 1664 01 076 0228 01 077 2367 01 086 1560 01 073 1 593 Quartz, syn Lanthanum Cobalt Oxide Berlinite, syn Magnesium Iron Oxide Quartz low Metacinnabar Si O 2 LaCo O 3 AlP O 4 (MgO ) 0.593 (Fe O) 0.407 Si O 2 Hg S KR 04 KR 05 6 39 24 2 29 01 089 0437 01 071 0910 01 071 1041 01 077 2368 00 046 1045 MMS Beryllium Fluoride Berlinite Magnesium Iron Oxide Quartz, syn (Hg 0.67 Mn 0.33 ) S Be F 2 AlP O 4 (MgO ) 0.432 (FeO ) 0.568 Si O 2 KR 06 61 19 15 1 1 4 01 077 1060 03 065 0466 01 084 0854 01 077 0191 03 065 3844 01 089 0437 Silicon Oxide Quartz low, syn Aluminum Phosphate Zinc O xide Copper Tin Phosphide MMS Si O 2 Si O 2 Al P O 4 Zn O Cu 4 Sn P 10 ( Hg 0.67 Mn 0.33 ) S KR 07 KR 12 Sipu River SR 06 47 13 10 16 14 01 077 1060 00 046 1045 01 076 0314 01 071 1041 01 085 1123 Silicon Oxide Quartz, syn Aluminum Arsenate Berlin ite Mercury Peroxide Si O 2 Si O 2 AlAs O 4 Al P O4 Hg O2 *MMS Mercury Manganese Sulfide ACS Aluminum Chromium Copper

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276 Appendix I Continued Table I 6. Guyana (Mahdia) XRD Mineralogical Profile. Sample ID Sample Name SemiQuant [%] Ref. Co de Compound Name Chemical Formula Mine 1 11, pump 3 29 33 34 01 086 0666 01 087 0082 00 046 1045 0 1 085 1123 Potassium Manganes e Berlinite, syn Quartz, syn Mercury Peroxide K 0.27 MnO 2 (H 2 O) Al(PO 4 ) Si O 2 Hg O 2 12, sluice 00 003 0249 Goethite, syn Fe +3 O(OH ) 12B, LHS 12C, RHS 12D, camp Diosmp Topsoil 01 076 0227 01 084 0853 03 065 3020 01 075 1522 01 089 6538 01 089 5895 01 070 1797 Berlinite, syn Aluminum Phosphate Indium Sodium Quartz Kaolinite Copper Oxide MHP* AlP O 4 AlP O 4 In Na Si O 2 Al 2 (Si 2 O 5 )(OH ) 4 Cu O Hg 2 (H 2 PO 4 ) 2 Mine 2 14, pit 00 011 0252 01 083 2475 high quartz Germanium Oxide Si O 2 Ge O 2 14B, tailing 01 076 0226 01 083 2476 01 085 1123 Berlinite, syn Germanium Oxide Mercury Peroxi de AlP O 4 Ge O 2 Hg O 2 15, tailings 16, sluice 17, tailings Mine 3 18, tailings 19, pump Mine 4 20 21, pump Tailings Mine 5 22, pump 00 013 0375 00 001 0527 00 032 0661 Halloysite Kaolinite Mercury Selenate H ydrate Al 2 Si 2 O 5 (OH) 4 Al 2 Si 2 O 5 (OH ) 4 HgSe O 4 2 O Mine 6 22b, sluice 01 084 0854 01 071 1610 03 065 2573 Aluminum Phosphate Nickel Chromium Fluoride Arsenic Iron Al P O4 Ni Cr F6 As2 Fe MHP Mercury Hydrogen Phosphate

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277 Appendix I Continued Table I 7 Bolivia (Lago Titicaca, Rivers, and Strea ms) XRD Mineralogical Profile Sample ID Sample Name Ref. Code Compound Name Chemical Formula B 1 Tajani 00 033 1161 00 031 1780 Silica Mercury methyl mercaptide Si O 2 C 2 H 6 Hg S 2 B 2 Escoma B3 Sojo Sojo 01 083 2465 00 005 0143 00 002 0050 01 084 0982 Quartz, syn Kaolinite Illite Albite low SiO 2 Al 2 Si 2 O 5 (OH ) 4 2K 2 O 3 MgOFeO(Al 2 O 3 ) 24 2 ) 12 2 O Na(AlSi 3 O 8 ) B4 Aqua Caliente B4B MinervaPotos B6 Villa Tacata 01 083 2466 00 029 0713 00 029 1497 00 001 0665 00 033 0118 00 001 1240 00 004 0770 00 036 1471 Quartz, syn Goethite Nontronite 15A PHI Stistaite Copper Tin Magnesiu m Potassium Bromide Si O 2 Fe +3 O(OH) Na 0.3 Fe 2 Si 4 O 10 (OH) 2 2 O KIO 3 3 Sb Sn Cu 3 Sn Mg K Br B7 Canton Humanata 00 033 1161 00 011 0237 01 087 0088 01 088 2470 Silica Boron Phosphate Berlinite, syn MBCCO Si O 2 BP O 4 Al(PO 4 ) Hg Ba 2 Ca 2 Cu 3 O 8.16 B8 Lago Titicaca B13 Ro Beni *PHI Potassium Hydrogen Iodate MBCCO Mercury Barium Calcium Copper Oxide

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278 Appendix J : BET Surface Area Analysis Table H 1. BET Surface Area Analysis for Hillsborough River, Tampa, FL Sample Name/units Kemiron 56 50 HS1 RCT1 TRT1 RTY1 ROW1 SRG1 CRH1 LWY1 Unit Standard 56th St. Overpass HR State Surface River crest Trout Creek Park Rotary Park Rowlett Park Sargent Park Curtis Hixon Park Lowry Park Zoo Area Vial G 10.529 10.523 10.53 10.523 10.523 10.298 10.298 10.523 10.298 10.526 Vial+sample G 10.609 10.829 11.119 11.31 10.708 10.416 10.463 10.705 10.375 10.676 Vial+sample+wool G 10.627 10.846 11.131 11.326 10.722 10.432 10.474 10.707 10.387 10.699 Sample G 0.08 0.306 0.589 0.787 0.185 0.118 0.165 0.182 0.07 7 0.15 Wool G 0.018 0.017 0.012 0.016 0.014 0.016 0.011 0.002 0.012 0.023 Outgas at 105C Hr 3 2 2 3 2 2 2 2 2 2 Vial+sample+wool after outgassing G 10.608 10.844 11.13 11.321 10.722 10.429 10.473 10.709 10.386 10.694 Sample after outgassing G 0.061 0. 304 0.588 0.782 0.185 0.115 0.164 0.184 0.076 0.145 Surface area m 2 /g 33.34 0.4341 0.2622 0.1897 0.7674 0.9796 0.822 0.7917 2.822 0.1897 Correlation Factor a.u. 0.9996 0.997419 0.997822 0.995877 0.865925 0.988688 0.758537 0.481354 0.966952 0.9958 278

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About Author University in Computer and Electrical Engineering. She then went on to obtain her f South Florida where she continued to pursue her Doctoral degree. Throughout her academic tenure she has conducted global research examining various aspects of water, sanitation, and sustainability in many remote areas of the world such as Mexico, Tanzan ia, Guyana, Trinidad and Tobago, and Bolivia. She has received travel grants and fellowship awards from the National Science Foundation and the University of South Florida. She was the co founder and former president of the Engineers for a Sustainable Wor ld USF Chapter and has since been an active member. She has served as a mentor to several youth in the community, co coordinator for a professional development organization (MSPHDS) and co coordinator for a community based participatory research program.


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Mercury in the environment :
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ABSTRACT: Tampa (US), Guyana (SA), and Bolivia (SA), are geographically, socially, economically, and politically unique which make them ideal sites to study issues of mercury and sustainability. Mercury's innate ability to bioaccumulate and biomagnify in aquatic and terrestrial ecosystems poses a severe threat to both human and environmental health. The most vulnerable populations affected by mercury consumption include coastal communities, children, women of child-bearing age, the indigenous poor and persons with high environmental/occupational exposure factors. Communities in the regions of Florida, Bolivia, and Guyana whose diets are high in fish and are environmentally/occupationally exposed to mercury may be at a higher risk of mercury intoxication, especially in the absence of education on the topic. Mercury loadings in rivers, streams, and mine tailing waters and sediments ranged from 0.9-114 ng/L and 29- 2891 ng/g, respectively; whilst fish mercury loadings were 0.02-1.034 mg/kg wet wt. Although mining sites had the highest mercury sediment and water loadings there were no significant differences when compared to pristine sites in Guyana. Fish loadings above recommended EPA/WHO regulatory limits were observed at all sites and none had signage, informational warnings or educational material available. A pilot study that included four elementary schools in Tampa showed that Water Awareness Research Education (WARE), a community based participatory environmental educational program, is a sustainable solution to addressing issues of mercury exposure.
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Environmental sustainability
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