Petrology and geochemistry of the Late Precambrian Balkan-Carpathian ophiolite, Bulgaria and Serbia

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Petrology and geochemistry of the Late Precambrian Balkan-Carpathian ophiolite, Bulgaria and Serbia

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Petrology and geochemistry of the Late Precambrian Balkan-Carpathian ophiolite, Bulgaria and Serbia
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Savov, Ivan Petrov
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Tampa, Florida
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University of South Florida
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English
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viii, 108 leaves : ill., (some col.) ; 29 cm.

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Ophiolites -- Bulgaria ( lcsh )
Ophiolites -- Serbia ( lcsh )
Geology, Stratigraphic -- Precambrian ( lcsh )
Dissertations, Academic -- Geology -- Masters -- USF ( FTS )

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Thesis (M.S.)--University of South Florida, 1999. Includes bibliographical references (leaves 20-23).

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University of South Florida
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Universtity of South Florida
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F51-00147 ( USFLDC DOI )
f51.147 ( USFLDC Handle )

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PETROLOGY AND GEOCHEMISTRY OF THE LATE PRECAMBRIAN BALKAN-CARPATHIAN OPHIOLITE BULGARIA AND SERBIA by ./ IV AN PETROV SA VOV A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science Department of Geology University of South Florida August 1999 Major Professor : Jeffrey G Ryan Ph D

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Graduate School University of South Florida Tampa Florida CERTIFICATE OF APPROVAL Master's Thesis This is to certify that the Master's Thesis of IV AN PETROV SA VOV with a major in Geology has been approved by the Examining Committee on March 18, 1999 as satisfactory for the thesis requirement for the Master of Science degree Examining Committee: MajJ G Ryan, Ph.D. Member: Sar a h Member: Eric Oches, Ph.D.

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DEDICATION I dedicate this work to my wife Galia, my brother Luben and to my parents Peter and Christina whose moral support is priceless.

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ACKNOWLEDGEMENTS Many thanks to all the people who made this project possible : Dr.Ivan Haydoutov from the Bulgarian Geological Institute for the encouregment and the valuable field assistance in the Balkan mountains of Bulgaria and Serbia, as well as for the help with the tectonic interpretations ; Dr. Johan Schijffor allowing us access to (and help with) the ICPMS facility at the USF Marine Science Department in St.Petersburg, FL. Many thanks to Dr. Kristina Kolcheva (University of Sofia Bulgaria) for her thoughtful review on our petrography and for her contribution to the sample set. The helpful insight from Dr. Pavel Kepezhinskas (USF) is much appreciated, as is Suzanne Norrell's assistance in the lab Field trips to the Appalachian Mountains with Mike Emilio and Dr. Jeffrey Ryan provided a whole new view on how complex ophilites can be. Dr.Chris Scotese (PALEOMAP Project) and Dr.Ronald Blakey (Northern Arizona Univeristy) helped with the paleogeographic maps. Dr. Emily Klein (Duke University) allowed the use of the GERM Project MORB data which significantly improved our interpretations. Most of this study was funded, thanks to grants from the Sigma Xi and USF Department of Geology. Finally I extend my deepest gratitude to Dr. Jeffrey Ryan from USF for giving me the opportunity to obtain valuable experience with the analytical equipment for being my project supervisor and for believing in me

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TABLE OF CONTENTS LIST OF TABLES ............................................................................... 111 LIST OF FIGURES ................................................................................ v ABSTRACT ....................................................................................... VI INTRODUCTION ................................................................................. 1 GEOT JOGJC SETTING ........................................ I 3 INTERNAL STRATIGRAPHY AND PETROLOGY ....................................... 5 Tchemi Vrah massif ................................................... ... ............................... .......... 5 Deli J ovan massif ................................................................................... 6 SAMPLING AND ANALYTICAL METHODS ............................................... 7 RESULTS ............................................................................................. 9 Petrography ................................................................................... 9 Effects of Metamorphism ........................................ ....... .... ............. . . ........ 11

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BULK CHEMISTRY ................................................................... 13 Major and Trace Elements ............................................................... 13 Rare Earth Elements .. ..................................................................... I 4 DISCUSSION ..................................................................................... 15 1. Petrogenesis of the B-C ophiolite ............................................... 15 2. Geodynamic Implications of the B-C ophiolite .................................... 17 CONCLUSIONS ................................................................................... 19 REFERENCES ..................................................................................... 20 A.PPEND ICES ...................................................................................... 24 APPENDIX A. PETROGRAPHYCAL DESCRIPTIONS .......................... 25 APPENDIX B PHOTOMICROGRAPHS AND FIELD RELA TIONS ........... 51 APPENDIX C FIGURES AND FIGURE CAPTIONS .............................. 70 APPENDIX D. BULK CHEMISTRY TABLES AND TABLE CAPTIONS ..... 81 APPENDIX E. ANALYTICAL STATISTICS ........................................ 94 APPENDIX F CIPW NORMATIVE MINERALS ................................... ... 97 APPENDIX G. COMPARISON BETWEEN B-C BASALTS AND MORB FROM MODERN OCEANS ....................... 1 00 APPENDIX H PALEOGEOGRAPHIC MAPS ....................................... 04 11

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LIST OF TABLES Table lA. Major and Trace element data for Deli Jovan ultramafic cumulates 82 Table lB. Major and Trace element data for Tchemi Vrah ultramafic cumulates 82 Table 2. Major and Trace element data for B-C mafic cumulates 83 Table 3 Major and Trace element data for B-C sheeted dykes 84 Table 4. Major and Trace element data for B-C basalts 86 Table 5 Rare Earth Elements data for B-C basalts 87 Table 6. Rare Earth Elements data for B-C sheeted dykes 87 Table 7. Rare Earth Elements data for ultramafic and mafic cumulates 88 Table 8. Haydoutov (1991) Major and Trace element data for cumulates 89 Table 9 Haydoutov (1991) Major and Trace element data for sheeted dykes 89 lll

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Table 10. Haydoutov ( 1991) Major and Trace element data for basalts 90 Table 11. Major and Trace element analytical statistics 95 Table 12. Rare Earth Elements analytical statistics 96 Table 13. CIPW Normative minerals in B-C u l tramafic cumulates 98 Table 14. CIPW Normative mineral s in B-C mafic cumulates 98 Table 15. CIPW Normative minerals in B-C pillow basalts 98 Table 16. CIPW Normative minerals in B-C basalt sheeted dykes 99 Table 17. CIPW Normative minerals in B-C diabase and microgabbro sheeted dykes 99 Table 18. Comparison between B-C basalts and North Atlantic MORB 101 Table 19. Comparison between B-C basalts and North East Pacific Rise MORB 102 Table 20. Comparison betw e en B-C basalts and Indian ocean MORB 103 IV

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LIST OF FIGURES Figure 1. Location map of the different B-C ophiolite massifs 71 Figure 2 Major and trace element covariation diagrams 72 Figure 3. Trace element based ophiolite discrimination diagrams 74 Figure 4. Rare Earth elements (REE) diagrams 77 Figure 5. Late Proterozoic paleogeographic map (650 Ma) 105 Fig ure 6. Late Precambrian paleogeographic map (600 Ma) 105 Figure 7 Late Precambrian paleogeographic map (570 Ma) 106 Figure 8 Late Cambrian paleogeographic map (514 Ma) 106 Figure 9. Middle Ordovician paleogeograph ic map (458 Ma) 107 Figure 10. Middle Silurian paleogeographic map ( 430 Ma) 107 Figure 11. Late Devonian paleogeographic map (370 Ma) 108 Figure 12. Late Pennsylvanian paleogeographic map (300 Ma) 108 v

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PETROLOGY AND GEOCHEMISTRY OF THE LATE PRECAMBRIAN BALKAN-CARPATHIAN OPHIOLITE BULGARIA AND SERBIA by IV AN PETROV SA VOV An Abstract Of a thesis submitted in partial fulfillment of the requirements for the degree of Master of Science Department of Geology University of South Florida August 1999 Major Professor: Jeffrey G. Ryan Ph D. VI

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The Balkan Carpathian ophiolite (B-C), which outcrops in Bulgaria, Serbia and Romania is a Late Precambrian (563 Ma) mafic / ultramafic complex unique in that it has not been strongly deformed and metamorphosed as have other basement rocks in Alpine Europe. Samples collected for study from the Tchemi Vrah and Deli Jovan segments of B-C include cumulate dunites, troctolites wehrlites and plagioclase bearing wehrlites ; olivine and amphibolebearing gabbros; anorthosites; diabases and microgabbros; and basalts representing massive flows dykes, and pillow lavas as well as hyaloclastites and umbers (preserved sedimentary cover). Relict olivine clinopyroxene and amphibole in cumulate peridotites indicate original orthocumulate textures, and the olivines and pyroxenes exhibit well-developed kelyphitic rims. Plagioclase in troctolites and anorthosites range from An60 to An70 Cumulate gabbro textures range from ophitic to poikilitic, with an inferred cry s tallization order of olivine(pla g ioclase + clinopyroxene) amphibole (hornblende). The extrusive rocks exhibit poikilitic ophitic and intersertal textures with clinopyroxene and/or plagioclase (Oligoclase-Andesine) phenocrysts. The major opaques are Timagnetite and ilmenite The metamorphic paragenesis in the mafic samples is chlorite + tremolite + epidote while the ultramafi c rocks show variable degrees of s erpentinization with lizardite and antigorite as dominant phases. The samples in this study are compositionally and geochemically consistent with modern oceanic crust. Major element trace element and rare earth element (REE) signature s in B-C ba s alts are comparable to those of modem MORB. In terms of cumulate composit i on the B-C is a "highTi" or "oceanic" ophiolite based on the Vll

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classification scheme of Serri (1981 ) Our petrologic and geo chemical results, combined with th e t ectonic position of the B-C massifs (overlain b y and in contact with Late Cambrian island arc and backarc sequences) suggest that the B-C may h ave formed in a midocean ridge setting. If the B-C complex records the existe nce of a Precambrian ocean basin, then there may be a relationship between the B-C and the Pan African ophiolites from the ArabianNubian Shield. We s uggest that the B-C ophiolite i s the mis si ng link bet wee n the PanAfrican and the Avalonian-Cadomian peripheral orogens of Murphy and Nance(l995). ffrey G. Ryan Ph.D ent of Geology D ate Approved : ----'-----'--=-------Vlll

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INTRODUCTION The volcanic and intrusive rock associations preserved in ophiolite complexes offer a means of assessing the processes and conditions of basaltic magmatism through time Ophiolites are also useful in the reconstruction of a region's tectonic history as these un i ts indicate the presence of sutures and the closure of ancient marine basins The lithologic associations and the chemical signatures of ophiolitic rock units can provide further tectonic insights, as complexes formed in arc, back-arc and oceanic settings can often be differentiated based upon cumulate sequences and the chemical signatures of their basaltic volcanics (Pearce 1982; Shervais, 1982; Beccaluva et al. 1979) Precambrian ophiolites are thus especially valuable as indicators of changing igneous processes and continental development through Earth history. Unfortunately, ongoing tectonic processes at the Earth's surface, and in crust can disaggregate and deform ancient ophiolitic rocks and metamorphose them extensively, so much so that it is often a significant achievement to recognize them as being ophiolitic in character (see Tenthorey et al., 1996; Morman et al., 1999 ; for discussions of possible ophiolitic rocks in the southern U.S. Appalachians) Thus a well-preserved and relatively unmetamorphosed ophiolite of Precambrian age is a resource of particular geologic value Just such a well-preserved ancient ophiolite complex exists in the Balkan mountains of Southeastern Europe. Named the Balkan-Carpathian Ophiolite (BCO) by Haydoutov (1991), this complex includes several major massifs which may be fault-

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block remnants of a single ophiolite thrust sheet (Haydoutov ( 1991 ). Stratigraphic relations and paleontological evidence place these units below earliest Cambrian volcanic and sedimentary sequences (Kalenic, 1966; Kalvacheva 1986) and newly reported radiometric dates from BCO gabbro suggest an age greater than 560 Ma (Quadt et al. 1999). Results on a selection of BCO basaltic volcanic rocks indicate very low metamorphic grades (greenschist facies) and compositions suggesting oceanic affinities (Haydoutov 1991 ). The goal of this study is to extend our knowledge for the petrologic relationships among the different mafic / ultramafic massifs within the Balkan-Carpathian ophiolite, testing the contention ofHaydoutov (1991) that the different BCO massifs have similar origins and evolutionary paths. Through careful petrographic and geochemical examination of a spectrum of BCO volcanic and cumulate sample s we defme the nature of the BCO in the light of the diversity of the ophiolites and via comparisons to modem oceanic mafic volcanic rocks. Our petrologic re s ults allow us to address the question of the tectonic environment in which the B-C ophiolite originated. In particular, we examine Balkan Carpathian ophiolite in the context of the Pan-African collisional events which affected Eastern Europe the Middle East and NE Africa in the Latest Pre cam brian. 2

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GEOLOGIC SETTING The Balkan-Carpathian ophiolite (BCO) i s one of the largest ophiolite bodies found in the Balkan Peninsula It comprises severa l massifs that were emplaced along the Tracian Suturepart of the so -called South European suture (Haydoutov, 1991) Similar ophiolite massifs, such as Kraubath and Hohgrossen massifs in the Eastern Alps (Ageed et al., 1980) and the Chamrousse massif in France (Bodinier, 1981) outline the South European s uture to the west (Haydoutov, 1989). To the eastthe Bolu massif in Turkey (Goncuo glu 1997 ; Ustaomer and Kipman, 1997) and the Pan-African ophiolites of the Arabian-Nubian Shield may reflect a continuation of the South European suture. These united suture zo ne s may represent the trace of the Pan -African (proto-Tethys) ocean (Haydoutov, 1991). The B-C ophiolite is expose d as several di stinct massifs: th e Tcherni Vrah (Bulgaria) Zag lavac and Deli Jovan (Serbia) and South Banat (Romania) massifs (Haydoutov 1989). The Tchemi Vrah and Zaglavac massifs are geo logically connected and together with Deli Jovan massif comprise a sing le ophiolitic seq uence separated by the Poretchko-Timoshki fault zone (Figure 1 ) (Haydo utov 1991) These mas sifs are unconformably overlain by a Cambrian age volcano-sedimentary and arc-related sequence known in Bulgaria as the Berkovitza group and in Serbia as the Vlasinski complex. Based on the occurre nce of Archaeocyathids in carbonates of the Vlasinski complex (Kalenic, 1966) the Tcherni Vrah and Deli Jovan massifs were placed in the Late 3

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Precambrian-earliest Cambrian. Recent U-Pb zircon dating results of gabbroic rocks from Tchemi Vrah massif confirm a Latest Precambrian age -563 Ma (Quadt et al. 1999). For the purposes of our study we have selec ted Tcherni Vrah and Deli Jovan ma ssifs, as they provide excellent exposures and have been well characterized in term s of field relations and major litholo g ies (Haydoutov 1989 1991; Kolcheva et al., 1984). 4

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INTERNAL STRATIGRAPHY AND PETROLOGY Tcherni Vrah massif: The Tcherni Vrah massif outcrops in the Stara Planina mountains ofNW Bulgaria and is the best-studied massif within the BCO. It includes cumulate, sheeted dyke and pillow lava units (Haydoutov, 1989). In the best preserved domains ofTcherni Vrah there are clear similarities in the strike ofthe cumulate layers in the upper gabbros and sheeted dykes and in the elongation of preserved volcanic cones (see Ballard and Moore 1977) in the pillow lava unit (Haydoutov, 1991). The relation between the different ophiolite units suggests that there has been little relative motion among the units since their formation as igneous sequences (Haydoutov, 1991)(see Appendix B, Plate 29). The Cumulate unit is composed of ultramafic cumulates and gabbros, and has a total thicknes s of 2.5 km. The unit's lower boundary is tectonic while the upper boundary grades into sheeted dykes through the isotropic gabbro. Mineralogic layering is prominent in outcrop (see Appendix B Plate 20). The lower Cumulate unit includes relatively thin (0.15 -6 m) alternating layers of pyroxene gabbros and ultramafic cumulates (wehrlites, plag-wehrlites, troctolites olivine gabbros pyroxenites and anorthosites). These horizons are distinguished by the gradual appearance of plagioclase. The upper Cumulate unit lacks ultramafic cumulates and is dominated by gabbros. The gabbros alternate with lenses of anorthosite pyroxenite and pegmatoid gabbro (see Appendix B Plate 21 ), giving the unit a layered appearance. The thickness of the layers 5

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varies from as small as 4 em in the gabbros, to up to 5-6 m in the w e hrlites and troctolites. The sheeted dykes unit has a total thickness of 1 km. The upper boundary with the extrusive rocks is gradational with dykes crosscutting lava flows made of ophitic basalts. Very often epidote len ses with different s ize mark the transition zone between the sheeted dykes and the pillow basalts (see Appendix B Plates 24 and 25) Dyke s intrude each other and many exhibit chill margins (see Appendix B Plate 22) Dyke thicknesses range from 7 em to 5 m, and all have similar strikes and dips ( 120-140 and 60-70 to the SW). The Pillow Lavas unit forms a 20-km long mappable body with a thickness of 700m. It consists of alternating pillow lavas lava tubes and massive basalt flows (see Appendix B Plates 26 28 29 and 30) overlain by hyaloclastites lava breccias and sediments Pillow lavas are more abundant than massive flows. Pillow hori z ons are 10150 m thick whereas massive flows and hyaloclastites are seldom more than 1-3m thick. Sediment s are preserved as len ses of black phyllites between pillows, or as bedded pink argillites near the top of the unit. Deli Jovan massif: The Deli Jovan ophiolite massif crops out in the Deli Jovan mountain ofNE Serbia It is composed of ultramafic and mafic cumulates, sheeted dykes and a volcanic section. Based on the relative volumes of mafic and ultramafic cumulates in Deli Jovan Haydoutov (1991) divided the cumulates into western and eastern parts The eastern part includes layers of dunites troctolites, olivine gabbros wehrlites and anorthosites which alternate with fine-grained gabbros. The western part i s composed of coar se -grained 6

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(locally pegmatoid) undeformed gabbros; ultramafic cumulates are absent or very rare According to Terzic (1981), these gabbros grade stratigraphically upwards into microgabbro and diabase sheeted dykes with 2 km total thickness. The sheeted dykes grade stratigraphically upwards into unpillowed aphanitic basalts (Terzic 1981 ). SAMPLING AND ANALYTICAL METHODS Detailed field studies in the summer of 1997 by Savov and Haydoutov confirmed the mapping results and lithologic relationships ofHaydoutov (1991) (see Appendix B, Plates 2030). A representative suite of samples from the Tcherni Vrah and Deli Jovan massifs was collected for petrographic and geochemical analysis. It covers all the rock types found in these massifs Textural and mineral relationships were examined in 70 thin s e ctions using standard petrographic techniques. Fifty samples representing all the major ophiolite lithologies (except pyroxenites ) were crushed and powdered using a WC ball mill in preparation for chemical analysis Major and trace element abundances were analyzed at the University of South Florida by direct current plasma emission spectrom e try (DCP) following LiB02 fluxed-fusion digestions. Dissolution techniques follow those described in Tenthorey (1994) in that furnace temperatures were maintained at 1115-1125 C to encourage complete digestion o f ultramafic samples Precision for major elements varies with element from < 1% to 3 %. Trace element reproducibility var i es strongly with concentration and ranges from 5% to 25%(see Table 11 in Appendix E) Rare Earth Element (REE) abundances were measured via ICP-MS u s ing the Fi s ons Plasma Quad PQS instrument at the USF Department of Marine Science in St. 7

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Petersburg, FL. Samples were digested via fluxed fusion with Na2C03. In this procedure a variation on the boron digestion technique of Ryan and Langmuir (1993), 4 : 1 flux to sample mixtures were heated for 2 hours to 1050 C in Pt crucibles. The fusion cakes were fust immersed in water at 1 00 C in sealed teflon jars, and then rinsed thoroughly to remove water soluble alkalies and Na4Si04. The insoluble fraction of the fus ion cake was dissolved for analysis in 1% HN03 spiked with 50 ppb concentration of Re and Cs internal standards Dilution factors were 1 000: 1 We used a combined calibration procedure, fitting REE intensities to those of the Re and Cs internal standards, and then generating working curves for the REE using synthetic matri x -matched standard solutions. In-rock detection limits vary with REE in the 0 1 to 0 .01 ppm range. Reproducibility is on the order of 5%-10%. Replicates of USGS standard basalts BIR-1 BHV0-1 NBS 688 and W 2 are within 10% of reported values except at the very low es t REE contents( 1 to 2 x chondrite abundanc e levels)(see Table 12 in Appendix E) 8

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RESULTS Petrography All ultramafic cumulate samples were serpentinized but relict olivine and clinopyroxene grains were relatively common (see Appendix B Plate 3 and 5). Amphibole is present in some cumulate thin sections (see Appendix B Plates 79) and probably represents near-solidus crystallization in a cooling ophiolite magma chamber (Herbert and Laurent, 1990). The dunites are entirely serpentinized and the serpentine exhibits typical mesh and hourglass textures (see Appendix B, Plates 1 and 2) The primary opaque appears to be magnetite as it is locally altered to hematite. Primary minerals in the wehrlites are olivine clinopyroxene and amphibole. Olivine grains commonly preserve their original shapes and locally form layers which suggests cumulate origins The clinopyroxene is diopsidic (Kolcheva et al., 1984) (pale green in thin section) and occurs as interstitial euhedral grains between the olivines (see Appendix B Plate 3 and 4). Secondary amphibole is rimming olivine or clinopyroxene crystals in typical corona textures. Troctolites from Deli Jovan are generally fresh while those from Tcherni Vrah are altered. Primary minerals are plagioclase olivine and clinopyroxene with accessory magnetite. Plagioclase is typically An70 (bytownite) and forms thick prismatic laths exhibiting albite and Carlsbad twinning Olivine is present as rounded grains that are sometimes rimmed by clinopyroxene Clinopyroxene also appears as short prismatic grains showing exsolution effects. Redbrown amphibole coronas locally 9

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surround the clinopyroxene grains. The troctolites preserve both ophitic and poikilitic textures (see Appendix B Plates 5 and 6) Anorthosites are relatively uncommon and show adcumulus textures The plagioclase from the anorthosites is labradorite in composition ( An55). Rocks from the gabbroic sections of the B C ophiolite massifs range widely in the relative proportions of plagioclase, clinopyroxene, amphibole and olivine: gabbro anorthosites, gabbros olivine gabbros olivineamphibole gabbros and amphibole gabbros all occur Texturally these rocks are dominantly pyroxene plagioclaseolivine cumulates. Plagioclase compositions range from bytownite(An75) in gabbro anorthosites to andesine ( An50) in upper cumulate unit gabbros Both Carlsbad and albite twining are common Diopsidic clinopyroxene crystallizes between the early formed plagioclase crystals. In the pyroxene-gabbros from Deli Jovan the clinopyroxene could poikilitically include plagioclase chadacrysts. The clinopyroxene is rimmed by red brown coronal amphibole. Olivine where present preserves its crystal shapes but is commonly altered to a fine-grained aggregate of serpentine tremolite and chlorite. Amphibole can comprise up to 45 % of the rocks Together with abundant sphene it is largely a product of clinopyroxene alteration; however magmatic amphibole (inferred from the prismatic amphibole crystal habits and the textural relationships) can comprise up to 10% of some rocks (Kolcheva et al ., 1984) (see Appendix B Plates 7 and 8) Accessory phases include sphene apatite ilmenite and magnetite (see Appendix B Plates 12and 13). Diabases consist of plagioclase and clinopyroxene (augite) in varying proportions Plagioclase forms large prismatic phenocrysts Textures are ophitic to porphyritic and rarely poikilitic Sometimes pyroxene is rimmed by brown amphibole Accessory 10

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minerals are Ti-magnetite (locally altered to sphene and ilmenite) apatite and zircon opaques and accessory minerals may comprise 2%-4% of the rock Basalts range from very fme-grained to aphanitic-porphyritic (see Appendix B Plates 14 and 15) Plagioclase compositions range from Andesine to nearly pure Albite and form swallow -end ed phenocrysts (see Appendix B Plate 16) Together with featherlike skeletal clinopyroxene aggregates (see Appendix B Plates 17 and 18), these crystals indicate fast cooling rates. Volcanic glass (now an ultra-fine grained matrix) can make up 85% of the rock Textures range from ophitic to variolitic and spherolitic in the volcanic glass-rich basalts (see Appendix B Plates 14 and 15). Accessory minerals (2%) are apatite zircon, sphene, Ti-magnetite and ilmenite (see Appendix B Plate 19) Based on textural relations in the cumulate and volcanic rocks the order of crystallization in Tcherni Vrah and Deli Jovan ma ssif samples is Olivine SpinelClinopyroxene = Plagioclase-Amphibole. Effects of Metamorphism Our s amples were collected from the best preserved portions of the ophiolite sequence, where metamorphic grade is in the lower greenschist facies. The following is an att empt to summarize the metamorphic effects in the studied ophiolite successions: 1. Pla g ioclas e is albitized (in the volcanic and in the upper parts of the dy ke section), sass uritized chloritized and epidotized (in the Upper Cumulate section) and fmally rodingitized (in the ultramafic and gabbroic sectio ns ). T he albitization process may be a res ult from ancient chemical exchanges with seawater. 1 1 1 1

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2 In the gabbroic and sheeted dyke sections the mafic minerals are uralised (forming tremolite actinolite and iddingsite ) as well as chloritized Extensive epidotization occurs in the upper gabbroic and especially on the transition between the sheeted dykes and basalt sections Epidote is not related to any tectonic reworking or later greenschist fluid input. 3 The Olivines from the Cumulate unit are serpentinized (into lizardite and chrysotile) and chloriti z ed i n the dyke and basalt units. 4 In pillow lavas chlorite is more abundant than actinolite whereas in the sheeted dykes this relationship is reversed. 5. Plagioclase alteration includes sericite only in the pillow lavas 6 Calcite was formed after plagioclase albitization. It s abundance decreases downwards in the ophiolite succession. In clinopyroxene-plagioclase cumulates calcite is missing Hence minerals typical of rodingites such as hydrogarnet clinozoisite, epidote hedenbe r gite chlorite and tremolite were formed The association tremolite-actinolite-chlorite-albite-calcite is indicative of greenschist facies metamorphic conditions Greenschist minerals were determined in all the 70 thin sections examined (see Apendix A). The formation of rodingites is believed to record the effects of typical ridge-related hydrothermal metamorphism (Nicolas 1989). Pos s ible seawater alteration is recorded in the petrography of the upper units of the B-C ophiolite ( e specially in the pillow lavas where alibitization ( = spilitization) is prevalent) The origins of the lower-greenschist alteration in the deeper BCO sequences are less clear but are not inconsistent with sub-seafloor metamorphic processes 12

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BULK CHEMISTRY Major and Trace Elements: Tables 14 list our major and lithophlle trace element results for the different units of the BCO. Although we chose the freshest and most unaltered rocks for geochemical study, metamorphlc effects are evident in all our samples. However the low metamorphlc grade of the BCO allow us to study geochemical profiles through the complex much as can be done in younger ophlolites, and even to compare it directly with other well characterized ophlolites throughout the world (see references in Nicolas 1989). Data for elements known to be mobilized during low-grade metamorphlsm are treated as suspect (Kepezhinskas et al., 1995 ; Bodinier et al. 1988; Frey et al., 1985 ; Staudigel and Hart, 1983) The degree of hydration in the ultramafic and mafic cumulates can be qualitatively estimated from our Loss on Ignition (LOI) values LOI varies from 2.515.37% for the unaltered troctolites, anorthosites and olivine gabbros, and from 9.68-13. 76% for the highly serpentinized dunites wehrlites, lherzolites and troctolites (Table 1). In the gabbroic sequence LOI values are very consistent, ranging between 1 34.4% irre s p ec tive of rock type (Table 2). In term s of major elements, our BCO samples show a compositional range consistent with genetically associated cumulate and volcanic rocks (Figures 2a and 2b). MgO abundances in basalts range from 7.09.7 wt%, and in the sheeted dykes range from 4.39-10.4 wt%. Mean Ti02 in the sheeted dykes (0.772.18 1 3

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wt%) is lower than in the basalts (1.45-1.83 wt%), though both are slightly high compared to MORBs at similar MgO. Alteration related to exchanges with Precambian seawater is suggested by the elevated N a20 contents in basalts and dikes (2 245.1 7 wt%) relative to the cumulates (Figure 2d). Ba and Sr both show wide variation in B-C basalts but are not markedly elevated in the freshest samples (Figure 2c). Variations inCa and Al abundances in BCO cumulate rocks (Tables 1 and 2) may suggest an important role of plagioclase accumulation in the BCO magma chamber. In figure 3a, a plot of FeO/FeO+MgO vs Ti02 (Serri 1981) almost all BCO basaltic rocks fall in the highTi ophiolite field On a range of discrimination diagrams (Figures 3b to 3e) rocks from the extrusive section of BCO appear indistinguishable from modem ocean ridge basalts. Our samples lack the high AI, low FeO*(total Fe) and low Ti02 considered by some authors to be the backarc basalt signature (behavior reflecting the higher water content ofbackarc magmas)(Fryer 1995; Hawkins 1995). Moreover both the basalts and diabases have on average relatively high Cr (591031 ppm) and Ni (371208 ppm) contents typical for mid-ocean ridge basalts and not typical for backarc basalts. Also the TiN discrimination plot (after Shervais 1982)(Figure 3e) postulates that if the basalt is with backarc origin it should clearly cluster between the MORB field (TiN ratio = 20-50) and island arc field (TiN ratio = 1 0-20). In figure 3e (and even in figure 3d), our samples plot only in the MORB field and have no evidence of any arc influence which should be expected if they have backarc origin (Hawkins, 1995; Fryer 1995). Rare Earth Elements: Twenty-two (22) samples from Tchemi Vrah and Deli Jovan representing both the upper cumulate and extrusive sections ofBCO, were analyzed for rare earth elements 14

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(Tables 5-7) REE patterns for extrusive rocks are flat and all show MORB-like Light Rare Earth Elements (LREE) depletions (Figure 4a and 4b ). This confirms that the B-C ophiolite volcanics originated from mid-ocean ridge setting not from backarc setting in which the LREE depletions would be influenced by the suprasubduction zone magmas and have variable sometimes enriched LREE patterens (Hawkins 1995). B-C ophiolite cumulates and sheeted dykes show stronger LREE depletions than the basalts. The REE abundances of the cumulate and extrusive rocks show nested REE patterns of progressively higher abundances consistent with genetic relationships among all BCO lithologies (i.e the cumulates are reasonable residual compliments to B-C extrusives (see also Figure 4c). The importance of plagioclase crystallization is marked by strong negative Eu anomalies in the mafic cumulates sheeted dykes and basalts. Amphibole crystallization may be indicated by the concave upward shape of REE patterns for samples from the upper cumulate unit (Figure 4c ). The RE E abundance patterns thus appear to confirm our petrographic inferences as to the order of crystallization: olivine followed by pyroxene and plagioclase, with late crystallization of amphibole. DISCUSSION 1) PETROGENESIS OF THE BALKANCARPATHIAN OPHIOLITE Our geochemical results, combined with stratigraphic, lithologic, and textural relations hips established by detailed field mapping and petrography of Haydoutov ( 1991) and this study allow us to place constraints on the environment of formation of the B-C ophiolite. Our data support the idea that the two BCO massifs studied represent cumulate and volcanic igneous rocks formed at a mid-ocean ridge Samples from both the Deli Jovan and Tchemi Vrah massifs define a single compositional array on the majority of 1 c 1.)

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chemical diagrams (see Figures 2-4) suggesting that they represent fragments of a single ophiolite thrust sheet. The observed transition from the sheeted dykes unit into pillow basalts and the petrographic and chemical relationships between these units and the cumulates are consistent with observations from ODP drilling in modern ocean-ridge settings and with well-studied ridge-related ophiolites (Nicolas, 1989). In terms of both lithophile trace elements and the rare earths the extrusive section of the B-C ophiolite possesses a strongly MORB-like signature (Figures 3 and 4). All of the basalts are tholeiitic and the section is thick which is typical of mature ocean floor ridge volcanism (BVSP, 1981). No intermediate composition volcanics were discovered nor any dioritic or trondjhemitic intrusions, as might be expected in back-arc or arc related complexes (Nicola s, 1989; Scott et al., 1991 Hawkins, 1995). Also, the se dimentary cover on BCO pillow lavas consists ofFe-rich umber s (with Fe contents up to 12.5 wt% ) which are typical of deep marine environments such as might be expected relatively close to an ocean ridge-cre s t and its associated hydrothermal sy s tems (Nicolas 1989). These points along with the order of crystalli z ation in B-C cumulate s, the absence of cumulate orthopyroxene the geochemical similarities between BCO basalts and MORBs (high Ni Cr, Ti and V; see also Fig 3a-e ), and strong compositional s imilaritie s between BCO basalts and Eas t Pacific Rise MORB (see also Tables 18-20 in Appendix G) (Ryan 1989 ; Langmuir et al. 1986 ; Basaltic Volcani s m Study Project 1981; Melson et al., 1976) all point to a mid-ocean ori gin for the B-C ophiolite Comparison between the BCO and recent data on backarc basin basalts (Mariana backarc ba s in ((Fryer 1995); Lau backarc basin (Hawkins 1995)) shows that there is enough differences to rule out the possibility ofbackarc (suprasubduction zone) origin for B-C ophiolite 1 6

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2) GEODYNAMIC IMPLICATIONS OF THE B-C OPHIOLITE : The petrology and geochemistry of the Balkan-Carpathian ophiolite strongly suggest a mid ocean ridge origin which indicates the existence of ocean basin in the Balkans region in the Latest Precambrian. Together with the overlying Cambrian island arc sequence, the BCO forms what is known as the Balkan Assemblage (Haydoutov and Yanev 1997). The Balkan Assemb l age is covered unconformably by an Early Ordovician in age (Kalvacheva, 1986) olistostromal sequence the Dalgi-Dial Group (Haydoutov 1991) which contains olistoliths of ophiolitic rocks and igneous rocks of island arc affiniites Because of its excellent exposure (50 000 km2 ) and preservation (only slightly affected by Variscan and Alpine metamorphic events) the Balkan Assemblage may offer key insights into the Late Proterozoic-Early Paleozoic tectonic evolution of western Gondwanaland (see Appendix H). The B-C ophiolite is located between the Pan-African ophiolites and the A valonian-Cadomian peripheral orogens (including the Bohemian mass if) and might be the missing link between them (Murphy and Nance 1995)(see Appendix H) Based both on radiometric and biostratigraphic constraints the ages of rocks from the Balkan Assemblage straddle the Precambrian Cambrian boundary (540 Ma; Odin et al., 1983 Compston et al. 1992; Bowring et al. 1993 ; 1998) and the age of the B C ophiolite (563 5 Ma; Quadt et al. 1998) is Neoproterozoic The main tectonothermal events of the late Proterozoic ( Pan-African) cycle in Western Gondwana fall in the time range of650-500 Ma (Kroner 1984 ; Unrug, 1993 ) Thus the rocks ofthe Balkan Assemblage are time-correlative with the latter part of the Pan-African orogenic episode (see Appendix H) 17

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The Balkan Assemblage which lies on the margin of the Balkan terrane (Haydoutov and Yanev 1997) is also proximal to the Arabian-Nubian Shield and the A valonian-Cadomian peripheral orogens (Murphy and Nance 1995). The comparison of the B-C ophiolite with ophiolites from the ArabianNubian Shield (Abdelsalam and Stem, 1993 and Sultan et al., 1993 (for ophiolites from the Nakasib suture); Bakor et al 1976 and Stem et al., 1990 (for ophiolites from the Onib-S Hamed suture)) demonstrates that the ophiolites from both regions have a number of common features: e .g composition of the cumulates ( dunites, wehrlites pyroxenites and gabbros); geochemical affinities of the volcanic rocks to MORB; type ofmetamorphism(greenschist facies) The clearest differences between them concern their age, associated sediments and the time s pan between their age of formation and the time of obduction. Arc-related sequences in the basement of the ArabianNubian Shield show a tendency to become younger from SE to NW, with ages ranging from 900-800 Ma along the southernmost margins of the shield to as young as 540 Main the north (Stoeser and Camp 1985 ; Stem and Hedge, 1985) The arc-related se quence s in the Balkan Assemblage thus appear to be time-corr e lative with arc-sequences around the NW part of the Arabian Nubian shield, another suggestion that the B-C ophiolite and associated rocks may be connected to Pan-African orogenic events. Also successor basins developed atop PanAfrican age basement rocks appear to have begun receiving s ediments between the latest Proterozoic and the early Paleozoic, some as late a s the Ordovician, (e.g. Parana Basin ; Rogers et al. 1995). In the Murzuk and Wajid basins the earliest sediments are Cambrian to Ordovician in age (Dabbah and Roger s, 1983). The age ofthe Dalgi Dial olistostromal sequence which represents the beginnings of se dimentation in Paleozoic successor ba si ns which developed atop Balkan 18

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Assemblage rocks is early Ordovician (Kalvatcheva 1986) again consistent with the age distributions for orogenic and post-orogenic events in the Pan-African orogeny. Thus both geochemically and tectonically the B-C ophiolite is consistent with an origin in the ProtoTethys ocean and emplacement during the Pan-African collisional event. (see Appendix H). A comparison between B-C ophiolite and the ophiolites ofNakasib suture (Abdelsalam and Stem 1993 and Sultan et al. 1993) shows that the latter associate with sediments from passive continental margin while over the B-C ophiolite such sequences have not been established. Another difference could also be underlined the time s pan between their age of formation and their obduction These differences probably reflect the diverse conditions of the ophiolite formation in incipient rift and in mature ocean CONCLUSIONS The Deli Jovan and Tcherni Vrah ophiolitic massifs are equivalent units both g eochemical and lithologically, and represent fragments of a single B-C ophiolitic mas s if. The B-C ophiolite overall s hows clear mid-ocean a ffinities and probably represents a crustal fragment from a large oceanic basin. The B-C ophiolite and overlying arc-related sequences of the Balkan A ss emblage along with the olistrostromal sequences of the overlying Dalgi Dial group show a strong chronologie connection to events in the later portions of the Pan-African orogeny a s recorded in units along the margins of the Arabian-Nubian s hield. We thus sugges t that the Balkan Carpathian ophiolite represent s crustal rocks from the ProtoTethys ocean basin emplaced in the closing stages of the Pan African collision. 19

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REFERENCES Ageed A., Saager, R. and Stumfl E. 1980 Pre-alpine ultramafic rock s in the Eastern Central Alps Au s tria in Panayotou A ., ( Ed ) Ophiolites: Cypru s, Proceedings Intern a tional Ophiolite Symposium 601606 Abdelsalam M G. and Stem R.J ., 1993 Structure ofthe late Proterozoic Nakasib suture Sudan Journal of the Geological Society London 150 393-404 ; 10651074. Ballard R. and Moore J ., 1977 Photographic atlas ofthe Mid-Atlantic Ridge rift valley.N Y Springer-Verlag p.l14. Beccaluva, L., Ohnenstetter. D. and Ohnenstetter M ., 1979 G e ochemical discrimination between ocean floor and i sland arc tholeiitesApplication to so m e ophiolite s, Can. Jour. ofEarth Sci., 16 18741882. Bakor A R. Gass I.G. Neary C.R ., 1976 Jebel al Wask northwe s t S o udi Arabia: an Eocambrian back-arc ophiolite, Earth Planet.Sci Lett, 30, 1-9. Bodinier J.L. Dupuy C and Dostal J. 1988 Geochemistry and petrogene s is of eastern Pyrenean peridotites Geochim. Co s mochim Acta., 52 28932907. Bodinier J .L., Dupuy C and Dos tal J. 1981 Geochemistry of ophiolite s from Charnrousse Complex (Belledone massif the Alps), Contrib. Min Pet. 78 379388. Bowring, S A., Gretzinger, J.P Isachsen C .E. Knoll A.N. Pelechaty S.M. and Kolosov, P ,1993 Calibrating rates o f Early Cambrian evolution Science 261 12931298. Bowring, S A and Erwine D.H. 1998, A new look at evolutionary rates in deep time: Uniting paleontology and highprecision geochronology GSA Today, 8 9, 1-6. BVSP Basaltic Volcanism Study Project, 1981 Pergamon pres s; N ew Yor k, 132-150 Compston W Williams I.S Kirchvink J L., Zichao Z and Guogan M.A.1992 Zircon U-Pb a g es for the Early Cambrian time s cale Journal of the Geol. Soc. London, 149, 171-184. Dabbah M.E and Roger s, J.J ., 1983 Depositional environments and tectonic significance ofthe Wajid Sandstone o f south e rn Saudi Arabia Jour. of African Earth Sci. 1, (1) 47 57 20

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Frey F A ., Suen, C.J. and Stockman H. W 1985 The Ronda high temperature peridotite: Geochemistry and Petrogenesis. Geochim Cosmoch im. Acta., 49, 24692491. Fryer, P., 199 5, Geology of the Mariana Trough, in Backarc basins: Tectonics and Magmatism, Bryan Taylor (ed) Plenum press New York 237-274. Gonco uglu M.C. 1997 Distribution ofLower Paleozoic rocks in the Western Black Sea Region Turkey Ear ly Paleozoic evolution in NW Gondwana, Proceedings IGCP Project 351, Ankara, 13-23. Hawkins J.W. 1995 The geology ofLau Basin, in Backarc basins: Tectonics and Magmatism, Bryan Taylor (ed) Plenum press New York, 63-130. Haydoutov I. and Yanev, S. 1997. The Protomoesian microcontinent ofthe Balkan Peninsulaa peri Gondvanian piece Tectonophysics 272, 303313. Haydoutov 1., 1991, Origin and evolution of the Precambrian BakanCarpathian ophiolite segment, Bulg. Acad. Sci., Sofia, 179 pp.(in Bulgarian with English summary) Haydoutov I., 1989, Precambrian ophiolites, Cambrian island arc and Variscan suture in South Carpat hianBalkan region, Geology 17, 905908. Herbert, R. and Laurent, R., 1990. Mineral chemistry of the plutonic sec tion of the Troodos ophiolite: New constrains for th e genesis of arc-related ophiolites. In: J. Malpas E. M. Moores, Panayiotou, A. and Xenophontos C. (Editors) Ophiolites: oceanic crustal analogues. Geol.Surv.Cyprus.Nicosia Cyprus, 149 163 Kalenic M. 1986 First find of Lower Cambrian in E. SerbiaS. Carpathian Mountain s, Rev. Bulg Geol. Soc., 58(2). Kalvatcheva R., 1986 Acritarch stratigraphy ofthe Ordovician system in Bulgaria. Abstract Final field meeting, IGCP Project 5, Sardinia, Italy 38-43. Kepezhinskas P. Sorokina N., Mamontova,S. and Savichev, A., 1 99 5, Rare Earth and Large Lithophile (Sr and Ba) element geochemistry of diabase dikes hole 504 B, Costa Rica Rift Leg 140, Proc. ODP Sci. Results 137 / 140 107 115 Kolcheva, K. and Jordanov, B., 1984 Ultramafics and rodingite-gabbro fragments of culmulative ophiolite in the region ofKopilovzi W.BalkanAbstracts conference Bulg.Geol.Soc. Mihailovgrad 15. Kroner, A., 1984 Late Precam brian plate tectonics and orogeny: a need to redefine the term Pan African in : Klerkx J. and Mishot J. (eds) African geo lo gy, Tervuren Belgium.2328. 2 1

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Langmuir,C H Bender J F and Batiza, R ., 1986 Petrologic and tectonic segmentation of the East Pacific Rise, Nature, 322 422429. Mel s on W. G ., Vallier T.L. Wright T .L., Byerly G and Nelen, J., 19 7 6 Chemical diversity of aby s sal volcanic g la ss erupted along Pacific, Atlantic, and Indian Ocean seafloor. In The Geophysics of the Pacific Ocean basin and it' s margin AGU monograph Washington DC p.351367. Morman S. Cochrane D. KatesK. Olesky M Paule y T., Thomas C ., Lee A., Lindenberg M., Liz ee T ., McCoyA. Meyers S., Rahl J. I.Savov J.G.Ryan V.L.Peterson, 1999, Petrog e nesis and metamorphism o f amphibolites from the Buck Creek mafic-ultramafic complex, Clay Co., NC, GSA Abstracts with Programs vol.31 3, 64. Murphy J. and Nance, R., 1995 Supercontinent model for the contrasting character of Late Proterozoic orogenic belt Geology 19(5) 469472 Nakamura N 1974, Determination ofREE, Ba, Fe Mg, Na and Kin carbonaceous and ordinary chondrites Geochim. Cosmochim. Acta., 38 757 775. Nicolas, A 1989 Structures of ophiolites and dynamics of oceanic lithosphere in Petrology and and structural geology monograph series Amsterdam Kluwer, 187200 Odin G S. Gale N.H., Aurvay, B. Bielski M. Dore, F., Lancelot J.R. and Pasteels P., 1983 Numerical dating ofPrecambrianCambrian boundary N ature 301 ,21-23. Pearce J.A, 1982, Trace s element s characteristics of lavas from destructive plate margins, In Andesites Thorpe R.S. (Ed's) John Wiley and Sons 525548 Pearce J.A. and Cann J. 1973 Tectonic setting ofbasic volcanic rocks determined using trace element analysis, Earth Planet.Sci.Lett., 19 2, 290-300. Quadt A.V ., Pe y cheva I. and Haydoutov I., 1999. UZr dating o f T c emi Vrah metagabbro, West Balkan Bulgaria. Comp. Acad Bulg.Sci., 51(1 2) 86-89. Roger s J J ., Unrug, R and Sultan M 1995, Tectonic assembly of Gondwana, J Geodynamics 19(1), 1-34. Ryan J G and Langmuir C.H ., 1993 The systematics ofofboron abundances in young volcanic rocks, Geochim. Cosmochim Acta. 57, 1489 1498. Ryan J G 1989 The s ystematics of Lithium Berillium and Boron in y o ung volcanic rocks PhD dissertation Columbia University 291293. 22

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Scott, D.J ., St-Onge, M. R., Lucas, S.B. and Helmstaedt, H., 1991 Geology and chemi s try of the Early Proterozoic Purtuniq ophiolite, Cape Smith Belt Northern Quebec, Canada, In: Peters Tj., Nicolas, A. and Coleman R.G.(editors) Ophiolite genesis and evolution ofthe oceanic lithosphere, K.luwer 818-844. Serri G. 1981 The petrochemistry of ophiolite gabbroic complexes: A key for the classification of ophiolites into lowTi and highTi, Earth Planet. Sci.Lett. 52, 203-212. Shervais J. W, 1982, Ti vesrsus V plots and the petrogenesis of modem and ophioitic Lavas Earth Planet.Sci Lett 59, 101118 Staudigel, H. and Hart S R. 1983, Alteration of basaltic glass: Mechanisms and significance for the oceanic seawater budget Geochim. Cosmochim. Acta. 4 7 337 Stem R.J. and C.E. Hedge 1985 Geochronologic and isotopic constraints on Late Precambrian crustal evolution in the Eastern Des s ert of Egypt. Amer.J. of Sci ., 285 97-127. Stem R.J, Nielsen, K.C., Best E., Sultan M Arvidson, R.E., and Kroner, A., 1990, Orientation oflate precambrian sutures in the Arabian-Nubian Shield Geology, 18, 1103-1106 Sultan, M. Beck er, R. Arvidson, R. E., Shore P ., Stem, R.J., E l Alfy, Z. and Attia, R.I. 1993 New Constraints on Red Sea rifting from correlations of Arabian and Nubian Neoprotero z oic outcrops, Tectonics 12 6, 1303-1319 Stoeser D. and V. Camp, 1985 PanAfrican microplate accretion of Arabian shield. Geol.Soc. Am. Bull. 96 817-826. Tenthorey E.A., Ryan, J.G and E.A. Snow, 1996 Petrogene s i s of sapphirin e -bearin g meta troctolites from the Buck Creek ultramafic body southern Appalachians Journal ofMetamorphic Geology, 14, 103-114. Terzic M. 1981 Geosynclinal igneou s activity in the CaledonianVariscan cycle of Eastern Serbia. In P etro vic K.( ed) Geology of Serbia, 3-1, Magmatism Belgrade Univ. ofBelgrade, 33 -47(in Serbo-Croatian ) Unrug, K, 199 3, The Gondwana s upercontinent: Middle Proterozoic crustal fragments Late Proterozoic assembly and unresolved problems. In Fidlay Unrug, Bank s, and Veevers (eds ) Gondwana Eight Balk ema, Rotterdam 3-8. Ustaomer, P .A. and E. Kipman, 1997 Remnant of PreE arly Ordo v ician Cadomian active margin in Wes t Pontide s, N.Turkey. Terra Nova, 9, 3 82 23

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APPENDICES 24

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APPENDIX A PETROGRAPHIC DESCRIPTIONS 25

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CUMULATES I ) DU-5 / I DU-5/2 Serpentinized Dunites (Appendix B, Plate I and 2) Relics of primary (magmatic) minerals are not preserved in these thin sections. The formal olivines are coarse-grained and regardless of the intense serpentinization their crystal s hape can be recognized. The olivine was the only silicate mineral. Fe-oxides were formed during the serpe ntinization proc esses and thi s points out that the olivine was Fa-rich. After precry sta lli zatio n the Fe-oxides were concentrated in thin veins cros scu tting the olivine grains or as dustlike and fibrous material within the serpentine. The int ers tice s between the olivine grains are filled with magmatic in origin opaque mineral filling %of the rocks. Often it i s altered to hematite and probably h y drated. It is possible that this mineral i s Fe-rich spinel. The metamorphic textures are hourglass and alpha-serpentine mesh textures. It appears that the primary texture of the rock was euhedral granular (panidiom orp hic ). 2) LR22/1, LR22/2 ANI /77 Serpentinized Wehrlite s (Appendix B, Plates 3 and 4) Although part of the primary minerals are replaced by secondary, metamorphic mineral s these samples are typical ultramafic cumulates. Clinopyroxene and hornblende are preserved as relic magmatic minerals The metamorphic mineral s are serpentine Fe oxide min era l fibrous clinopyroxene tremolite, chlorite and boulingite. 26

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The olivine was originally the most common mineral It is now serpentinized and pyi-oxenized, but in LR-1/77 an olivine relics are still preserved. Sometimes the olivine grains are arranged in cumulate layers. Most of the former olivine grains have preserved their euhedral (authomorphic) crystal habit and this confirms their cumulate origin. The serpentinization is expressed in a typical for the process mesh textures in which very low birefringence fine-grained serpentine is divided into small blocks by numerous veinlets of serpentine with slightly higher birefringence. Fibrous 'clinopyroxene inclusions crystallize in the center of these window-like serpentine grains. The serpentine is two types: Type 1-lizardite typewith hourglass textures and fibrous to micaceous habit. Type 2later serpentinecrystallizes in rock cracks and in association with opaque Fe oxide grains. These Fe-oxides are evidence that the olivine was Fa-rich. Iddingsite boulingite minerals are present around the opaque Fe-oxide grains and they are related to this (Type 2) serpentine. The second most common mineral ( 15%) is the clinopyroxene diopside (optically + ). It crystallize s in the interstices between the olivine grains. The clinopyroxene is often metamorphosed to tremolite. Chloritization of the clinopyroxene is also common. Sometimes secondary metamorphic clinopyroxenehedenbergite (optically-) is present. Magmatic in origin hornblende is building up to 1 0% of the rock. As the clinopyroxene it fills the interstices between the euhedral (authomorphic) olivine grains It is colorle s s (rarely brown and pleochroic) and often metamorphosed to tremolite. 27

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About 1520% of these rocks are filled with very finegrained polymorphic aggregates occurring between the euhedral olivines or partially surrounding them. The typical rodingite-representative mineral assemblage clinozoisite + hydrogarnet was found between the formal olivine grains This is a good evidence for the existence ofrodingitization processes (especially in LR-1/770. Corona textures are present almost in all thin sections: the original olivines are mantled by coronas that mark the contact with the magma residue. The rock is an orthocumulate with crystallization order: olivine clinopyroxenehornblende 3) AN9/77 Anorthosite The plagioclase is saussuritized but in several relatively fresh grains labradorite compositions are recognizable. Grains exhibiting zoning were not found. 4) TR -1 GabbroAnorthosite This rock is with mediumto coarsegrain texture. The two main minerals are plagioclase and clinopyroxene. Amphibole is also present as magmatic mineral. It preserves evidence for reaction processes between the primary phases and the intergranular melts. The plagioclase forms elongated lathshaped euhedral crystals that fill up to 60 % of the rock They exhibit fine lamellae twinning of both albite and Carlsbad types. It's An content is 75% (Bytownite). Usually it is unaltered but along cracks it may be L.O

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replaced by clay minerals The plagioclase is a cumulate mineral because the later clinopyroxene is situated in the intercumulus space between the already accumulated plagioclase grains. The clinopyroxene is building ofthe rock. It is mantled by reaction rims of red brownish amphibole (sometimes pseudomorphing the clinopyroxene) Exsolution lamellae are common within the interiors of the clinopyroxene whereas their rims have clear appearance. A fine-grained mineral aggregate fills the interstitial space between the plagioclase and clinopyroxene grains It appears that it is a product of residual magmatic melts. A clear zonal appearance of this aggregate was observed: interiors with medium to finegrained tremolite and exteriors consisting of very fme-grained chlorite and hydro micas. Often the chlorite is concentrated in monomineralic zones. The intergranular residual melts also crystallize in fractures within the plagioclase and clinopyroxene crystals. Accessory mineral is an opaque mineral (probably ilmenite). Cumulate, corona and poikilitic textures are present. The crystallization order is plagioclaseclinopyroxeneamphiboletremolitechlorite. 29

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5) TR2 TR3 Troctolites (Appendix B Plates 5 and 6) These rocks are unaltered and coarse grained. They contain plagioclase olivine and minor clinopyroxene. Accessory mineral is magnetite Plagioclase is the predominant mineral in these rocks (-55%) and occur as thick prismatic laths with granular (allotriomorphic) shape and with well-developed albite and Carlsbad twins. It is unaltered but sometimes along cracks is partially saussuritized. Anorthite content is 70% (Bytownite) The olivine forms irregular and spherica l in shape grains rimmed by clinopyroxene The ol ivine builds up to 30% of the rock. It is unaltered but orange and green in color micaceous in habit boulingiteiddingsite minerals may partially replace it along cracks. Product of the same alteration is Fe-oxide mineral. The clinopyroxene appears not only as rims around the olivine but also as a short prismatic xenomorphic grains. In many cases brownred amphibole peritecticly surrounds them. Many of the clinopyroxenes h ave fibrous inclusions that are result of exsolution processes. The accessory mineral is magnetite (Ti-magnetite). The texture is granular (allotriomorphic)all the rock forming minerals are xenomorphic. 30

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6) TR-4 Troctolite This rock is almost identical to TR-2 and TR-3 both compositionally and texturally. The main differences are: l.TR-4 is more deformed then TR-2 and TR-3. 2.TR-4 is enriched in mafic minerals (olivine and clinopyroxene) and the ratio between the plagioclase and the mafic minerals is 50:50. 3.The mafic mineral in TR-4 is mostly olivine (clinopyroxene is rare) 7) TR-24 Olivine cumulate The rock is with pseudoporphiric texture outlined by the accumulation of big euhedral olivine crystals that flow within the intercumulate graundmass. The olivine builds up to 80% of the rock. Originally it formed euhedral (authomorphic) crystals that are now entirely pseudomorphosed by oriented fibrous clinopyroxenehedenbergite aggregates (hedenbergite can be easily identified by its high relief comparing to the cryptocrystalline chlorite that grows together with it). The original shape of the olivine grains is underlined by boulingite minerals that outline the xenomorphic nature of the intercumulate aggregates. The matrix that surrounds the cumulate olivine is build mainly by chlorite that is with crypto-to fine-grained micaceous habit. This chlorite is mixed with hydro-micas ofmonthmorillonite type (including the boulingite). Sphene is not 31

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uncommon and crystallizes in the interstices between the formal olivine grains. A few relics of magmatic amphibole that is partially altered to chlorite were observed They surround the euhedral olivine grains but the relationship with the other minerals is impossible to reconstruct 8) GB23 Olivine gabbro The cumulate phases of the rock reacted with the residual melts and therefore the dividing of primary and secondary magmatic phases is very hard. This reaction was very intense and took place within the entire thin section. The olivine is preserving euhedral crystals that are pseudomorphosed by very fine-grained assemblage of serpentine tremolite, chlorite and monthmorillonite. The olivine crystals tend to concentrate in certain parts of the thin sections and are relatively rare Plagioclase is the predominant mineral in the thin section and builds up to 50% of the rock As the olivine it has euhedral crystals that are relatively coarsegrained Only in few cases it's lamellae appearance can be seen due to the intense saussuritization Clinopyroxene is unevenly spread out within the rock and crystallize as finegrained diopside crystals It is more abundant then the olivine and builds up to 15% of the rock. It is unaltered, but sometimes it is mantled by redbrownish amphibole. This amphibole is one of the last phases to crystallize and builds up to 1 0% of the rock It may be interpreted as a product of reaction between the clinopyroxene and magnetite (formed earlier) and the residual melts The red brownish amphibole mantles a pseudomorphosed 32

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by cryptocrystalline monthmorillonite fernie mineral. This mineral fills up to 5% of the i:ock and resembles biotite but fresh relics are absent. Tremolite is the most common fernie mineral is the rock ( 20%). It crystallizes as finegrained prismatic crystals or in gridlike aggregates It is metamorphic in origin and often mantles early formed fernie minerals (mostly amphibole and olivine). Accessory minerals are anhedral in shape magnetite and rare apatite The apatite is with brownish color and this proves that even after it's crystallization there was still residual liquid (the apatite from the volcanic rocks is "smoky i.e. yellowbrownish). The rock preserves typical cumulate gabbroophitic and even poikilitic textures. 9) GB-20 Gabbro Plagioclase ( 65%) and clinopyroxene ( 25%) are the main minerals in the rock Plagioclase crystallizes as euhedral grains with albite twinning. It is unaltered and only along mineral fractures may be slightly saussuritized Anorthite content is 7075% (Bytownite). Euhedral plagioclase grains as inclusions in the clinopyroxene form the common poikilitic texture. Clinopyroxene is diopside and comparing with the plagioclase is more xenomorphic and finegrained It is unevenly spread out in the thin section. The clinopyroxene occurs also as twins Rarely it is partially rimmed by brown amphibole. Magnetite (Ti-magnetite) is present as accessory mineral as well as several clinozoisite grains probably product of the plagioclase alteration The rock texture is gabbroic. "" .).)

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10) GB-2 Gabbro (Appendix B Plates 9 and 1 0) The main rock forming minerals are plagioclase clinopyroxene and amphibole. The plagioclase occurs as prismatic grains that often crystallize as albite or Carlsbad twins. It is mostly unaltered but along mineral fracture zones is partially saussuritized. Zoned crystals are rare. The An con tent is -6570% (Labradorite). The clinopyroxene builds up to 30% of the rock It forms grains with the size of the plagioclase. Throughout the entire thin section but in different degree it is metamorphosed to tremolite. This uralitization process is developed from the fringe zones of the clinopyroxenes towards their center. Sometimes they are entirely pseudomorphosed by tremolite. Probably the tremolite is a product of clinopyroxene residual melt reaction. 25 to 30% of the rock is made of grid-like, finegraine d tremolite that is a result of the same reaction. A few tremolitized clinopyroxene grains are rimmed by redbrown amphibole. Accessory minerals are magnetite pyrite apatite and rare calcite. The primary texture was gabbroic which later on turned into corona. 11) GB-1 Gabbro This rock is almost identical with GB2. The following differences between the two rocks should be noticed: 34

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l.Gb-2 is coarsergrained. 2.The tremolitization in GB-1 is more advanced. 3 The tremolite in GB2 has crystallized not only via clinopyroxene metamorphism but also after plagioclase alteration In this case together with the tremolite crystallizes a finegrained aggregate of clinozoisite and calcite. 12) GB4 Gabbro The primary minerals in this rock had suffered precrystallization processes and are replaced by secondary metamorphic in origin mineral association. A few relics are still preserved and in some cases the original crystal shape of the primary minerals can be identified The rock was coarse grained and was build of plagioclase and clinopyroxene. The plagioclase was filling up to 50% of the rock volume as thick and prismatic in habit grains. It is now altered to saussurite tremolite, chlorite, carbonates and clinozoisite The remnants of unaltered plagioclase are clear in plain polarized light (ppl) and exhibit lamellae structures. Anorthite content is -65-70% (Labradorite). Relics of clinopyroxene are rare. They have been metamorphosed to few generations of amphibole but the original clinopyroxene grain shape is still preserved In some cases the boundaries between the primary minerals are impossible to reconstruct. The amphiboles build up to 45% of the rock. Most of them are clinopyroxene metamorphic products. Also associated with the plagioclase alteration is the very finegrained tremolitechlorite aggregate, which is filling the interstitial space between the ,t: .).)

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plagioclase grains or fractures in them Chlorite is also associated with the plagioclase alteration. The precrystallization of the rock should be entirely linked to the remaining fluidrich magma melts (i.e the process is with the signatures of authometamorphism and partial chemical exchange) No accessory minerals were found but one opaque mineral grain The rock texture is gabbroic 13) GB-5 (Appendix B, Plate 7 and 8) Gabbro This rock is similar to rock GB-4 but it is finergrained and more extensively metamorphosed Relics of primary clinopyroxenes are absent with only two exceptions of clinopyroxene chadacrysts included in the plagioclase host grains. The clinopyroxene is otherwise entirely replaced by amphibole. When the clinopyroxene grains are big enougha few generations of amphibole can be determined. Most of the amphibole is tremolite ( 35%). Other source for tremolite is the plagioclase. Sometimes it is metamorphosed to cloths of fibrous tremolite and chlorite This type of tremolite is building up to 25% of the rock and thus the total amphibole content of the rock is -60%. The plagioclase is present as small, fractured but clear in plane polarized light (ppl) relics It's An content is 50-55% (AndesineLabradorite) It has been saussuritized, tremolitized and sometimes carbonatized. The rock is very poor in accessory minerals and only a few opaque minerals were found The primary texture of the rock was ophitic to poikilitic (CPX inclusions in PI and PI inclusions in CPX). 36

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14) GB6, GB7, GB 8/2 Pegmatoid Gabbro The rock contains coarse to very coarsegrained amphibole and plagioclase. They occur very irregularly within the rock The plagioclase is enclosed in the amphibole, which rims the clinopyroxene. Sometimes it is altered to zoisite clinozoisite that are randomly spread within a clear plagioclase substance. The clear plagioclase material has relatively low N and vary rare is with fine lamellae structure. The plagioclase usually form a coarse grained crystals which are highly fractured. These fractures are filled with the same clear plagioclase material. In areas, which exhibit pressure solution structures, the plagioclase precrystalizes into very finegrained aggregate with development of triple junctions Even when the amphibole resembles a sing le grainit i s an aggregate build of acicular or radial in s h ape broomlike aggregates. The amphibole replaces the clinopyroxene. This conclusion was made based on the sphene grains that occur in close relation with the amphibole (both as a metamorphic products of the clinopyroxene). The texture is poikilitic to poikiloophiticthe amphibole is rimming a fernie mineral (clinopyroxene) that is a host of the plagioclase laths. In TS 8 /2 the mineral grains grade in size and are coarser then the relatively finegrained GB-6 and GB-7. 37

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15) GB 8/1 Finegrained I pegmatoid gabbro boundary (Appendix B, Plate 11) This boundary is very sharp but there is no difference in the mineral composition of the two types of gabbroic rocks. The finegrained gabbro is an amphibole gabbro. In this gabbro the amphibole is a secondary mineral that forms very finegrained fibrous to prismatic aggregates with light green color. Primary plagioclase is altered mostly to clinozoisite and sometimes to Anpoor secondary plagioclase. Grainsize in this type is up to 3x 1 em. The pegmatoid gabbro is with the same characteristics as the fine-grained gabbro but the grainsize of the plagioclase and amphibole crystals is much bigger (from 4xlcm up to 22x 1 Ocm observed in the field and in hand specimen). Here the primary mafic mineral is replaced by colorless tremolitic amphibole. The plagioclase is altered to clinozoisite and almost pure albite The plagioclase and amphibole content vary throughout the thin sections. The texture is gabbroic. 38

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. SHEETED DYKES 1) DB-4 Microgabbro The main rock forming minerals are plagioclase and clinopyroxene in equal quantities (sometimes the plagioclase is more abundant). The plagioclase is forming prismatic grains but because of the later metamorphism sometimes their crystal habit is partially destroyed. It is also albitized and therefore clear under plain polarized light (ppl) and with very low relief. This albitization is causing also the formation of very fine grained aggregates of plagiclase exhibiting undulose extinction. Epidote forms when the plagiclase is albitized. When this process is not presentthe plagiclase is euhedral and with lamellae structures. It's An content is 20-25 Relic clinopyroxene is preserved as prismatic in habit grains that sometimes are overgrown by amphibole The same amphibole crystallizes as fineg rained radial fibers that sometimes cross the plagioclase grains or form aggregates. This amphibole is tremolite-actinolite type formed during the later stages of the rock metamorphism. Other common greenschist minerals are epidote and chlorite. The rock has ophitic texture formed by plagioclase prisms and the development of the clinopyroxene grains in the angular interstices between them. 39

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. 2) BA-5 Basalt The rock is made of over 80% volcanic glass. Partially this glass is epidotized. Also common in the volcanic glass are plagioclase microliths that have been altered to muscovite or tremolite. The greenschist mineral assemblage chlorite + epidote is present along cracks or filling a small geods Small sphene grains are very common throughout the entire rock. Sometimes they are arranged along linear in shape cracks The rock textures are spherolithic and microintersertal. 3) BA 9, BA-10 BA-11, BA-12 Plagioclase-porphyric Diabases Common in all of these rocks is the abundant plagioclase phenocryst phase. BA-12 and BA9 are with slightly bigger (up to 0.8cm) and more abundant plagioclase phenocrysts They are with lammel ae structures and exhibit both Carlsbad and albite twins. The phenocrysts are relatively clear, with rare formations of chlorite and calcite along grain fractures. Some of them are partially altered to sericite. The anorthite content is 2025% Almost all of the plagioclase grains are elongated along the rock foliation In BA-11 the plagioclase grains form cataclasts exhibiting milonitic textures The groundmass is dominant in BA9 and BA-1 0 relative to the phenocryst phase. It is interesting that the foliation in this case is underlined by the chainlike arrangement of small sphene grains along the lineation planes In BA-12 the dominant phase is the plagioclase phenocrysts Here the groundmass contains chlorite tremolite epidote sphene and finegrained plagioclase. Overgrowing of these minerals is common 40

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and it is clear that all of them are products of the precrystalization of the matrix during the foliation (deformation) events. The primary rock textures are porphyric (BA12) and aphyric (BA9 ; BA1 0) and the secondary metamorphic textures are granolepidoblastic. 4) DB17 Diabase Palegreen amphibole (replacing primary fernie mineral) and plagioclase are the main rockforming minerals. The plagioclase : fernie mineral ratio is 50:50. The plagioclase crystallizes as small and elongated euhedral crystals. Phenocrysts also occur but are rare It has been entirely saussuritized and is now clear (in ppl) and with low N. The fernie mineral is replaced by pale green tremolite that is elongated and with tailended grains that are strongly oriented along the foliation planes. Accessory mineral is Ti-magnetite later replaced by sphene and hematite Other accessory minerals are epidote and pyrite commonly filling small geods. The rock is foliated but the ophitic texture is still clear 5) DB-15 Gabbro The rock has been exposed to intensive lowtemperature metamorphism. This metamorphism is the reason for the albitization of the plagioclase, the uralitization (tremolitization) and chloritization of the fernie mineral and the development of abundant epidote It is very possible that these processes are caused by the intrusions of later more fluid enriched portions of magma that originate from the same magma chamber A 1 "tl

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The plagioclase forms big and clear euhedral grains. They exhibit both Carlsbad and albite twins and lamellae structures The anorthite (An) content is 2025%. Together with the clear plagioclase grains there is also grains that are rimmed by very finegrained fibrous tremolite and coarser epidote This tremolite together with a finegrained micaceous chlorite and epidote form cluster structures. There are several generations of amphibole in this rock, which differ from each other by the intensity of their green colors. Some of them are tremolitic pale green to colorless associated with the low-grade metamorphism of the plagioclase. Others are replacing mafic mineralprobably clinopyroxene and have green colors The rock is relatively enriched inTi-magnetite that sometimes is replaced by sphene. The primary texture was ophitic but it has been reworked by the later development of the greenschist facies minerals 6) GB-19 Gabbro The two main rockforming minerals are plagioclase and green amphibole The plagioclase is more abundant and coarsergrained compared to the amphibole. Plagioclase grains are sometimes partially saussuritized and highly fractured They have prismatic habit and the grains are oriented (lineated) parallel to the foliation The amphibole forms short, euhedral and tailended grains that are also oriented parallel to the foliation Sometimes the amphibole forms fibrous crystals and together with chlorite plagioclase and carbonates is filling the rock fractures Accessory sphene is replacing primary Ti-magnetite. The texture of the rock is poikilitic to ophitic

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7) DB5 Gabbro The rock is equigranular and not deformed Most of the primary minerals are now metamorphosed with the exception of the clinopyroxene preserved as irregular and corroded relics. The premetamorphic rock textures were ophitic and poikilitic These textures are still identifiable, regardless of the greenschist metamorphic overprint and the foliation processes The plagioclase fills up to 3035% of the rock It is preserved either as big individual euhedral grains or as a small oikocrysts included in the mafic minerals (mostly in the clinopyroxene). The plagioclase was originally with relatively high anorthite content but now it is intensively albitized. The plagioclase twinning patterns can be seen where the saussuritization processes are not completed The clinopyroxene fills up to 15 % of the rock. It appears as relic grains that are now pseudomorphosed by actinolite-tremolite amphiboles The pseudomorphism starts from the grain exteriors and sometimes can be complete. The clinopyroxene is colorless (rarely is pale pink); c/z is up to 45; biaxial optically positive(+). The amphibole rimming the clinopyroxene is metamorphic in origin and fills up to 35% of the rock It is actinolite-tremolite type (with green color) Amphibole was found also as small individual euhedral grains within cloths with gridlike appearance. Coarse-grained Ti-magnetite and/or ilmenite represent the accessory phase They are usually altered to Fe-oxides and sphene. Altogether the accessory minerals comprise up to 1 0% of the rock A..., 't.)

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. 8) GB-14 GB-18 Plagioclase-porphyric diabases The plagioclase is the dominant mineral. It can be found as phenocrysts (up to 0 6-07 em) or in the groundmass (building up to 50 % of it). The plagioclase phenocrysts are thick prismatic grains with euhedral shape. The plagioclase from the groundmass crystallized as elongated crystal laths (sometimes even with fibrous appearance) now partially saussuritized The interstices between the plagioclase grai ns from the groundmass are now filled w i th colorless to pale green amphibole (tremolite-actinolite type) that clearly replaces a fernie mineral (probably pyroxene) Another common mineral is chlorite Together with epidote and carbonates it fills geods and rock fractures or it rims the opaque accessory minerals. The main accessory minerals are pyrite, calcite apatite and zircon Other less common accessory minerals are the precrystallization products of Ti-magnetite: magnetite hematite and sphene. Sphene is more abundant in GB-14 then in GB-18 and commonly rims the opaque mineral forming sideronit i c structures These rocks have porphyric textures with finegrained groundmass with ophitic te x ture (very well developed in GB-14) Both of them are not foliated 9) BA-20 Diabase This rock exhibits a clear mineralogical and textural similarity to GB-14 and GB-18. The only difference is that in BA-20 the plagioclase phenocrysts are not present. The rock has ophitic texture-just like the groundmass in GB-14 and GB-18.

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. 10) BA-16 Diabase The main rock forming minerals are fibrous tremolite amphibole (sometimes forming cluster structures) and very fine to cryptocrystalline epidote Sometimes albitized (low N and very clear in ppl) plagioclase can be seen as a background of the tremoliteepidote aggregates. Accessory minerals are sphene and Ti-magnetite. Because this rock suffered strong foliation and advanced precrystallization is has now very fine nematogranoblastic texture and the original textures can not be identified. 45

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PILLOW BASALTS 1) BA3 Basalt This rock is hollocrystalline (volcanic glass is very rare) The clinopyroxene is the dominant m i neral and builds up to 55% of the rock It appears as small euhedral grains or as skeletal aggregates The clinopyroxene crystalli z es within the interstices of the spherical and elongated plagioclase grains. The rock texture is intersertal. The plagioclase fills up to 35% of the rock Although metamorphosed to cryptocrystalline epidote group minerals (rarely calcite and chlorite) it preserves its premetamorphic euhedral crystal habit. Clear (in ppl) plagioclase material is very common It is i n close relations with the greenschist metamorphic products and therefore the plagioclase anorthite content cannot be determined. Finegrained cloths of sphene grow together with spherical or irregular in shape vesicles filled with epidote and chlorite. 2) BA-26 Fine-grained basalt The petrography this rock is very similar to BA-3 The only difference is that BA-26 is coarser and with more abundant plagioclase (in BA-26 the ratio CPX: Plagioclase =50: 50) Skeletal pyroxene grains are bigger then in BA-3 but again very common and with 46

PAGE 59

euhedral shape. Plagioclase crystallizes as euhedral grains but with a tendency to be coarser and even to form large phenocrysts Some plagioclase grains are replaced by secondary mineral and their anorthite content cannot be determined Geods with irregular shape were identified also. They are now filled with cryptocrystalline chlorite Fine grained sphene is the major accessory mineral. The texture is intersertal and porphyric. 4) BA24 Microgabbro This rock is fmegrained Plagioclase and amphibole are the major rock-forming minerals They crystallize in identical in size mineral grains with ratio between them 50:50. The plagioclase is with albite and Carlsbad twins It's An content is 20-25% (oligoclase). The amphibole form small euhedral grains or fibrous aggregates with pale green color. Sometimes the amphibole fibers penetrate the interiors of clear (in ppl) plagioclase grains. This is evidence that both of them were formed after precrystallization of plagioclase with higher An content and probably pyroxene. A fmegrained sphene crystals or cloths of them were found throughout the entire rock. Less common are epidote and epidote group minerals. A vein filled with carbonates epidote and chlorite, crosscut the examined thin section but as a whole the rock is not foliated and fresh. This enables the identification of the ophitic rock texture. 47

PAGE 60

5) BA-25 Basalt The rock is very finegrained and hollocrystaline (volcanic glass was not found) Most of the mineral grains are less then 0 .01 mm in size but cristallites (small rodlike micro lites that are too small to show polarization colors) were also found. The dominant mineral is the clinopyroxene (60-65%). It forms anhedral grains or aggregates. Plagioclase is presented as small columnar microlits or as rare rectangular phenocrysts Sometimes it is altered to chlorite + epidote + calcite aggregates but even then the primary euhedral grain-shape is preserved Secondary minerals are epidote and calcite crystallizing as big anhedral grains The rock textures are micro intersticial and porphiric (phenocryst is the plagioclase). 6) BA-21 Spherolithic hyalobasalt (Appendix B, Plate 15) Most of the rock is build of partially crystallized volcanic glass and therefor it is almost holohyaline with clear spherolitic texture The spherolites are build up of radiate clusters of plagioclase and clinopyroxene crystallites. The volcanic glass may build up to 85% of the rock. The plagioclase is forming swallowtailed elongated prismatic grains It is rarely altered to epidote and chlorite. When altered it is albite-oligoclase in composition. Some of the plagioclase crystals contain inclusions of volcanic glass. Epidote is filling rock 48

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fractures or circular vesicles Sometimes it is replacing the volcanic glass Very finegrained fibrous zeolite and chlorite are the other secondary minerals 7) BA-22 Basalt This rock differs from BA -21 by its degree of devitrification (BA-22 is holocrystalline, whereas BA-21 is hypocrystalline). The plagioclase lath-shaped phenocrysts are more abundant in BA-22 compared with BA21. Also one very big plagioclase phenocryst with lamellae structure was identified. Plagioclase is forming Swallow-tailed euhedral crystals. Sometimes it is altered to cryptocrystalline epidote and chlorite It builds up to 20% of the rock A large part of the thin section ( 60%) is made of skeletal feeder-like clinopyroxene forming typical spinifex textures In the other areas of the thin section the spherolites characteristic for BA-21, are dominant. Epidote is very common in the rock (15%). It occurs as large crystals associated with vesicles and cracks or as inclusions within the plagioclase and clinopyroxene grains. Chlorite calcite and quartz occur together with the epidote as major secondary minerals Small sphene grains are also common. 8) BA23 Spherolithic hyalobasalt (Appendix B Plate 14) This rock differs from BA-21 only b y it's larger plagioclase phenocrysts The plagioclase An content is 35-40%. It is clear that after saussuritization the plagioclase is now albitized

PAGE 62

9) HL1 Basaltic hyalloclastite Under the microscope it is hard to distinguish the different clasts identified in the hand samples This is because they all have similar composition and structure The majority of clasts are build up of volcanic glass. The clasts are either partially crystalline (with development of plagioclase microlits and rare carbonates arranged in a microintersertal textures) or glassy 50

PAGE 63

APPENDIX B PHOTOMICROGRAPHS AND FIELD RELATIONS 51

PAGE 64

/ serp --Plate 1: Serpentinized dunite Deli Jovan massif, Serbia; XPL, (FOV)= 2 mm; Serp = serpentine. 52

PAGE 65

pv . 53

PAGE 66

', / / ... .. .. Plate 6 : Troctolite Deli Jovan ma s sif, S e rbia ; PPL field of view ; FOV= 3 5 mm ;Pl= plagioclase ; cpx= clinopyro x ene ; amph = amphibole ; mt= magn etit e 54

PAGE 67

I i I I \ :....-\ j('pl 55

PAGE 68

Plate 9: Gabbro Tchemi Vrah mas sif, Bulgaria, XPL FOV=3.5 nun; hb l = hornb lende ; pl = plagioclase; cpx = clinopyroxene. -. ---'t _.,. .. . \ ....... _, _.,.. 'pi ' / .............. .. -Plate 10: Gabbro Tchemi Vr a h massif Bulgaria, PPL FOV=3.5 mm ; pl = p l agioclase; cpx = clinopyroxene. 56 \ ... J ..... I : ,.. ....

PAGE 69

, ' I I I ... ... ... ,. ,:-, .. . t I ;'' 57 ..... ..,. . t

PAGE 70

, ' ) ..... ... ' ... i' I \ . . J t . ' \ I . \ . ( Plate 13: Gabbro, Tchemi Vrah massif, Bulgaria, PPL, FOV=2 mm; timt= Timagnetite; ap= apatite. 58

PAGE 71

. P l ate I 6 : Swallowended plagioclase (pi) phenocryst (indicative for fast cooling rates) in basalt ; Tcherni Vrah massif Bu l garia, PPL, FOV = 2 mm; p i = p l agioclase; cpx= clinopyroxene. 59

PAGE 72

Plate 17 :Feat herlike g ra in s of clinop y ro xe ne (a u g ite) and p lagioclase ( pl) (see arrow) in basalt ; Tcherni Vrah massif Bulgaria, PPL, FOV = 2 mm. 18: Plagioclase (p i ) and clinopyroxene grains with a featherl ike grains (center of the picture) i n basalt ; Tchern i Vrah massif Bulgaria, XPL FOV = 2 mm. 60

PAGE 73

.. : y . .. ' t .v ;..,... ) . :_; -.. . 4: .......... ., '.---. (", : .__ '\' _. ' I . j ..... ..... ;.;p \it .. ; i .. ;.,\ .. r .. . . ..... :. , .... "' .... t '.. t '""'.r, . . ... -:.. ". "' ... t J''-"" \ l ....... . \, .. .. .. 'V .,J .. . . .. t . t J I , ... f ... J / ',. -. . : .. '. ..... "'---, ,.. J .. .. r-: ""'.. .-... f _. .f 'to' t ; . ., J \ ..,J, J l S .,. ....... . .. . -('_ I ; ... ,. J ... 1<_,. ( l '\ ... .,. '. P . ...... .,. .,_ .. ... ' \ I w I .,_"', .. \ .. .. : \ : : -... : ; ..,. ..... .. "'!JI ,.. 'l I-. ,.. . ,. J c ,.-,; v -; ... _.. : . ........ .. :J":.J .-., . ; .,. 1 II -=... 0 t 1 ........ "::1..'\ ............. ., .. J . ' l \ ."' ( I Plate 19 : Hematite (hem) and apatite(ap) are common accessory minerals in the basalts: !chemi Vrah massif Bulgaria PPL FQV=3:? m.m; pi = p 4 ... ... ., .. _.. ... ... Plate 20: Rhythmic a l ternation of cumulate layers in the layered gabbros ; Tchemi Vrah massif, Bulgaria: (the hammer is 35 em. long) 61

PAGE 74

Plate 21: Pegmatoid gabbro lenses (a) within finegrained gabbro (b) ; Tcherni Vrah massif Bulgaria ; the h a mmer is 35 em long 62

PAGE 75

'( t jl: '. .. Plate 23: Gradational contact between finegrained basalt dyke(a) and diabase dyke(b);Sheeted dykes unit Tcherni Vrah massif Bulgaria; 63

PAGE 76

L . -r1: "' ; : Plate 24: Epidote lenses (ep) occur in the transition zone between the sheeted dykes and the pillow basalts; Tchemi Vrah massif Bulgaria (the hammer is 35 em. l ong). 64

PAGE 77

: _. , : '" Plate 25: Single epidot e len (-30 em long ) within diaba se dyke; Sheeted dykes unit; Tcherni Vrah massif Bulgar ia . --:, .,. .. .... ; ... I 65

PAGE 78

Plate 27: Chill margin (a) in pillow lava (b) from the Pillow lava unit, Tcherni Vrah massif Bulgaria; the hammer is 35 em. long 66

PAGE 79

Plate 28: Pillowed basalt s with a varying s i ze (labeled a-e) from t he Pillow lava unit Tchemi Vrah massif, Bulgaria ; the hammer is 35 em. l ong 67

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Plate 29: A system of large lava tubes (labeled 1-4) laying over each other from the lower parts of the Pillow lava unit Tcherni Vrah massif, Bulgaria; the hammer i s 35 em. long. 68

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Plate 30: Lava flows (each separate flow outlined with dashed arrow) with different thicknesses from the Pillow lava unit Tcherni Vrah massif, Bulgaria; the hammer is 35 em. 69

PAGE 82

APPENDIXC FIGURES AND FIGURE CAPTIONS 70

PAGE 83

DELl JOVAN MASSIF /! I P-T FAULT ZONE SERBIA ' .. .. ZA5LAYAC MASSIF I r _.i , ... ; 1 j . I i r .. ; / Africa ;> ........ J I! Sheeted 1tu dyke unit 1 ' .' CHERNIVRAH Figure I: Location map of the differ ent B-C ophiolite massifs. 71

PAGE 84

$ ("'-I 0 J3 MORB 2 1 0 ... .. 0 10 20 30 40 so MgO% wt Figure 2A: MgO vs.Ti02 30.------------------------------------------, 20 10 .... ioclase CJ Clinopyroxene 10 20 30 MgO% wt Figure 2B: MgO vs Al203 72 40 50

PAGE 85

500 + ............... 400 E c.. MORBs Ct. 300 6 ...._, f,J'j 200 100 4 s 6 7 8 9 10 11 12 Mg(wt%) Figure 2C : MgO vs Sr(ppm) s 6 ,.,.---. .. ..J-j s 4 '-' <:::> 6 9 N ro ::z 2 4 6 B 10 12 MgO (wt%) Figure 2D : MgO vs NmO 73

PAGE 86

+-1 s High Ti Ophiolites N 1 0 -r- 0 0 0 0 i 0 Low Ti Ophiolites 0 UO Ul U2 U3 U4 US U6 U7 UB tFeO/(tFeO+MgO) Figure 3A: HighTi/Low Ti ophiolite discrimination diagram after Serri (1981 ). 74

PAGE 87

1000 MORB E a.. 100 c. > 10 10 100 1000 Cr(ppm) Figure 3B: Cr vs. V discrimination diagram after Pearce at al. (1973). 1 10 100 Y(ppm) Figure 3C: Y vs. Cr discrimination diagram after Pearce et al. (198 2). 75

PAGE 88

1000 OFT .. 100 !..-. 0 (._) r-10 IAT ... 0 1 10 100 1000 Ni(ppm) F igure 3D: i vs Ti/Ni discrimination diagram after Beccaluva et al. (1979). 800 Figure 3 E : Ti vs V discrimination diagram after Shervais (1982). 76

PAGE 89

a. B-C Basalts (/) (].) +-J -""0 c 0 ..!: u c 10 Q -.J....J ro l.-+-J B-C Dykes c Q.) u c: Q u LaCe Pr N d 9nEu Wlb DyHo Er TmYb L.u Figure 4 A&B: Rare Earth element (REE) diagram s for the B-C ophiolite basalts (a) and dykes (b) 77

PAGE 90

10 Vl Q..l +-J -""0 c 0 ..c u (f) c 0 --4-J c. Basalt and Dikes ro .,_; c (J) u c 0 Cumulates u LaCe Pr Nd SnEu Wlb DyHo Er TmYb lu Figure 4C: Rare Earth element (REE) diagram fo r the B-C cumu l ates. 78

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FIGURE CAPTIONS: FIGURE 1: Map showing the location of the different B-C ophiolite massifs relative to each other as well as the major outcropping areas of the different units within the Tcherni Vrah massif (lower right comer inset) PT fault= Poretchko Timoshki fault zone Also shown is the location of the B-C ophiolite relative to the Arabian Nubian Shield (ANS)(upper right comer inset). FIGURE2: Major and trace element covariation diagrams. Symbols represent different stratigraphic levels in the B-C ophiolite. Symbols as follows : black squares : ultramafic cumulates; open circles: cumulate gabbros ; black triangles: microgabbros and diabase dykes ; open triangles : pillowed and massive basalts; crosses: basalts (after Haydoutov, 1991 ) ; filled circles : cumulates in figure 2D and sheeted dykes (after Haydoutov, 1991) in all other figures. MORB fields based on data compiled in Ryan (1989) BVSP (1981) and Klein et al. (1999 GERMsources) a) MgO vs. Ti02 b) MgO vs Al203 c) MgO vs. Sr d) MgO vs. Na20. 79

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FIGURE 3: Trace element based ophiolite discrimination diagrams. Symbols as in Figure 2. a) HighTi/Low -Ti ophiolite discrimination diagram after Serri (1981 ). b) Cr vs. V discrimination diagram after Pearce at al. (1973). MORB field sources as in Figure 4 c) Y vs. Cr discrimination diagram after Pearce et al. (1982) IA T = island arc tholeiites d) Ni vs Ti/Ni discrimination diagram after Beccaluva et al. (1979); IAT = Island Arc Tholeiites ; OFT= Ocean Floor Tholeiites. e) Ti vs V discrimination diagram after Shervais (1982). IAT = island arc tholeiites FIGURE 4 : Rare Earth element (REE) diagrams for the B-C ophiolite rocks. Normalization factors from Nakamura (1974). Sample names are listed in tables 5-7 Sample locations are listed in tables 1-4. a) BC basalts. b) B-C diabases and microgabbros. c) B-C cumulates. Shaded field s represent B-C basalt and diabase suites. "Nested REE plots for all B-C rocks indicate they represent a cogenetic magmatic suite 80

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APENDIXD BULK CHEMISTRY TABLES 81

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TABLE IA: ULTRAMAFIC CUMU LA TES FROM B-C D ELI JOVAN MASSIF rock type d unite troctolites Location Deli Jovan massif Sample DU 5 TR-1 TR-2 TR-3 TR-4 Si (wt%) 42.47 47.62 44.39 45.95 44.94 M n (wt%) 0.36 0.08 0 .09 0 .09 0 .10 Fe (wt%) 12.49 5.65 6.40 6.03 7.27 Ti (wt%) 0 .03 0.23 0.12 0.10 0.10 M g (wt%) 42.87 9.72 16.58 13.85 17.42 Ca (wt%) 0.00 12.62 10.01 10.62 9 .75 AI (wt%) 1.66 23.14 18.11 22.63 19.78 K (wt%) 0 .00 0 .06 0.03 0.03 0 .03 Na (wt%) 0.00 1.83 1.28 1.53 1 .38 TOTAL 99.87 100.95 98.42 98.41 100.76 LO I(%) 13.76 5 .22 3.09 2 51 4.56 Sr (ppm) 5 .08 111.44 111.97 204.28 141.34 Ba (ppm) 16.94 17.34 10.90 63.40 8 .65 N i(ppm) 2617.31 266.94 596.61 438.56 1522.62 Sc (ppm) 13.72 34.32 44. 61 28.24 13.73 Cr (ppm) 10041.15 180.22 574.81 251.40 160.84 V (ppm) 143.93 217.14 168.82 162.39 79.43 Zn (ppm) 178.1 0 52.42 54.39 59.67 76.31 Cu (ppm) 1001.39 39.90 103.60 26.87 62.74 TABLE IB: ULTRAMAFIC CUMULATES FROM B-C TCHERNI VRAH MASSIF rock type wehrlite a north. wehrlite troctolite 1 gabbroid Location Kopilovzi massif Sample SAM.1-77 AN-9/77 LR-22 TR-24 GB-23 Si (wt%) 41.34 44.68 40.79 42.32 47.73 Mn (wt%) 0 21 0 .11 0.22 0 21 0 .14 Fe(wt%) 16.93 8.08 16.56 18.90 9 .81 Ti (wt%) 0.14 0.13 0.15 0 .39 0 .62 Mg (wt%) 32.07 13.70 31.98 30.99 13.66 Ca (wt%) 2.85 11.23 3 .32 2.72 9.34 AI (wt%) 7.17 21.01 5.86 4.60 15.69 K (wt%) 0.02 0.03 0 .03 0.04 0.09 Na(wt%) 0.06 1.61 0.10 0.37 2.77 TOTAL 100. 81 100.59 99.00 100.55 99.84 LOI (%) 11.18 6.09 10.64 9.68 5.37 Sr (ppm) 23.92 260.04 27.71 30.61 696.27 Ba (ppm) 7 .56 9.51 54.93 24.79 39.75 Ni (ppm) 1350.85 1073.02 1818.98 1958.04 1387.76 Sc (ppm) 11.54 11.26 13.15 20. 71 25.75 Cr (ppm) 152.54 234.20 125.65 320.19 343.73 V (ppm) 52.04 59.58 58.84 79.49 125.54 Zn(ppm) 83.56 67.35 110.87 112.62 74.18 Cu (ppm) 20.14 39.65 23.30 18.26 30.28 82

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T ABLE 2: MAFI C CUM ULATE S FROM B -C Rock type Lower gabbros Upper gabbros unit Location G.Lom Sikole Kitka Sample GB-4 GB5 GB-6 GB-7 GB-20 GB-1 GB-2 Si (wt%) 50.68 48.35 49 .78 53.40 49.69 49.97 50.42 Mn (wtO/o) 0.11 0 .11 0.15 0.06 0 .08 0 .12 0.11 Fe (wtO/o) 5 .62 6 .96 8.15 2.60 3.92 6.81 5 .58 Ti (wtO/o) 0.34 0 .15 0 .41 0.25 0.42 0 .37 0.37 Mg (wtO/o) 10.88 12.20 8.86 2 .14 6.44 11.17 9.06 Ca (wtO/o) 13.90 1o.n 12.39 11.94 14.95 14.13 15.10 AI (wtO/o) 15.96 19.38 15.26 23.86 21.05 16.50 16.71 K (wfl/o) 0.83 0.81 0 .08 0.08 0.12 0.11 0.13 Na (wtO/o) 1.91 1.74 2.45 4.70 2 .37 1.76 1 .92 TOTAL 100.23 100 .47 99.54 99.02 99.03 100 .94 99.40 LOI(%) 4.37 4.40 1.99 1 35 2.11 2 .89 2.08 Sr(ppm) 130.02 140.76 140.64 243.92 112.05 137.51 126.83 Ba(ppm) 109.64 146.45 16.42 41.44 8.32 10.36 12.58 Ni (ppm) 2172.57 1259.27 2367.69 188.38 1349.79 843.57 98.04 Sc(ppm) 46.26 22.60 39.63 21.47 17.73 17.72 48.57 Cr(ppm) 532.82 322.95 107.14 56.48 524.76 464. 23 672.14 V(ppm) 174.85 97.22 176. 40 120.66 85. 93 96.69 211.48 Zn (ppm) 56.15 67.51 56.96 54.49 64.67 68.46 58.00 Cu (ppm) 85.57 153.31 50.29 25.52 84.33 73.52 100.39 83

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TABLE 3A: MIC R OGABBRO AND D IABASE SHEETED DYKES FROM B-C Rock type diabase microgabro Location G .Lom Gnili Dol Ostra Tchuka G. Lom Sample DB-17 DB-15 GB-24 BA5 GB-18 GB-19 GB-14 Si (wt"'o) 49.2 51. 88 50.28 52.45 48.74 50 13 48.43 Mn (wt"'o) 0.16 0 09 0.15 0.12 0.12 0.13 0.1 Fe (wt"'o) 10.52 11. 67 9 .27 8 22 8.76 8 15 7.1 Ti (wt'k) 1.51 2 18 1 08 1.36 0 9 0 86 0 77 Mg (wt"'o) 8.24 4 39 9.23 6.93 8.3 8 .28 7.31 Ca (wt"'o) 10.87 8.09 12.34 8.67 13.03 12.56 11.49 AI (wt'/o) 14.43 14.37 16 16 16 75 19.82 16.77 22.28 K (wt'/o) 0 05 0 07 0.07 1.28 0.18 0 17 0 .38 Na {wt'/o) 2.36 4.39 2.24 3.76 2.59 2 57 3 06 P(wt%) 0 .25 0 .44 0.22 0.25 0 19 0 19 0.17 TOTAL 97.34 97 .11 100 83 98.51 102 .46 99 63 100.92 LOI("'o) 2 73 2 .21 3 3 3 .41 3.36 2 .42 4.14 Sr (ppm) 108.01 560.31 144.73 90.79 146.12 177.47 24 1. 47 Ba (ppm) 6 .25 46.35 16.43 78.92 12.48 46 .65 31.74 N i (ppm) 1208.89 471 09 339 99 75 .41 219.47 132.14 599.39 Sc (ppm) 12.9 248.79 35.93 34.24 33 66 39.92 37 28 Cr (ppm) 646.05 79.05 1031.67 299.41 59.21 317.86 313 85 V (ppm) 84.07 45. 08 150 08 197 7 253.46 262.64 212.67 Zn(ppm) 60. 98 56.58 55.94 65. 72 49.33 54. 06 71.11 Cu (ppm) 47 6 20.76 91.22 85.08 28 75 25 95 37.15 Zr(ppm) 52.02 64.47 87.73 109.87 39.57 37.46 34.26 Y(ppm) 42.46 72.16 25 83 28.53 28.96 31. 06 26 09 84

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TABLE 3B: BASALT SHEETED DYKES FROM B-C Rock type basalt basalt basalt basalt basalt basalt basalt Locat ion G.Lom I Ostra Tchuka Sample BA-16 BA-12 BA-11 BA-10 BA-9 08-4 DB5 Si (wt%) 49.35 52 .11 50 76 56 63 49.27 50.16 50.52 Mn (wt%) 0.14 0 .11 0.17 0.14 0 19 0 .21 0.21 Fe (wt%) 11.39 10.82 12.07 11. 57 12.14 11. 77 11. 88 Ti (wt%) 1.44 1.19 1 .64 1.39 1.25 1 73 1.75 Mg (wt%) 9.18 7 66 8.80 9.71 10.38 7 .2 2 7 .27 Ca (wt%) 9.34 6 .11 6 .92 1.22 3 12 11.29 11.35 AI (wt%) 16.50 18.09 15 .49 14. 46 19.12 15 19 15.26 K (wt%) 0.10 0.16 0.06 0.31 0.29 0.10 0.09 Na (wt%) 3.54 4.67 3.97 2 .44 5.17 2.54 2.57 P(wt%) 0.22 0 .21 0.24 0 .2 2 0 20 0.24 0 .24 TOTAL 100.96 100.92 99 88 97.86 100 94 100.19 100 .91 LOI(%) 3.37 3.87 8.36 5.62 6.20 3.55 2.56 Sr (ppm) 177.55 156.03 85. 53 16.88 45. 20 167.65 141.41 Ba (ppm) 15.37 27 30 15 .48 32.83 24.39 14.67 14. 71 Ni (ppm) 69.44 72 27 132.18 37.95 91.45 92.34 107.44 Sc (ppm) 29.51 26.16 38.24 18.51 24 .84 41.47 40 .46 Cr (ppm) 191.69 142.43 229.19 138 .04 243.61 201.78 197.97 V (ppm) 257.89 212.27 272 58 156.42 199 92 313.54 322.88 Zn (ppm) 35 66 40.43 79.72 70.93 83 .94 67.18 62.16 Cu (ppm) 19 43 17.31 134.99 176.63 147.48 38.54 37 .04 Zr(ppm) 44.07 43.17 43.23 37.74 36.69 132 96 67 .3 5 Y(ppm) 38.11 40. 54 38.99 35 .13 28 03 23.95 36.33 85

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TABLE 4 : PILLOW BASALTS FROM B-C rock type pillow basalts Location GniliDol Sample BA-3 BA-24 BA-25 BA-21 BA-22 BA-23 BA-26 Si (wt%) 49.40 54 32 51. 39 47.74 48.02 50 33 49 57 Mn (wt%) 0.17 0.14 0.18 0 17 0.17 0.21 0 .17 Fe (wt%) 10.43 9.58 10.73 13.01 12.00 11.17 11.18 Ti (wt%) 1.46 1.54 1.83 1.66 1.65 1.61 1.45 Mg (wt%) 7.63 7.30 7.03 9.24 7.15 9.66 7.15 Ca (wt%) 11.65 7.20 9 12 7.71 12.42 9.22 9.40 AI 15.21 13.27 14 64 17.08 16 .25 13.49 18 .20 K (wt%) 0.12 0.07 0 05 0.30 0.07 0.06 0 13 Na 2.97 4.99 3 45 3 .2 1 2.76 3.59 3 67 p 0.26 0.23 0.28 0 .29 0.25 0 .26 0.23 TOTAL 99.03 99 85 100 82 100 13 100.50 99 34 100 93 LOI(%) 2.86 4 15 4 10 4.68 3.35 3 49 4.50 Sr (ppm) 150.64 177.75 117.03 133.98 177.76 57 .26 211. 52 Ba {ppm) 18.32 14.19 24 72 30.21 18.89 16.02 51. 77 Ni (ppm) 108.60 72.06 63.27 73.00 88.17 119 54 89 .31 Sc (ppm) 41.46 41.21 38.37 32 58 43.47 41.92 37 99 Cr (ppm) 325 38 272 .4 5 197.30 207.98 273.18 272 .2 8 269.17 V(ppm) 266.93 286 62 288.03 232.81 298.70 265.26 277.34 Zn (ppm) 81.86 66.23 84.34 68.07 89.65 89.68 82.89 Cu (ppm) 93.54 25.69 62.12 35 .84 71.85 64.76 74.84 Zr(ppm) 148 47 68.27 168.08 95 63 58.22 86 04 51. 83 Y(ppm) 28.6 23. 75 29 89 33.48 28.69 28 59 26.44 86

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TABLE 5 REE IN B C B A SALTS sample BA-26 BA-3 BA-22 BA-23 BA-24 BA-25 La 3 .26 4.2 3 63 3 47 2 .81 5 34 Ce 9 83 11.8 11.7 10.9 9.59 14.67 Pr 1.77 2 12 2 .11 1 98 1 75 2 59 Nd 9.07 10.03 10.64 10.03 8 83 12.77 Sm 3.26 3.44 3.78 3.59 3 17 4 .35 Eu 1.08 0 96 1 03 0 65 0.64 1 17 Gd 4 67 4 24 5 06 4 73 4.36 5 .61 Dy 5 35 5 27 6.04 5.83 5 24 6 .75 Ho 1 17 1 19 1.29 1.27 1 12 1.48 Er 3.4 3 5 3 79 3 7 3.32 4 .24 Tm 0.52 0 52 0 55 0.55 0 .49 0 63 Yb 2 95 3.12 3.34 3.25 2 98 3.76 Lu 0 46 0.5 0.52 0 52 0 .47 0 6 TABLE 6 REE IN B C SHEETED DYKES sample BA12 DB5 GB-19 GB 18 GB-14 GB 24 La 9.58 3.77 1 88 2.07 1 09 2.14 Ce 21. 55 11.29 5.93 5.94 3.74 6 46 Pr 3.26 2 06 1.11 1.05 0.71 1.19 Nd 13 3 9.73 5.58 4.92 3 02 5 63 Sm 3.78 3.35 2 13 1.81 1 13 2 11 Eu 0.81 0 94 0 72 0.52 0 .26 0.56 Gd 4.53 4 15 2.76 2.36 1.33 2 .61 Dy 5 4 5.19 3 5 3 1 82 3 42 Ho 1.2 1 17 0.76 0.66 0 4 0.77 Er 3.51 3 42 2.19 1 .91 1 .2 2 .23 Tm 0.54 0.5 1 0 32 0 .28 0 18 0 33 Yb 3.37 3.2 1 1 8 1.57 1 05 1.95 Lu 0.55 0.52 0 3 0.26 0 18 0.31 87

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TABLE 7 REE IN B-C CUMULATES sample GB-6 LR-22 TR-1 GB-23 GB 2 GB-20 GB-24 GB-4 La 0.22 0 28 0 38 4 06 0.19 0 .34 2.19 0 .06 Ce 1.28 0.99 1 37 10.16 1.26 1 60 6.83 0 .82 Pr 0.32 0.20 0.27 1.55 0 .31 0 .35 1.23 0.23 Nd 1 .57 0.55 1 .01 7.16 1.56 1.76 6.08 1 .18 Sm 0.89 0.29 0.44 2.23 0 86 0 90 2.24 0.75 Eu 0.28 BDL 0.13 0.61 0.24 0.30 0.63 0.20 Gd 1.25 0.42 0.55 2.85 1.26 1.34 3.08 1.53 Dy 1.83 0.36 0.64 2.78 1.67 1.71 3.68 1.52 Ho 0.41 0.08 0.14 0 57 0 36 0.38 0.79 0.34 Er 1.16 0.25 0.42 BDL 1.04 1.08 2 .31 0.96 Tm 0.17 0.04 0 06 0.23 0.15 0.16 0.33 0 .14 Yb 0.88 BDL BDL 1.16 0.75 0.77 1.94 0.64 Lu 0.15 0.04 0.05 0.19 0.13 0.14 0.31 0.12 Note: BDL= Below Detection Limit 88

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rock type Location Sample Si (wt<'/o) Mn (wt<'/o) Fe (wt<'/o) Ti (wt<'lo) Mg (wt<'/o) Ca (wt<'/o) AI (wt<'/o) K (wt<'/o) Na (wt<'/o) TOTAL Sr (ppm) Ba (ppm) Ni (ppm) Sc (ppm) Cr(ppm) Zn (ppm) Cu (ppm) Zr(ppm) rock type Location Sample Si (wt<'/o) Mn (wt<'/o) Fe (wt<'/o) Ti (wt<'/o) Mg (wt<'/o) Ca (wt<'/o) AI (wt<'/o) K (wt<'/o) Na (wt<'/o) TOTAL Sr (ppm) Ba (ppm) Ni (ppm) Sc (ppm) Cr (ppm) V(ppm) Zn (ppm) Cu (ppm) Zr(ppm) TABLE 8 : CUMULATES (afte r Haydoutov 1991) Wehrlites Gabbro Troctolites Gabbros Kopilovzi massif Tshemi Vrah massif 46b 7a 46a 8 4 182 253 37.7 39.76 39.8 47.21 49. 53 48.01 49. 37 0 23 0.19 0 17 0 097 0.09 13.02 12.68 10.2 5.53 5.99 5.63 3 73 0.21 0.18 0.2 1.23 0.46 0.26 0 37 25 45 23.35 21.65 9 06 8.6 10.29 8 4.08 5.3 6 35 11.23 13.51 13.61 14.14 8.38 8 .5 13.25 18.22 18.93 16.94 16.88 0.1 0.06 0 12 0.11 0 28 0.21 0.31 0.53 0 66 2.67 2 29 1 .64 2.13 99.63 99.8 99.65 98 .85 101.64 99 .14 98.92 30 27 283 6500 335 145 211 70 177 70 131 25 70 192 428 350 295 124 94 104 86 7.3 4.2 20.5 28.5 --179 113 201 311 800 929 1359 78 103 95 0 -25 12 19 8 7 71 7 106 83 28 32 22 15 22 56 29 TABLE 9: SHEETED DYKES (afterHaydoutov, 1 991) diabase 1 3 47.83 48.48 0 135 0.129 8.61 8.97 1 12 1.36 10 8.78 8 .26 9.07 16.3 15.81 0.06 0.06 3.34 3.52 100.26 100.16 198 250 15 17 115 66 27 .5 31.6 330 340 187 274 --27 8 52 76 basalts Tsherni Vrah massif 202 189 47 93 53 64 --9.8 5.8 1.19 1.23 8.58 7.45 12.14 10.87 15.69 14.34 0 28 0.37 2 33 4.5 99.25 99.47 132 195 70 70 83 47 --318 231 220 229 18 5 33 8 103 122 on 252 46 .31 11.05 1 37 7.84 10 86 16.33 0.27 3.06 99 .24 187 70 52 -225 266 54 22 118 microgabros 48 58 3a 48.74 48.6 49.48 0 25 0 .14 0.126 11.38 10 .34 8.94 1.24 1.58 1.35 7.05 5.59 8.65 9.85 10.89 9 .04 14.88 15 87 15.82 0.66 0.6 0.04 2.68 2.7 3.56 98.71 98.48 99.59 -346 30 --51 -28.6 -300 -309 -----27 --62 Pilatovtzi 230a 46.89 -7.71 0 .54 7.4 11.84 18.33 0.12 2.22 99.42 606 70 42 -184 35 5 65 201 46. 86 10 6 1.41 6 73 11 .26 16 .88 0.17 2.09 99.68 109 82 40 -193 278 34 52 92

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TABLE 1 0 : BASALTS (after Haydoutov, 19 91) rock type basalt I basalt basalt basalt basalt basalt basalt I basalt basalt Location Javor dol Rupskidol I Gnili Dol Sample 5b 172 170 174 175 225 18 28 38 S i (wr'lo) 47.7 49.93 46.52 50 .13 46.36 45.36 48.95 50.08 53 86 Mn (wr'/o) 0 .16 0.19 0.16 -0 .16 -0.23 0.18 0.15 Fe (wr'/o) 8.35 10 54 9.91 9 09 11.49 11.05 11.76 10.42 11.15 li (wr'/o) 1 6 1.62 1.28 1 25 1.47 1.68 1 08 1 06 1.04 Mg (wr'/o) 7 52 7 .75 8 2 5.03 7 04 7.23 5.57 6 82 5.8 Ca (wr'/o) 9.92 7 28 10.18 11. 95 10.6 10. 92 7 2 9.82 7.86 AI (wr'/o) 16. 62 13.73 15.18 14. 86 14.78 16.41 16.51 14.98 13.33 K (wr'/o) 0.06 0.22 0.29 0.18 0 2 0 37 0 22 1.58 Na (wr'lo) 2 99 4.63 2.9 2 6 2 7 2 56 3 67 3 .21 2 48 TOTAL 99.51 99.79 99 93 99 09 100 .04 99.13 98.81 99 05 99.45 Sr(ppm) 300 165 238 507 210 206 ---Ba(ppm) 13 139 65 21 108 70 ---Ni (ppm) 61 34 73 35 47 57 ---Cr(ppm) 350 208 335 230 317 264 --V(ppm) 391 360 255 169 309 196 --Zn (ppm) -61 52 42 68 65 ---Cu (ppm) 50 20 23 51 67 62 ---Zr(ppm) 74 128 115 169 104 96 -90

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TABLE CAPTIONS : Table 1 : Major and trace element data for ultramafic cumulate rocks from the B-C ophiolite. LOI= Loss oflgnition Sampled areas are from Deli Jovan massif (Table 1A) and Tcherni Vrah (Kopi lovt zi) massif(-1 km North ofKopilovtzi village) (Table 18). Table 2 : Major and trace element data for mafic cumulate rocks (Upper and Lower cumulate units) from the BC ophiolite LOI= Loss oflgnition. Sampled areas include Deli Jovan (North ofSikole village) as well as Tcherni Vrah (-3 km South ofG.Lom village and 0.5 km West ofKitka summit) ophiolitic massifs. Table 3: Major and trace element data for microgabbros and diabases (table 3A), and basalts (table 38) from the Sheeted dykes unit of the BC Tcherni Vrah massif Samples are from Golema river gorge (South ofG.Lom village); Gnili Dol valley ( 2.5 km North of the town ofTchiprovtzi) and from the southern slope ofOstra Tchuka summit (North ofMartinovo village). LOI= Loss of Ignition. Table 4 : Major and trace element data for basalts from the pillow lava unit of the BC Tcherni Vrah massif. Sampled areas are from Gnili Dol valley( 2.3 km North of the town ofTchiprovtzi). LOI= Loss of Ignition. 91

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Table 5 : Rare Earth Element (REE) d ata for basalts from the pillow lava unit of the BC ophiolite Sample localities are the same as in table 4. Table 6: Rare Earth Element (REE) data for microgabbros diabases and basalts from the Sheeted dykes unit of the BC ophiolite. Sample localities are the same as in tables 3A and 3B Table 7 : Rare Earth Elements (REE) data for ultramafic and mafic cumulate rocks from the BC ophiolite. BDL = Below Detection Limit. Sample localities are the same as in tables IA, IB and 2. Table 8: Major and Trace element data for ultramafic and mafic cumulate rocks from the BC ophiolite after Haydoutov ( 1991 ). Samples areas are from Pilatovtzi (South of Zhelezna village on the southwestern slope ofTcherni Vrah summit), Kopilovzi (North of Kopilovzi village on the southern slopes ofLandzina Tchuka and Aldentzi summits) and Tcherni Vrah (3.5 km South ofG.Lom village; 0 5 kmWest ofKitka summit) ophiolite massifs. Table 9: Major and Trace element data for sheeted dykes from the BC ophiolite (after Haydoutov, 1991 ). Sampled areas from Go l ema river gorge (South of D Lorn village and West ofG.Lom village). 92

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Table 10: Major and Trace element data for basalts from the pillow lava unit of the BC Tchemi Vrah massif. Sampled areas are Javorov Dol valley ( 2.5 km North of Martinovo village); Rupski Dol valley ( 3 km. North ofTchiprovska river) and Gnili Dol valley(2 5 km North ofthe town ofTchiprovtzi) Table 11: Major and Trace element analytical statistics Table 12: Rare Earth Elements (REE) analytical statistics Table 13: CIPW Normative minerals in BC ultramafic cumulates Table 14 : CIPW Normative minerals in BC mafic cumulates Table 15: CIPW Normative minerals in BC pillow basalts Table 16: CIPW Normative minerals in BC basalt sheeted dykes Table 17 : CIPW Normative minerals in BC diabase and microgabbro sheeted dykes 93

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APPENDIXE ANALYTICAL STATISTICS 94

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TABLE 11: MAJOR AND TRACE ELEMENT STATISTICS RR-1, Diabase, PA element avg RR-1 std. RR-1 std* STD DEV*** Si (wt%) 50.5 50 .2 2 0.20 Mn 0.19 0.18 0.01 Fe 12.46 12.15 0.22 Ti 0.76 0.73 0.02 Mg 14.28 14.19 0.06 Ca 9.28 9.31 0.02 AI 10 69 10.52 0.12 K 0.39 0.41 0.01 Na 1.46 1.47 0.01 p 0.22 na ---Total 100.05 99 18 -----Sr (ppm) 131.08 142 7 72 Ba 106.89 113 4 32 Ni ** 871 78 -626 173.79 Sc 34.38 35 0.44 Cr ** 637.09 -686 34.58 v 210.93 -242 21.97 Zn 85.52 86 0 34 Cu 81.64 78 2.57 Zr 109.64 na ------y 32.53 na ----NOTE: *Calcu lated after 15 analysis during USF's REU ( 1997 & 1998) program ** Ni (ppm), Cr (ppm) and V (ppm) contents in RR-1 *have coeff. ofvariation= 10-20% and are suggested va lue s only due to DCP instument calibration problems *** STD DEV = standard deviation na = not analysed 95

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TABLE 12: RARE EARTH ELEMENTS STATISTICS BIR1 ,USGS lslandic basalt element (in ppm) avg* BIR -1 std. BIR -1 USGS std. STD DEV* ** La Ce Pr Nd Sm Eu Gd Dy Ho Er Tm Lu 0.39 0.88 1 .69 -2.5* 0.38 -0.5* 1 94 2.5 1 04 -1.08* 0.26 -0.54* 1.63 1 9 2.42 -2. 4 0.57 0.5 1.69 1.8 0.26 0 27 0.25 0.26 NOTE: *USGS suggested value only **avg =average of 4 separate ICP-MS analysis ***STD DEV =stand ard deviation 96 0.34 0 57 0.08 0.39 0.03 0.20 0.19 0 .01 0 05 0.08 0.01 0.01

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APPENDIXF CIPW NORMATIVE MINERALS 97

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TABLE 13: CIPW NORMATIVE MINERALS IN B-C ULRTAMAFIC CU MULAT ES MINERAL DU-5 AN 1m AN 9fT7 LR22 TR-24 GB-23 TR-1 TR 2 TR-3 TR-4 or 0.12 0 18 0.18 0.24 0.53 0 35 0 18 0.18 0 18 ab 0.51 11. 29 0.85 3.13 23.08 15 49 10.83 12 95 11. 68 an 14 14 50.02 15.45 1o.n 30.11 54.75 43 58 52 69 47 69 di 4 57 0 .81 2.18 13.05 6 29 4.83 0.54 hy 21.98 19.09 13.67 18 98 5 44 5.64 6.69 2 26 ol 73.36 60 97 31.19 64.01 60.22 29.48 16.9 30.27 26 36.58 mt 1.81 4.45 1 .17 2 .41 2 .74 1.42 0.83 0 93 0.87 1.06 il 0.06 0.27 0.25 0 28 0.74 1.18 0.44 0.23 0.19 0.19 ap c 1.6 1.87 o n ne 1 26 0 2 Pl. An% 100 97 82 95 n 57 78 80 80 80 TABLE 14: CIPW NORMATIVE MINERALS IN B-C MAFIC CUMULATES MINERAL GB-4 GB-5 GB-6 GB 7 GB-20 GB-1 GB 2 or 4.91 4 .79 0 .47 0 47 0.71 0.65 0 77 ab 16.16 14.72 20.73 38.61 20.05 14.89 16.25 an 32.53 42.68 30.41 43.77 46. 45 36.8 36.59 di 29.09 8.61 25 16 12.61 22.19 26 69 30. 71 hy 2.47 6.67 10 45 1.62 7.79 7.35 ol 13.15 21.13 7.68 1.87 6 .3 4 11. 88 5 .77 mt 0.81 1.01 1.17 0.38 0.57 0.99 0 .81 il 0.65 0.28 0.78 0.47 0.8 0.7 0.7 ne 0.63 Pl. An% 67 74 59 53 70 71 69 TABLE 15: CIPWNORMATIVE MINERALS IN B-C PILLOW BASALTS MINERAL BA-3 BA-24 BA-25 BA-21 BA-22 BA-23 BA-26 or 0.71 0.41 0 3 1 .77 0.41 0.35 0 .77 ab 25.13 42.22 29.19 27.16 23.35 30.38 31.05 an 27.82 13.6 24.31 31.31 31.75 20.52 32.81 di 23 1 16.8 15.63 4.12 23.21 19.11 10.11 hy 7.05 16 .39 22 4 8 22 0.66 8.93 4.07 ol 9.76 3.58 21.05 14.92 14. 12 16.52 mt 1.51 1 39 1 .55 1.88 1.74 1.62 1 62 il 2.77 2.92 3 48 3.15 3.13 3.06 2.75 ap 0 6 0 53 0 .65 0.67 0.58 0 6 0.53 Q 0 .31 Pl. An% 53 24 45 54 58 40 51 98

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TABLE 16: CIPW NORMATIVE MINERALS IN B-C SH EETE D DYKES BASALTS MINERAL 8A-12 8A-11 8A-10 8A-9 8A-16 08-4 085 Q 18.24 or 0.95 0.35 1.83 1 .71 0 59 0.59 0.53 ab 39.52 33.59 20 .65 43.75 29.95 21.49 21.75 an 27.93 24.27 4.62 14.17 28.84 29.75 29.84 di 0.83 6 .94 13.08 20.27 20.45 hy 11.63 15.86 38.56 2.55 2.48 20.66 20.86 ol 15.04 12.69 28.25 20.43 1.17 1.15 mt 1.57 1.75 1.68 1 75 1 65 1 71 1.73 il 2 26 3.11 2 .64 2.37 2.73 3 29 3 .32 ap 0.49 0.56 0 .51 0.46 0.51 0.56 0.56 c 8.42 5 .11 Pl. An% 41 42 18 24 49 58 58 TABLE 17: CIPW NORMATIVE MINERALS IN B -C SHEETED DYKES DIABASES AND MICROGARBBOS MINERAL 08-17 G8-18 G8-19 8A-20 08-15 G8-14 8A-5 Q 1.34 or 0.3 1.06 1 0.47 0.41 2.25 7 56 ab 19.97 20.14 21.75 21.75 37.15 22.86 31.82 an 28.63 41.93 33.72 33.22 19.3 45.94 25.05 di 19.28 17.43 22.15 20.72 14.95 8.06 13.27 hy 22.82 9.33 7 .3 6 16.6 8 08 ol 0.76 16.98 7 93 13.21 16.88 8 99 mt 1.52 1.28 1.17 1.57 1.7 1.03 1.19 il 2.87 1 .71 1.63 2 .37 4.14 1.46 2 58 ap 0.58 0 .44 0 .44 0.56 1.02 0.39 0.58 ne 0 96 1 .64 Pl. An% 59 68 61 60 34 67 44 99

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APPENDIXG COMPARISON BETWEEN BALKANCARPATHIAN BASALTS AND MORB FROM THE MODERN OCEANS 100

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TABLE 18. COMPARISON BETWEEN B-C AND N.ATLANTIC BASALTS ELEMENT N.Atlantic MORB B-C oph.basalts STD DEV Si02 49.85 50 .11 0.18 Al203 15.12 15.45 0.23 FEO .. 10.48 11.16 0.48 MgO 8.179 7.88 0.21 CaO 11.62 9.53 1.48 Na20 2 357 3.52 0.82 K20 0.166 0.11 0 04 Ti02 1.312 1.60 0.20 P205 0.176 0.26 0.06 MnO 0.185 0.17 0.01 Ba 30.37 24.87 3.89 Sr 118.1 146.56 20.13 Sc 40.1 39.57 0.37 Zr 91.42 96.65 3.70 y 31.56 28.49 2.17 Cu 82.01 61.23 14.69 Cr 315.3 259.68 39.33 Ni 117.2 87.71 20.85 La 5 673 3.79 1.34 Ce 11.88 11.42 0.33 Nd 8.507 10.23 1.22 Sm 3.094 3.60 0 36 Eu 1.109 0.92 0.13 Gd 2.959 4.78 1.29 Er 2.732 3.66 0.66 Yb 2.855 3.23 0.27 Lu 0.429 0.51 0 06 The average MORB data was taken from the GERM Project web page and used with the permission of Emily Klein 101

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TABLE19 COMPARISON B E TWEEN B-C AND N .E AST PACIFIC RISE BASALTS ELEMENT N EPRMORB BC oph. basalts STD DEV Si02 50 17 50 .11 0.04 Al203 15.07 15.45 0.27 FEO* 10. 27 11.16 0.63 MgO 7 623 7.88 0.18 CaO 11.67 9.53 1.51 Na20 2.783 3.52 0.52 K20 0 .161 0.11 0.03 Ti02 1 656 1 60 0.04 P205 0 169 0.26 0.06 MnO 0.192 0 17 0.01 Ba 31. 4 24.87 4.61 Sr 145.6 146.56 0.68 Sc 39.12 39.57 0 32 Zr 121 7 96 .65 17.71 y 36 75 28.49 5 .84 Cu 85.85 61.23 17.41 Cr 254 4 259.68 3.73 Ni 95 67 87.71 5.63 La 4.973 3.79 0 84 Ce 13.74 11.42 1 .64 Nd 10.35 10 23 0.09 Sm 3 507 3 60 0.06 Eu 1.285 0 92 0.26 Gd 4.713 4.78 0 05 Er 3.961 3.66 0.21 Yb 3 074 3.23 0.11 Lu 9 453 0.51 6.32 The average MORB data was taken from the GERM Project web page and u sed with the permission of Emily Klein 102

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TABLE20 COMPARISON BETWEEN B-C AND INDIAN OCEAN BASALTS ELEMENT Ind. Ocean MORB BC oph. basalts STD DEV Si02 51. 45 50.11 0.95 Al203 15.91 15 .45 0.33 FEO* 8 479 11.16 1.90 MgO 8.216 7.88 0.24 CaO 10.91 9.53 0.97 Na20 3.259 3.52 0.18 K20 0.15 0.11 0 03 Ti02 1.267 1.60 0.24 P205 0.266 0.26 0 .01 MnO 0 148 0 17 0.02 Ba 14.08 24.87 7.63 Sr 144.5 146.56 1.46 Sc 31.8 39.57 5.49 Zr 125 96.65 20.05 y 31.9 28.49 2.41 Cu 86 61.23 17.51 Cr 714.3 259.68 321.47 Ni 154.7 87.71 47.37 La 3.882 3.79 0.07 Ce 11.86 11.42 0.31 Nd 9 .541 10.23 0.49 Sm 2.95 3.60 0.46 Eu 1.104 0 92 0 13 Gd 3 944 4.78 0.59 Er 3.011 3.66 0.46 Yb 2.745 3.23 0.35 Lu 0.408 0.51 0 07 The average MORB data was taken from the GERM Project web page and used with the permission of Emily Klein 103

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APPENDIXH PALEOGEOGRAPHIC MAPS 104

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APP EN DI X H Fig 5 Late Proterozoic paleogeographic map (650 Ma) Fig 6 Late Precambrian paleogeogr a phic map (600 Ma) 105

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APPENDIX H (Continued) Fig. 7 Late Precambrian paleogeographic map (570 Ma) Fig. 8 Late Cambrian paleogeographic map (514 Ma) 106

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APPENDIX H (Continued) Fig. 9 Middle Ordovician paleogeographic map (458 Ma) Fig. 10 Middle Silurian paleogeographic map (430 Ma) 107

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APPENDIX H (Continued) Fig. 11 Late Devonian paleogeographic map (370 Ma) Fig. 12 Late Pennsylvanian paleogeographic map (300 Ma) 108


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