Theoretical and Applied Karstology

Citation
Theoretical and Applied Karstology

Material Information

Title:
Theoretical and Applied Karstology
Series Title:
Theoretical and Applied Karstology
Creator:
Emil Racovita Institute of Speleology
Publisher:
Emil Racovita Institute of Speleology
Publication Date:
Language:
English
French

Subjects

Subjects / Keywords:
Geology ( local )
Genre:
serial ( sobekcm )
Location:
Romania
Coordinates:
46 x 25

Notes

General Note:
Contents and Abstracts: Constantin, S. Editorial. p. 4. TAK Meetings:White, W.B. The Friends of Karst. pp. 5-6. TAK Anniversaries: Onac, B.P. Iosif Viehmann - a life for karst, p. 7. TAK Articles: White, W.B., White, E.L. - Conduit fragmentation, cave patterns, and the localization of karst ground water basins: the Appalachians as a test case. pp. 9-23. Because conduit systems in maturely developed karst aquifers have a low hydraulic resistance, aquifers drain easily and karst aquifers are subdivided into well-defined ground water basins. Ground water elevations are highest at basin boundaries; lowest at the spring where the ground water is discharged. Parameters that control the type of conduit development are (1) the effective hydraulic gradient, (2) the focus of the drainage basin, and (3) the karstifiability of the bedrock. Moderate to highly effective hydraulic gradients permit the runaway process that leads to single conduit caves and well ordered branchwork systems. Low hydraulic gradients allow many alternate flow paths and thus a large degree of fuzziness in the basin boundaries. Low gradient ground water basins also tend to merge due to rising water tables during periods of high discharge. Focus is provided by geological constraints that optimize discharge at specific locations that can evolve into karst springs. Karstifiability is a measure of the bulk rate at which aquifer rocks will dissolve. Fine grained, pure limestones and shaley dolomites mark the opposite ends of the range. The cave surveys of the Appalachian Highlands provide a data base that can be used to classify the lateral arrangements of conduit systems and thus determine the relative importance of the factors defined above. Tamas, T., Causse, C. - U-Th TIMS chronology of two stalagmites from V11 Cave (Bihor Mountains, Romania). pp. 25-32. Two stalagmites (S22, S117) from V11 Cave (Bihor Mountains, Romania) were dated by thermal ionisation mass-spectrometry (TIMS). The 40 subsamples dated had uranium contents between 0.229 and 0.676 ppm, a 234U/238U actual ?1 and generally low detrital contamination. Ages obtained range between 138.3 ± 1.6 ka and 5.6 ± 0.1 ka and are distributed in six growth periods separated by hiatuses. Growth rates calculated show that calcite deposition was slow in both stalagmites for most of the depositional periods recorded during oxygen isotope (OI) stage 5 (1.3-3 mm/ka), with the exception of the OI substage 5e, when S117 experienced fast growth (50 mm/ka). After an interruption of 22 ka, calcite deposition in S22 resumed during OI stage 3 (2.5 mm/ka). The age of 23.4 ± 0.12 ka recorded in S117 confirms previous evidence for a short depositional period during OI stage 2. Termination I was determined in S117 at 16.08 ka. The last growth interval during OI stage 1 is marked by a strong increase in growth rates of both stalagmites, determined by warming and by a significant increase in precipitation. The presented dataset frames the main climatic events that occurred in the last 140 ka and brings a precise chronology in this time span, in good agreement with previous studies from Europe and NW Romania. Onac, B.P. - Mineralogical studies and Uranium-series dating of speleothems from Scarisoara Glacier Cave (Bihor Mountains, Romania). pp. 33-38 Recent mineralogical investigations carried out in Scarisoara Glacier Cave pointed out the presence of speleothems made up of monohydrocalcite and hydromagnesite. Although both minerals were documented earlier from other Romanian caves this is for the first time when a speleothem is described as being entirely composed of monohydrocalcite. Crocoite, a rare mineral was also identified; however, this is not a real cave mineral being transported into the cave by the percolating waters. U-Th dating of some speleothems from Scarisoara Glacier Cave enabled us to draw some considerations concerning the palaeoclimate changes and the age of the cave. Constantin, S., Lauritzen, S.-E., Stiuca, E., Petculescu, A. - Karst evolution in the Danube Gorge from U-series dating of a cave bear skull and calcite speleothems from Pestera de la Gura Ponicovei (Romania). pp. 39-50. Two bone samples taken from a cave-bear skull discovered in Pestera de la Gura Ponicovei (Danube Gorge, Romania) have been dated by U-series liquid-liquid extraction procedure. They allowed the determination of a minimum age of the cave as well as the minimum age of Danube's fourth terrace at c. 277 ka. This age has been also used to ascertain the paleontologic determination of the bear species as Ursus deningeri v. Reichenau. Datings on speleothem calcite indicate that the minimum age of the active level of the cave is ~30 ka and enabled rough estimations of the incision rate of the underground river and of the fluvial erosion rate of the Danube at 0.05 m/ka and 0.67 m/ka, respectively. Mylroie, J., Jenson, J. - The Carbonate Island Karst Model applied to Guam. pp. 51-56. The karst of tropical carbonate islands is unique because: 1) fresh water-salt water mixing occurs at the base and margin of the fresh-water lens; 2) glacioeustasy has moved the freshwater lens up and down through a vertical range of over 100 m; and 3) the karst is eogenetic, i.e., it has developed in young carbonate rocks that have never been buried beyond the range of meteoric diagenesis. Carbonate islands can be divided into three categories based on basement-sea level relationships: simple carbonate islands (no non-carbonate rocks), carbonate cover islands (non-carbonate rocks beneath a carbonate veneer), and composite islands (carbonate and non-carbonate rocks exposed on the surface). These ideas form the Carbonate Island Karst Model (CIKM) which can be visualized in terms of a three-dimensional framework, with island size on the x-axis, sea-level change on the y-axis, and bedrock relationships on the z-axis. On Guam, tectonic uplift and glacio-eustatic sea level change have produced a complex history on this composite island. The aquifer is partitioned in the subsurface by the antecedent topography of the volcanic core of the island, and lens discharge is both diffuse and conduit controlled. Florea, L., Mylroie, J., Carew, J. - Karst genetic model for the French Bay Breccia deposits, San Salvador, Bahamas. pp. 57-65. the Island of San Salvador in the Bahama archipelago 30 breccia deposits can be found along the French Bay sea cliffs on the southeastern coast of the island. Breccia deposits of this type have not been observed on any other location on the island. These deposits have traditionally been interpreted as paleo-talus deposits from an eroding sea cliff formed on a transgressive eolianite deposited at the start of the oxygen isotope substage 5e sea-level highstand (ca. 125,000 years before present). New evidence supports a karst genesis. A survey of several deposits revealed a vertical restriction of +2 to +7 meters above sea level consistent with flank margin caves developed during the substage 5e still-stand. The morphologies of the features were found to be globular and contain distinct caliche boundaries, overhung lips, and smooth undulating bases. Petrographic results support a model in which voids are created and then infilled with a soil breccia. It can be concluded from these results that the deposits reflect qualities of a lithified soil breccia filling in breached flank margin caves. Diaconu, G., Dumitras, D. - Sur la présence de l'ardéalite dans la Grotte de Topolnita (Plateau de Mehedinti, Roumanie). pp. 67-73. Il y à 70 années, dans la Grotte de Cioclovina (Monts Sebes, Roumanie) un nouveau minéral - l'ardéalite - a été découvert en association avec le gypse et la broushite (HALLA, 1931; SCHADLER, 1932). Les auteurs ont identifié la même association minéralogique dans la Galerie Suspendue de la Grotte de Topolnita (Plateau de Mehedinti). L'échantillon prélevé a été analysé en RX, IR, TDA et chimiquement. Les données obtenues, comparées avec les données standard, ont mis en évidence l'ardéalite, le gypse et la broushite. Le travail présente de même un point de vue original sur les conditions du milieu spéléique qui ont facilité la genèse de cette association minéralogique. Ljubojevic, V., Pacevski, A., Calic-Ljubojevic, J. - On the genetic conditions of black manganese deposits from two caves of Eastern Serbia. pp. 75-79. Portions of cave passages often have a black colour due to manganese deposits that occur as coatings on cave walls and ceilings, on clastic sediments, as well as on speleothems. On samples from the cave Buronov Ponor chemical analysis, infrared spectroscopy, X-ray diffraction and DTA analysis confirmed the presence of birnessite. In cave Cerjanska Pecina, the presence of manganese compounds in the black coating has been confirmed by chemical tests. In both caves it has been noted that cave passages with black coating have a distinct morphology. They are highly weathered showing an abundance of sharp protusions, potholes in the streambed and scallops. The paper studies these occurrences and the possible link between the manganese deposition, hydrology and morphology of the passages and petrologic composition. Although this link was not identified, some interesting questions regarding manganese deposition arose. It remains unclear why manganese deposition is limited only to a certain part of cave Cerjanska Pecina, and what caused the cyclicity in manganese deposition in the cave Buronov ponor. Feier, N., Munteanu, G., Onac, B. P. - Mineralogy and speleogenesis of the Ice-Cave from Poiana Vârtop (Bihor Mountains, Romania). pp. 81-85. The cave of Poiana Vârtop in the NW Bihor Mountains hosts the fourth largest underground perennial glacier in Romania with a volume estimated to 12,000 m 3 . The ice accumulated within the cave as a result of trapping of subzero winter air through its single entrance near the top of the cave. The speleothem mineralogy is dominated by calcite, with minor amounts of included aragonite. Crusts of carbonate-hydroxylapatite (associated with bat guano) and goethite (associated with pyrite in the host limestone) are found at a few locations. Based on structural observations, dye traces, and cave galleries orientations, it is inferred that the cave is part of a much larger hydrologic karst system that also includes the nearby Humpleu-Poienita cave network. Constantinescu, T., Constantin, S. - La genèse et l'évolution des grandes dolines (obans) de la zone karstique de Mangalia (Dobroudja du Sud, Roumanie). pp. 87-92. Pour expliquer la genèse et l'évolution des grandes dolines ou obanes de la zone karstique de Mangalia, Obanul Mare est le plus représentatif, du fait qu'ici ont été effectués de nombreux forages et qu'à son bord s'ouvre la célèbre Grotte de Movilé. Les sédiments accumulés dans l'oban sont des repères pertinents qui argumentent la genèse du celui-ci par effondrement karstique. Au cours de leur évolution, ces grandes dolines ont connu trois phases principales : de doline-lac, de doline-marécage et de doline-sèche. Ross, J.-H., Serefiddin, F., Hauns, M., Smart, C.C. - 24 h Tracer Tests on Diurnal Parameter Variability in a Subglacial Karst Conduit: Small River Valley, Canada. pp. 93-99. Repeated dye tracer tests were undertaken for two complete diurnal discharge cycles at Small River Glacier, British Columbia. The injection site is a well developed glacier moulin. Monitoring was done at a karst spring in a cave entrance 1530 m down valley. The spring is the major outlet of glacial meltwater and also drains karstified glacier forefields. High flow velocities and low dispersivities indicate a very well developed conduit flow system. Discharge and velocity show strong diurnal cycles and are controlled by the amount of meltwater. The relationship of increasing velocity with discharge is approximately linear. Dispersivity values do not show any significant variation under diurnal discharge cycles. These results show the importance of diurnal variation in a transient groundwater system. Vesper, D.J., Loop, C.M., White, W.B. - Contaminant transport in karst aquifers. pp. 101-111. Contaminants are easily injected into karst aquifers through sinking streams, sinkholes, or through open fractures and shafts in the carbonate rock. Transport of the contaminants through the aquifer is by a variety of mechanisms depending on the physical and chemical properties of the contaminant. Contaminants consist of (1) water soluble compounds, both organic and inorganic, (2) slightly soluble organic com-pounds, less dense than water (LNAPLs), (3) slightly soluble organic compounds, more dense than water (DNAPLs), (4) pathogens, (5) metals, and (6) trash. Water soluble compounds (e.g. nitrates, cyanides, carboxylic acids, phenols) move with the water. But rather than forming a plume spreading from the input point, the contaminated water forms linear stringers migrating down the conduit system toward the discharge point. LNAPLs (e.g. petroleum hydrocarbons) float on the water table and can migrate down the water table gradient to cave streams where they tend to pond behind obstructions. DNAPLs (e.g. chlorinated hydrocarbons), in contrast, sink to the bottom of the aquifer. In the conduit system, DNAPLs pond in low spots at the bottom of the conduit and infiltrate sediment piles. Transport of both LNAPL and DNAPL is dependent on storm flow which can force LNAPL through the system as plug flow and can move DNAPLs by mobilizing the sediment piles. Pathogens (viruses, bacteria, parasites) are transported through the karstic drainage system because of the absence of filtration and retain their activity for long distances. Metals (e.g. chromium, nickel, cadmium, mercury, and lead) tend to precipitate as hydroxides and carbonates in the neutral pH, carbonate rich water of the karst aquifer. Metal transport is mainly as particulates and as metal adsorbed onto small particulates such as clays and colloids. Metal transport is also episodic. Metals migrate down the flow path under flow conditions that take small particulates into suspension. Trash is carried into karst aquifers through sinkholes and sinking streams. It is, in effect, a form of clastic sediment, and can be carried deep into the conduit system where it can act as a source term for other contaminants leached from the trash. Brunet-Lecomte, P., Paunesco, A.-C. - Microtus (Terricola) grafi miciaensis (Rodentia, Mammalia), une nouvelle sous-espèce du site moustérien de Gaura Lupului (Craciunesti, Roumanie). pp. 113-117. Les particularités morphométriques de la population de M. (Terricola) grafi du site moustérien de Gaura Lupului (village de Craciunesti, département de Hunedoara, Roumanie), nous a incités à lui donner un rang sub-spécifique. Elle est décrite sous le nom de Microtus (Terricola) grafi miciaensis. Book Reviews Constantin, S. - Speleological Atlas of Serbia. p. 119. Onac, B. P. - Speleogenesis. Evolution of karst aquifers. p. 120. Racovita, G. - Précis de Karstologie. pp. 121-122. Roata, S. - Geologia regiunilor carstice. p. 122. Constantinescu, T. - Scarisoara Glacier Cave. Monographic study. p. 123. Iurkiewicz, A. - Geological engineering in karst. p. 124. Constantin, S. - Caves Beyond Time. p. 125. Moldovan, O. - The protection of the subterrannean environment.p. 126. In Memoriam Petre-Mihai Samson, 1930-2001.
Restriction:
Open Access - Permission by Publisher
Original Version:
Vol. 13-14 (2000-2001)
General Note:
See Extended description for more information.

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University of South Florida Library
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University of South Florida
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K26-04804 ( USFLDC DOI )
k26.4804 ( USFLDC Handle )
11647 ( karstportal - original NodeID )
1012-9308 ( ISSN )

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Description
Contents and
Abstracts: Constantin, S. Editorial. p. 4. TAK Meetings:White,
W.B. The Friends of Karst. pp. 5-6. TAK Anniversaries: Onac,
B.P. Iosif Viehmann a life for karst, p. 7. TAK Articles:
White, W.B., & White, E.L. Conduit fragmentation, cave
patterns, and the localization of karst ground water basins:
the Appalachians as a test case. pp. 9-23. Because conduit
systems in maturely developed karst aquifers have a low
hydraulic resistance, aquifers drain easily and karst aquifers
are subdivided into well-defined ground water basins. Ground
water elevations are highest at basin boundaries; lowest at the
spring where the ground water is discharged. Parameters that
control the type of conduit development are (1) the effective
hydraulic gradient, (2) the focus of the drainage basin, and
(3) the karstifiability of the bedrock. Moderate to highly
effective hydraulic gradients permit the runaway process that
leads to single conduit caves and well ordered branchwork
systems. Low hydraulic gradients allow many alternate flow
paths and thus a large degree of fuzziness in the basin
boundaries. Low gradient ground water basins also tend to merge
due to rising water tables during periods of high discharge.
Focus is provided by geological constraints that optimize
discharge at specific locations that can evolve into karst
springs. Karstifiability is a measure of the bulk rate at which
aquifer rocks will dissolve. Fine grained, pure limestones and
shaley dolomites mark the opposite ends of the range. The cave
surveys of the Appalachian Highlands provide a data base that
can be used to classify the lateral arrangements of conduit
systems and thus determine the relative importance of the
factors defined above. Tamas, T., & Causse, C. U-Th TIMS
chronology of two stalagmites from V11 Cave (Bihor Mountains,
Romania). pp. 25-32. Two stalagmites (S22, S117) from V11 Cave
(Bihor Mountains, Romania) were dated by thermal ionisation
mass-spectrometry (TIMS). The 40 subsamples dated had uranium
contents between 0.229 and 0.676 ppm, a 234U/238U actual ?1 and
generally low detrital contamination. Ages obtained range
between 138.3 1.6 ka and 5.6 0.1 ka and are distributed in
six growth periods separated by hiatuses. Growth rates
calculated show that calcite deposition was slow in both
stalagmites for most of the depositional periods recorded
during oxygen isotope (OI) stage 5 (1.3-3 mm/ka), with the
exception of the OI substage 5e, when S117 experienced fast
growth (50 mm/ka). After an interruption of 22 ka, calcite
deposition in S22 resumed during OI stage 3 (2.5 mm/ka). The
age of 23.4 0.12 ka recorded in S117 confirms previous
evidence for a short depositional period during OI stage 2.
Termination I was determined in S117 at 16.08 ka. The last
growth interval during OI stage 1 is marked by a strong
increase in growth rates of both stalagmites, determined by
warming and by a significant increase in precipitation. The
presented dataset frames the main climatic events that occurred
in the last 140 ka and brings a precise chronology in this time
span, in good agreement with previous studies from Europe and
NW Romania. Onac, B.P. Mineralogical studies and
Uranium-series dating of speleothems from Scarisoara Glacier
Cave (Bihor Mountains, Romania). pp. 33-38 Recent mineralogical
investigations carried out in Scarisoara Glacier Cave pointed
out the presence of speleothems made up of monohydrocalcite and
hydromagnesite. Although both minerals were documented earlier
from other Romanian caves this is for the first time when a
speleothem is described as being entirely composed of
monohydrocalcite. Crocoite, a rare mineral was also identified;
however, this is not a real cave mineral being transported into
the cave by the percolating waters. U-Th dating of some
speleothems from Scarisoara Glacier Cave enabled us to draw
some considerations concerning the palaeoclimate changes and
the age of the cave. Constantin, S., Lauritzen, S.-E., Stiuca,
E., & Petculescu, A. Karst evolution in the Danube Gorge
from U-series dating of a cave bear skull and calcite
speleothems from Pestera de la Gura Ponicovei (Romania). pp.
39-50. Two bone samples taken from a cave-bear skull discovered
in Pestera de la Gura Ponicovei (Danube Gorge, Romania) have
been dated by U-series liquid-liquid extraction procedure. They
allowed the determination of a minimum age of the cave as well
as the minimum age of Danube's fourth terrace at c. 277 ka.
This age has been also used to ascertain the paleontologic
determination of the bear species as Ursus deningeri v.
Reichenau. Datings on speleothem calcite indicate that the
minimum age of the active level of the cave is ~30 ka and
enabled rough estimations of the incision rate of the
underground river and of the fluvial erosion rate of the Danube
at 0.05 m/ka and 0.67 m/ka, respectively. Mylroie, J., &
Jenson, J. The Carbonate Island Karst Model applied to Guam.
pp. 51-56. The karst of tropical carbonate islands is unique
because: 1) fresh water-salt water mixing occurs at the base
and margin of the fresh-water lens; 2) glacioeustasy has moved
the freshwater lens up and down through a vertical range of
over 100 m; and 3) the karst is eogenetic, i.e., it has
developed in young carbonate rocks that have never been buried
beyond the range of meteoric diagenesis. Carbonate islands can
be divided into three categories based on basement-sea level
relationships: simple carbonate islands (no non-carbonate
rocks), carbonate cover islands (non-carbonate rocks beneath a
carbonate veneer), and composite islands (carbonate and
non-carbonate rocks exposed on the surface). These ideas form
the Carbonate Island Karst Model (CIKM) which can be visualized
in terms of a three-dimensional framework, with island size on
the x-axis, sea-level change on the y-axis, and bedrock
relationships on the z-axis. On Guam, tectonic uplift and
glacio-eustatic sea level change have produced a complex
history on this composite island. The aquifer is partitioned in
the subsurface by the antecedent topography of the volcanic
core of the island, and lens discharge is both diffuse and
conduit controlled. Florea, L., Mylroie, J., & Carew, J. -
Karst genetic model for the French Bay Breccia deposits, San
Salvador, Bahamas. pp. 57-65. the Island of San Salvador in the
Bahama archipelago 30 breccia deposits can be found along the
French Bay sea cliffs on the southeastern coast of the island.
Breccia deposits of this type have not been observed on any
other location on the island. These deposits have traditionally
been interpreted as paleo-talus deposits from an eroding sea
cliff formed on a transgressive eolianite deposited at the
start of the oxygen isotope substage 5e sea-level highstand
(ca. 125,000 years before present). New evidence supports a
karst genesis. A survey of several deposits revealed a vertical
restriction of +2 to +7 meters above sea level consistent with
flank margin caves developed during the substage 5e
still-stand. The morphologies of the features were found to be
globular and contain distinct caliche boundaries, overhung
lips, and smooth undulating bases. Petrographic results support
a model in which voids are created and then infilled with a
soil breccia. It can be concluded from these results that the
deposits reflect qualities of a lithified soil breccia filling
in breached flank margin caves. Diaconu, G., & Dumitras, D.
- Sur la prsence de l'ardalite dans la Grotte de Topolnita
(Plateau de Mehedinti, Roumanie). pp. 67-73. Il y 70 annes,
dans la Grotte de Cioclovina (Monts Sebes, Roumanie) un nouveau
minral l'ardalite a t dcouvert en association avec le
gypse et la broushite (HALLA, 1931; SCHADLER, 1932). Les
auteurs ont identifi la mme association minralogique dans la
Galerie Suspendue de la Grotte de Topolnita (Plateau de
Mehedinti). L'chantillon prlev a t analys en RX, IR, TDA
et chimiquement. Les donnes obtenues, compares avec les
donnes standard, ont mis en vidence l'ardalite, le gypse et
la broushite. Le travail prsente de mme un point de vue
original sur les conditions du milieu splique qui ont
facilit la gense de cette association minralogique.
Ljubojevic, V., Pacevski, A., & Calic-Ljubojevic, J. On
the genetic conditions of black manganese deposits from two
caves of Eastern Serbia. pp. 75-79. Portions of cave passages
often have a black colour due to manganese deposits that occur
as coatings on cave walls and ceilings, on clastic sediments,
as well as on speleothems. On samples from the cave Buronov
Ponor chemical analysis, infrared spectroscopy, X-ray
diffraction and DTA analysis confirmed the presence of
birnessite. In cave Cerjanska Pecina, the presence of manganese
compounds in the black coating has been confirmed by chemical
tests. In both caves it has been noted that cave passages with
black coating have a distinct morphology. They are highly
weathered showing an abundance of sharp protusions, potholes in
the streambed and scallops. The paper studies these occurrences
and the possible link between the manganese deposition,
hydrology and morphology of the passages and petrologic
composition. Although this link was not identified, some
interesting questions regarding manganese deposition arose. It
remains unclear why manganese deposition is limited only to a
certain part of cave Cerjanska Pecina, and what caused the
cyclicity in manganese deposition in the cave Buronov ponor.
Feier, N., Munteanu, G., & Onac, B. P. Mineralogy and
speleogenesis of the Ice-Cave from Poiana Vrtop (Bihor
Mountains, Romania). pp. 81-85. The cave of Poiana Vrtop in
the NW Bihor Mountains hosts the fourth largest underground
perennial glacier in Romania with a volume estimated to 12,000
m 3 The ice accumulated within the cave as a result of
trapping of subzero winter air through its single entrance near
the top of the cave. The speleothem mineralogy is dominated by
calcite, with minor amounts of included aragonite. Crusts of
carbonate-hydroxylapatite (associated with bat guano) and
goethite (associated with pyrite in the host limestone) are
found at a few locations. Based on structural observations, dye
traces, and cave galleries orientations, it is inferred that
the cave is part of a much larger hydrologic karst system that
also includes the nearby Humpleu-Poienita cave network.
Constantinescu, T., & Constantin, S. La gense et
l'volution des grandes dolines (obans) de la zone karstique de
Mangalia (Dobroudja du Sud, Roumanie). pp. 87-92. Pour
expliquer la gense et l'volution des grandes dolines ou
obanes de la zone karstique de Mangalia, Obanul Mare est le
plus reprsentatif, du fait qu'ici ont t effectus de
nombreux forages et qu' son bord s'ouvre la clbre Grotte de
Movil. Les sdiments accumuls dans l'oban sont des repres
pertinents qui argumentent la gense du celui-ci par
effondrement karstique. Au cours de leur volution, ces grandes
dolines ont connu trois phases principales : de doline-lac, de
doline-marcage et de doline-sche. Ross, J.-H., Serefiddin,
F., Hauns, M., & Smart, C.C. 24 h Tracer Tests on Diurnal
Parameter Variability in a Subglacial Karst Conduit: Small
River Valley, Canada. pp. 93-99. Repeated dye tracer tests were
undertaken for two complete diurnal discharge cycles at Small
River Glacier, British Columbia. The injection site is a well
developed glacier moulin. Monitoring was done at a karst spring
in a cave entrance 1530 m down valley. The spring is the major
outlet of glacial meltwater and also drains karstified glacier
forefields. High flow velocities and low dispersivities
indicate a very well developed conduit flow system. Discharge
and velocity show strong diurnal cycles and are controlled by
the amount of meltwater. The relationship of increasing
velocity with discharge is approximately linear. Dispersivity
values do not show any significant variation under diurnal
discharge cycles. These results show the importance of diurnal
variation in a transient groundwater system. Vesper, D.J.,
Loop, C.M., & White, W.B. Contaminant transport in karst
aquifers. pp. 101-111. Contaminants are easily injected into
karst aquifers through sinking streams, sinkholes, or through
open fractures and shafts in the carbonate rock. Transport of
the contaminants through the aquifer is by a variety of
mechanisms depending on the physical and chemical properties of
the contaminant. Contaminants consist of (1) water soluble
compounds, both organic and inorganic, (2) slightly soluble
organic com-pounds, less dense than water (LNAPLs), (3)
slightly soluble organic compounds, more dense than water
(DNAPLs), (4) pathogens, (5) metals, and (6) trash. Water
soluble compounds (e.g. nitrates, cyanides, carboxylic acids,
phenols) move with the water. But rather than forming a plume
spreading from the input point, the contaminated water forms
linear stringers migrating down the conduit system toward the
discharge point. LNAPLs (e.g. petroleum hydrocarbons) float on
the water table and can migrate down the water table gradient
to cave streams where they tend to pond behind obstructions.
DNAPLs (e.g. chlorinated hydrocarbons), in contrast, sink to
the bottom of the aquifer. In the conduit system, DNAPLs pond
in low spots at the bottom of the conduit and infiltrate
sediment piles. Transport of both LNAPL and DNAPL is dependent
on storm flow which can force LNAPL through the system as plug
flow and can move DNAPLs by mobilizing the sediment piles.
Pathogens (viruses, bacteria, parasites) are transported
through the karstic drainage system because of the absence of
filtration and retain their activity for long distances. Metals
(e.g. chromium, nickel, cadmium, mercury, and lead) tend to
precipitate as hydroxides and carbonates in the neutral pH,
carbonate rich water of the karst aquifer. Metal transport is
mainly as particulates and as metal adsorbed onto small
particulates such as clays and colloids. Metal transport is
also episodic. Metals migrate down the flow path under flow
conditions that take small particulates into suspension. Trash
is carried into karst aquifers through sinkholes and sinking
streams. It is, in effect, a form of clastic sediment, and can
be carried deep into the conduit system where it can act as a
source term for other contaminants leached from the trash.
Brunet-Lecomte, P., & Paunesco, A.-C. Microtus
(Terricola) grafi miciaensis (Rodentia, Mammalia), une nouvelle
sous-espce du site moustrien de Gaura Lupului (Craciunesti,
Roumanie). pp. 113-117. Les particularits morphomtriques de
la population de M. (Terricola) grafi du site moustrien de
Gaura Lupului (village de Craciunesti, dpartement de
Hunedoara, Roumanie), nous a incits lui donner un rang
sub-spcifique. Elle est dcrite sous le nom de Microtus
(Terricola) grafi miciaensis. Book Reviews Constantin, S. -
Speleological Atlas of Serbia. p. 119. Onac, B. P. -
Speleogenesis. Evolution of karst aquifers. p. 120. Racovita,
G. Prcis de Karstologie. pp. 121-122. Roata, S. Geologia
regiunilor carstice. p. 122. Constantinescu, T. Scarisoara
Glacier Cave. Monographic study. p. 123. Iurkiewicz, A. -
Geological engineering in karst. p. 124. Constantin, S. Caves
Beyond Time. p. 125. Moldovan, O. The protection of the
subterrannean environment.p. 126. In Memoriam Petre-Mihai
Samson, 1930-2001.



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Theoretical and Applied Karstology Volumes 13-14

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Theoretical and Applied Karstology EDITORIAL BOARD Managing Editor: Silviu Constantin, "E. Racovija"lnstitute of Speleology, Bucharest Romania. Associated Editors: Bogdan P. Onac, "E. Racovija" Institute of Speleology, and University, Romania. Adrian ltirkiewicz, UN, FAO expert, Bucharest, Romania. Horia Mitrofan, s. l;)tefiinescu" Institute for Geodynamics, Bucharest Romania. Cristian Lascu, "E. Racovijii" Institute of Speleology, Bucharest Romania. Editorial Assistant: Marius Vlaicu, "E. Racovijii" Institute of Speleology, Bucharest, Romania. Board of Reviewers: Michel Bakalowicz, (Montpellier, France) Andy Baker (Newcastle, UK) Marcian Bleahu (Bucharest, Romania) Pavel Bosak Czech Republic) -Jose-Maria Calaforra (Almeria, Spain) Gabriel Diaconu (Bucharest, Romania) Wolfgang Dreybrodt (Bremen, Germany) Derek Ford (Hamilton, Ontario, Canada) Paolo Forti (Bologna, Italy) Silvia Frisia (Trento, Italy) Dominique Genty (Saclay, France) Cristian Goran (Bucharest, Romania) Pierre-Yves Jeannin (La Chaux-de-Fonds, Switzerland) Naruhito Kashima (Ehime, Japan) Alexander Klimchouk (Kiev, Ukraine) Stein-Erik Lauritzen (Bergen, Norway) David J. Lowe (Nottingham, UK) Paul Marinos (Athens, Greece) Jacques Martini (Pretoria, South Africa) Andrej Mihevc (Postojna, Slovenia) Petar Milanovic (Belgrade, Yugoslavia) John Mylroie (Missisippi, USA) lancu (Bucharest, Romania) Arthur Palmer (Oneonta, USA) loan Povara (Bucharest, Romania) Gheorghe Racovita (Ciuj-Napoca, Romania) Costin Radulescu (Bucharest, Romania) Jean-Noel Salomon (Marseille, France) Ira Sasowski (Akron, Ohio, USA) Yavor Shopov (Sofia, Bulgaria) Augustin Tenu (Bucharest, Romania) Franco Urbani (Caracas, Venezuela) Yuan Daoxian (Guilin, China) William White (Pennsylvania, USA) Paul Williams (Auckland, New Zealand) Florian Zamfirescu (Bucharest, Romania) Indexation: Georef I EoiTURA AcADEMIEI RoMANE vol. 13-14/2000-2001 ISSN: 1012-9308 Theoretical and Applied Karstology (TAK) is an annual journal dedicated to the karst and caves sciences. The first four issues were published by the 'Emil Racovita'lnstitute of Speleology, as a series, between 1983 and 1991. Since 1992, TAK has been edited by the Institute and published by the Romanian Academy's Publishing House. TAK publishes original contributions (review articles, research papers, short notes and book reviews) covering the whole range of karstology and physical speleology: karst geology and mineralogy, chemistry and physics of karst processes, karst geomorphology, karst hydrology and hydrogeology, speleo-chronology and landscape evolution, speleogenesis, climate and subterranean environment, speleo-paleontology, engineering and environmental problems in karst, karst managment, etc. The Editors welcome the submission of contri-butions from all over the world. The 'Emil Racovita' Speleological Institute encourages the exchange between TAK and specialized journals. Past TAK issues are also available to the Institute. Please address any inquiries concerning publication exchanges, subscriptions, and any article submission to: Theoretical & Applied Karstology Editorial Board lnstitutul de Speologie "Emil Racovita" str. Frumoasa 11, C.P. 220-12, R-78114 Bucuresti, Romania. tel: +40-1-6503465; tel/fax: +40-2113874 email: karstology@yahoo.com http:// www.geocities.com/karstology Cover photographs by Cristlan Lascu: Front cover: A passage of epiphreatic origin with an elliptical cross-section in the Epuran Cave (Topolnita-Epuran Cave System, see paper page 67). Back cover: Ice stalagmites in 'The Church' Chamber, Scarisoara Ice-Cave (Bihor Mountains, see paper page 33). Language revisions: Rodica Florescu DTP Editor: Silviu Constantin This volume was supported by the Romanian Federation of Speleology. Galea 13 Septembrie 13, P.O. Box 5-42, 76117 Bucurejjtl, Romania. te1:+40-1-4119008

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Romanian Academy Editura Academiei Romane "Emil Racovita" Institute of Speleology Bucureti, 2001 Theoretical and Applied Karstology Volumes 13-14/2000-2001 ::.-,_-_ ...

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4 Editorial To the usual T AK readers this double-issue may look familiar, in spite of some obvious changes to its layout. For us, editors, as seen from 'the inside' the journaJ. has changed from many other viewpoints. The following lines will attempt to reveal some of those changes. Traditionally, TAK articles were selected from those papers presented to the annual "Symposiums of Theoretical and Applied Karstology". Unfortunately, for several reasons, among which the economic challenges that Romania in gen eral and research institutions in particular have to face, the organizers of this symposium (the "Emil Racovitlf' Institute of Speleology and the "Prospectiuni" Company for Geologi cal Research) were forced to disrupt its annual organization. The last 'independent' T AK Symposium was held in the spring of 1998, in Baile Herculane; the next one was held in 2000, in Cluj, in conjunction with the 15th "Friends of Karst" Meeting and the first workshop of the IGCP 448 Committee. As a first, predictable, consequence of this decrease in peri odicity, the number and the frequency of contributions sub mitted to our journal strongly diminished. In an inertial at tempt to 'keep the pace' with the T AK-Symposium, the jour nal appeared in 1999 for the first time as a doubleissue (11-12). However, we were well aware that this 'solution' was unacceptable: there are very few authors (if any!) that would submit their contributions toT AK knowing that the publish ing time will exceed one year. In order to 'keep alive' the journal, its dependence on the T AK Symposiums should come to an end. This, again, double-issue has a 'transitional' structure. Some of its articles were submitted at the above-mentioned joint meeting in Cluj 2000, while other were independently received during the year 2001. It is the first time when T AK does not (almost) exclusively rely on symposium contributions. Independent submission, however, demands an increased exigency. Symposium presentations often benefit by helpful criticism; in most cases the result of this was a noticeable improvement of the quality of the 'final form' of the contri butions. As a newly direct-submission journal, TAK had to Theoretical and Applied Karstology, 13-14 (2000-2001) boost its peer-review system in order to ensure a high scien tific standard. In May 2001, the Editorial Board was renewed and the Board of Reviewers was substantially enlarged. The peer-review system was fully enforced and we benefit now of the exper tise and the support of 36 established specialists in almost all fields of caves and ka,rst sciences. At the same time, we de cided to make our way on the Internet: the first T AK homepage has been created at http://www.geocities.com/karstology. Of course, for the time being this page is still in its infancy and could be improved in many ways. Still, the contents and ab stracts of all T AK issues are there and we have also offered a temporary access to the full text of the articles in the latest issue. This and our future efforts will aim to increase the ac cessibility and scientific circulation of the journal for the ben efit of all our contributors. This issue features articles belonging to various domains, from mineralogy, to paleoclimate reconstructions, speleogen esis, karst modeling and karst hydrogeology. The common points of its eclectic content are and karst and this is something that we would like to inherit from the 'old TAK'. After all, there are not so many scientific journals where one can publish the results of researches carried on in karst and, at the same time, feel "in the family". Since many of the ar ticles were presented at the joint T AK-"Friends of Karst" meeting in Cluj, we considered that a brief presentation of the latter would be appropriate. This was done right in the next pages by professor White, one of the FOK's 'inventors'. As a novelty, we have also introduced a new section, of "Book reviews", which was thought to be useful. Volume 13-14 ofTAK is the result of a collective, enthusi astic work, carried out not only by the editorial staff but also by our friends all over the world that have made valuable suggestions and, sometimes have assumed some 'less scien tific' tasks such as_ suggesting language corrections or ways oflayoutimprovement. We thank them all and assure everybody that we'll continue our work to make TAKa better jour nal. Silviu Constantin

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Theoretical and Applied Karstology, 13-14 (2000-2001) TAK Meetings B ecause the Friends of Karst is a very low profile organi zation (or non-organization) some explanation and a short history is given here. The Friends of Karst has operated quite effectively for more than 30 years with no officers, nor organizational structure, no dues, and no membership. Its primary function is to host occasional meetings, some with field trips, when regular pro fessional meetings are deemed insufficient. These meetings are intended for open discussion of work in progress. In prac tice some of the meeting have been highly informal with little or nothing in the way of printed records. Other have been more formal with published abstracts and in several cases, published proceedings. Decisions about the level of formal ity are the responsibility of the organizers. Field trips have been an important part of the meetings The idea is to have the participants get a first hand look at the host's favorite field areas. Open discussion of karst prob lems in the field promotes understanding at a very funda mental level. Participants to the Friends of Karst Meeting in Cluj, July 2000, in front of the "Emil Racovita" Institute, just before the start of the field-trip (Photo: Bogdan Onac). 5 The Friends of Karst Those karst researchers present at the annual meeting of the Geological Society of America have met in Will and Bet White's hotel room where they talk, drink some beer, and devote not more than five minutes to an annual business meeting. In recent years, others have volunteered their hotel room but thus far no more formal arrangement has been nec essary Meetings are organized when someone expresses an interest in hosting a meeting. The host then makes the neces sary arrangements and organizes the program and field trips. The meeting of the Friends of Karst in Cluj was number 15 in the series and the first such meeting held in Europe The complete list of meetings is given below 1. Hamilton, Ontario, September, 1968. Hosted by Derek Ford at his farmhouse outside of Hamilton. About 25 .in attendance including Marjorie Sweeting and Paul Will iams. This meeting set the format of informal discussions of on-going work; not professional meeting summaries of completed work.

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6 :2:" Penn State University; May, 1970. Hostedby W:B: White, R. R. Parizek, and D. Langmuir as a special con ference for members of the karst working group of the International Hydrologic Decade. A field trip was orga nized for this conference. 3. McMaster University, October, 1971. Joint meeting with the Cave Research Associates. Abstracts published in Cave Notes 13, 37-44, 8-51 (1971). 4. West Virginia University, Morgantown, 1974 Hosted by Henry R.auch. A more formal meeting with a published proceedings: Fourth Conference on Karst Geology and Hydrology Proceedings, H.W. Rauch and E. Werner, Eds., West Virginia Geological Survey, Morgantown, 187 p. (1974). 5 Mammoth Cave, Kentucky, April, 1978 Hosted by James F. Quinlan. Intensive technical sessions and sur face and underground field trips. This was the first meet ing to formally call itself the "Friends of Karst". The first version of the Central Kentucky Karst drainage basin map by J.F. Quinlan and J.A. Ray was called Special Publica tion No. 1 of the Friends of Karst. Abstracts published in Geo, 5, 22-28 (1978). 6. Ely, Nevada, September, 1979. Hosted by Jack Hess and Roger Jacobson. Abstracts published in Geo 7, 27-30 (1980). 7. McMaster University, April, 1982 Hosted by Derek Ford. Although listed as a meeting of the Friends of Karst, this meeting was (more or less) by invitation only and had 22 people in attendance. 8 University of Puerto Rico, Mayaguez, February, 1984 Hosted by Joseph W Troester. First "off shore" meeting. Good field trip though the cone and tower karst. Abstracts published in Geo, 11, 44-49 (1984). 9. State University College, Oneonta, New York, March, 1987. Hosted by Arthur and Margaret Palmer. Informal meeting with no published abstract. 37 people in atten dance. I 0. San Salvador Island, Bahamas, February 1988. Hosted by John Mylroie. 42 people in attendance. Abstracts pub lished in Geo, 15, 29-34 (1988). .W. B. White H.: Decorah, Iowa, April, 1990. Hostedby George Huppert. Abstracts published in Geo, 17, 59-87 (1990). 12.Radford University, Radford, Virginia, March 1991. .Hosted by Ernst and Karen Kastning. Part of special sym posium on Appalachian Karst. 72 people in attendance. Proceedings volume: Appalachian Karst, E.H. Kastning and K.M. Kastning, Eds., National Speleological Soci ety, Huntsville, AL, 239 p. (1991). 13. Tennessee Technological University, Cookeville, Tennessee, April, 1992. Hosted by Albert Ogden. 122 people in attendance. Abstracts and a guidebook for two days of field trips were distributed at the meeting but not other wise published. 14. Bowling Green, Kentucky, September, 1998 Hosted by Chris Groves and Joe Meiman. Joint meeting with IGCP Project 379. At this meeting there were a large number of attendees from overseas. 15. Cluj, Romania, July, 2000 Hosted by Bogdan Onac and the Babe-Bolyai University, Speological Institute "Emil Racovita" and Romanian Speleological Federation. 131' people in attendance from 17 countries. First European meeting of the Friends of Karst. Proceeding volume: Karst Studies and Problems: 2000 and Beyond (Onac, B.P. and Tamas, T. Eds.), Presa Universitara Clujeana, Cluj, 196 p. (2000). Both proceedings and a guidebook were distributed at the beginning of the meeting. At the time of the early meetings of the Friends of Karst, were few karst papers at professional meetings. During the 30 years that the Friends of Karst has been functioning, the number of papers at meetings such as the Geological So ciety of America has grown and has the number of karst sci entists attending the meeting. Other specialist conferences such as those organized by the Karst Waters Institute, the In ternational Association ofHydrogeologists, the National As sociation of Water Scientists and Engineers and the Sinkhole Conferences have appeared in increasing numbers. SCien tific communication between the US and Europe has contin ued to grow. However, it seems likely that future meetings of the Friends of Karst will continue to be scheduled, if for no other reason than that karst researchers appreciate the oppor tunity to display their favorite karst areas to their friends and colleagues. William B; White Department of Geosciences, The Pennsylvania State University, University Park, PA 16802 USA

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Theoretical and Applied Karstology, 13-14 (2000-2001) TAK Anniversary On the first of September 2000, our colleague Dr. Iosif (Pepi) Viehmann celebrated his 75111 birthday anniversary. Pepi Viehmann's activity identifies with the post-war beginnings of scientific speleology in our country. His interest for karst research appeared since he was still a student, and at the very beginning he was coordinated by Emil Racovita. the founder of the first Speleological Institute in the world. Pepi Viehmann dedicated more than 50 years to the exploration and study of several karst regions of Romania, Apuseni and Rodnei Moun tains being the closest to his heart. His activity, longer than half a century, has been highlighted by many achieve ments in both exploration and publica tion fields. He was member of the teams that during the '50s and '60s consider ably increased the inventory of Roma nian caves through their exceptional dis coveries and explorations. Together with Mihai Marcian Bleahu, Emilian Cristea, Dan Coman, V ali Crliciun, Theo Rusu and Gheorghe he sur veyed caves such as Pojarul PoliJei, Cetilfile Ponorului, A venul din $esuri, Cilput, Petera Neagri:i, Avenul Gemi:inata, Ti1UOare, Jgheabul lui Zalion, Petera Urilor, to remind only a few of them. A brief survey of the four books released with the same title: Peteri din Romania (Caves of Romania), reveals the name of Pepi Viehmann on numer ous cave maps, suggesting an intensive field activity. From a scientific point of view, our colleague Pepi Viehmann published more than a hundred papers in Romanian and for eign journals. Among these, there are to be remarked the monographs concerning karren and stream potholes (whirl pools), as well as the series of studies on the genesis and morphology of cave pearls. He is the main author of the pic ture book of Ghetarul de la Sclirioara, also co-authoring two other books illustrating and describing the caves of Romania. Added to these is the release, in this anniversary year, of his General Speleology textbook for students. A particular place in Pepi Vl.ehmann' s scientific activities was occupied by the field trips to the GheJarul de La Scarioara, where, each month over 40 years, he gathered climatic and 7 losif Viehmann-a lifetime for karst glaciologic data which were used in several papers published in collaboration or as a single author. His biospeleological obser vations were fructuously used by his biologist colleagues. Gifted with a special capacity of observation, knowing how to value each detail, master in designing original methods to explain various genetic processes, Pepi Viehmann surprised the scientific community by some very ingenious experiments. He marked with paint numerous cave pearls and cave rafts to examine their evolution, he ringed eccen tric speleothems with a chemical pencil to prove the antigravitational crystallogenesis process and he revealed the presence of the permanent drop on top of crystallictites. Pepi Viehmann's name is linked to the sen sational discoveries of the prehistoric hu man footprints in the clay of Ciur-Izbuc Cave or in the moonmilk of the Viirtop Glacier (Casa de Piatrli). Added to these are his thorough observations on the cave bears traces and their cohabitation with the prehistoric humans. Excellent pedagogue and good mate in the field campaigns, he led with professional ism several series of students in the fasci nating world of caves. He attracted them and made them love speleology with the help of his charming slide shows and his unforgettable caving camps. He helps any one looking for advice and knows bow to be loved and appreciated by all. His major merit, as Cristian Lascu pointed out, was not only that he discovered some of the outstanding Romanian caves, but mostly that he has con tinuously discovered people who, in their turn, discover and studied new caves. The boundless love and passion for the magnificent world of karst is the secret of his youth and power of work. All these characteristics make Pepi Viehmann to be a living stimulus for the young generation in the Speleological Institute. For all above-m_;:ntioned reasons we all wish to have him near us as long as possible. Bogdan P. Onac

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Theoretical and Applied Karstology, 13-14 (2000--2001), pp. 9-23 Conduit fragmentation, cave patterns, and the localization of karst ground water basins: the Appalachians as a test case William B. & Elizabeth L. White2 1 Materials Research Laboratory and Dept. of Geosciences, The Pennsylvania State University, University Park, PA 16802, USA. 2 Envimnmental Resources Research Institute, The Pennsylvania State University, University Park, PA 16802, USA. Abstract Because conduit systems in maturely developed karst aquifers have a low hydraulic resistance, aquifers drain easily and karst aquifers are subdivided into well-defined ground water basins. Ground water elevations are highest at basin boundaries; lowest at the spring where the ground water is discharged. Parameters that control the type of conduit development are (1) the effective hydraulic gradient, (2) the focus of the drainage basin, and (3) the karstifiability of the bedrock. Moderate to highly effective hydraulic gradients permit the runaway process that leads to single conduit caves and well ordered branch work systems. Low hydraulic gradients allow many alternate flow paths and thus a large degree of fuzziness in the basin boundaries. Low gradient ground water basins also tend to merge due to rising water tables during periods of high discharge. Focus is provided by geological constraints that optimize discharge at specific locations that can evolve into karst springs. Karstifiability is a measure of the bulk rate at which aquifer rocks will dissolve. Fine grained, pure limestones and shaley dolomites mark the opposite ends of the range. The cave surveys of the Appalachian Highlands provide a data base that can be used to classify the lateral arrangements of conduit systems and thus determine the relative importance of the factors defined above. Keywords:conduits, triple permeability, karst parameters, karstifiability, lithologic controls, structural controls. Resume Fragmentation des conduits, modeles des reseaux souterraines et localisation des bassins hydro-karstiques: etude de cas sur les Monts Appalaches A cause de La faihle resistance hydraulique des systemes de conduits des aquiferes karstiques matures ceux-ci sont facilement draines et peuvent etre suhdivises dans des bassins hydrogeologiques distincts. Les altitudes des nappes karstiques sont maxima au bords des bassins et plus basses vers les sources. Les parametres qui controlent le type de developpement des conduits sont: (1) le gradient hydraulique effectif, (2) La concentration du bassin de drainage et (3) La karstifiabilitb> de La roche. Des gra dients lzydrauliques moderes ou eleves permettent le drainage rapide qui, a son tour,favorise La formation des grottes a galerie unique et des systemes dendritiques bien ordonnes. Les gradients hydrauliques bas permettent La formation de plusieurs voies d'ecoulement et, par consequente, les limites des bassins karstiques sont moins nettes. En plus, les bassins a gradients bas ont Ia tendance de fusionner l'un a ['autre en suivant La remontee du nivequ des nappes phreatiques pendant les crues. La concen tration est donnee par les contraintes geologiques qui optimisent le drainage vers des points bien dejinis, pouvant devenir des sources karstiques. La karstifiabilite est une mesure de Ia vitesse globale de dissolution des roches qui constituent l'aquifire. Les calcaires fines, pures, et les dolomies marneux se situent aux extremes du domaine de karstifiabilite. La topographie des grottes des Monts Appalaches constitue une base de donnees qui peut etre utilisee pour Ia classification des modeles des syste mes de conduits et, par consequente, pour determiner /'importance relative des facteurs dejinis ci-dessus. Mots-cles: conduits, triple permeabilite, parametres karstiques, karstifiabilite, contrOle lithologique, controle structural. *corresponding author. E-mail address: wbw2@psu.edu. 200 I, Editur.t Academiei Romane. All rights reserved.

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10 Introduction Karst aquifers have (among others) two characteristics that distinguish them from most other aquifers. One is an extreme permeability distribution generally described by the "triple porosity" model, one component of which is a system of pipes (known as "conduits") The second is an intimate connection between ground water and surface water. Any functional model of karst aquifers must take account of the conduit system In general, this is difficult because the complete conduit system can only rarely be directly observed and there are no really reliable techniques for mapping the conduit system from the land surface. The only data usually available are the results of tracer experiments which give overall connections and transit times, measurements of hydro graphs and chemographs at the springs, and such segments as may be accessible to cave explorers. This leaves an immense amount of uncertainty in the proper placing of conduits and the internal functioning of ground water basins. The most direct information on conduit patterns is obtained from the maps of caves that occur within the drainage basin. Caves consist of those fragments of active and abandoned portions of the conduit system large enough to permit human exploration. However, cave maps require interpretation. Cave explorers regard all accessible passages as part of the same cave Thus, a large cave can be composed of a sampling of conduit system fragments that may be separated in both time and space Higher (and generally dryer) parts of t h e cave are portions of conduits that were formed under earlier conditions sometimes extending far back into the Pleistocene and may not be related to contemporary drainage basins. A single accessible cave may also represent portions of the conduit system of more than one drainage basin The most serious limitation is that almost all caves represent only small fractions of the complete conduit system. A great deal of effort has gone into modeling the evolution of karst aquifers along the time axis. Recent papers, e.g. PALMER (1991 ), DREYBRODT (1992; 1996), GROVES & HOWARD ( 1994 ), HOWARD & GROVES (1995), SIEMERS & DREYBRODT (1998), KAUFMANN & BRAUN (1999, 2000), have shown that iris possible to describe the evolution from an initial fracture to a fully developed conduit and place the proeesses on a reasonable time scale. Although a tremendous number of caves systems have been examined in many parts of the world ( KuMCHOUK et al., 2000), the geological constraints that limit ground water basin development have not been as well systematized. In this paper we return to issues of the development of karst ground water basins that were first raised long ago (WHITE, _1969; 1977). Using examples from the Appalachian Highlands to illustrate points, we attempt to understand the geological factors that control development of karst drainage basins and their associated conduit systems. The Appalachian Mountains of eastern United States have regions of karst development including the W.B. White & E.L. White complexly folded and fau lted Cambrian, Ordovician, and Devonian carbonate rocks of the Valley and Ridge Province and the dissected Appalachian Plateaus with low dip Mississippian l imestones overl ain by caprocks of shale and quartzite (DAVIES & LEGRAND, 1972; DAVIES eta[., 1984). The varying geologic settings in the Appalachian Mountains provide examples of many combinations of geologic constraints on karst drainage basin development. Aquifers, Karst Aquifers, and Surface Water Basins As a point of reference, we briefly describe what may be called a "textbook aquifer" ("textbook" means such standard references as FREEZE & CHERRY (1979), DoMENico& ScHWARTZ (1990), or FETIER (1994)). A 'textbook' aquifer consists of these parts, arranged vertically: (1) The land surface where recharge is provided by precipitation. (2) The soil with its vegetative cover where precipitation is distributed between stored soil moisture, water that is infiltrated downward into the aquifer, and water that is returned to the atmosphere through evaporation and transpiration. (3) The vadose zone, a region of bedrock and regolith with air-filled pore spaces, that serves as a pathway for water in excess of soil moisture to move downward into the aquifer. (4) The water table, the surface that delineates the boundary between saturated and unsaturated portions of the aquifer. (5) The phreatic (or saturated) zone where all void spaces are water filled. The "textbook aquifer" is characterized by the aquifer thickness (the total thickness of the rock unit for a confined aquifer and the thickness of the saturated zone for an unconfined aquifer), and the hydraulic conductivity of the medium. There are, in addition, hydraulic boundaries set in place by impermeable beds and structural constraints such as folding, and faulting. However, the width of the aquifer is usually unspecified the aquifer is limited only by the limits of the rock unit. Flow fields are set by highs and lows in the water table which in tum are controlled largely by surface topography. Surface streams act as zones of ground water discharge. Karst aquifers are rather more complicated. The essential components have been discussed at length in several textbooks (WHITE, 1988; FoRD & WILLIAMS, 1989) and in recent papers (WHITE, 1998; 1999) and are sketched in Figure 1. As with the "textbook" aquifer, there is a diffuse component of recharge infiltrating through the soil and moving downward through fractures into the aquifer As an additional factor, there may be some storage in the epi.karst. Closed depressions on the land surface act as catchments for storm runoff which enters the aquifer through drains in the bottoms of the closed depressions. The third source is from sinking surface streams that provide what is known as allogenic recharge. The fraction of the ground water basin occupied by the catchment areas for sinking surface streams is one of the important parameters characterizing karst ground water basins.

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Conduit fragmentation, cave patterns and localization of karst ground water basins 11 LOSING STREAM BASINS SINKING STREAM BASINS --SHAFTS LEJ SURFACE OVERFLOW CHANNEL ... SINKING STREAM BASINS EXCHANGE t PHREATIC LIFT CONDUIT SYSTEM BASELEVEL STREAM Fig. I. Conceptual model for a karstic aquifer. From WHITE (1999) with modification by J. A. Ray. Modide d'un aquifire karstique. D'apres White (1999), modifie par J. A. Ray. Sinking surface streams and the drains from closed depressions feed directly into the conduits which act as master drains transmitting water at high velocities to their discharge points at karst springs. Well developed conduits have low hydraulic resistance and often create troughs in the water table. Hydraulic gradients within the surrounding bedrock thus point toward the conduits rather than toward the springs (EwERS & QuiNLAN, 1981). Because of the arrangements of hydraulic gradients, each conduit system with its up-gradient infeeders and its set of sinking surface strearris a ground water basin. The better the development of the conduit system, the better defined is the ground water basin. Hydraulic heads are low along the conduit and high between adjacent conduit collection systems. Thus the shallow part of the aquifer becomes segregated into cells, each functioning as a separate ground water basin. The downstream ends of the basins are located at springs where the drainage returns to sm:face routes. The boundaries of the ground water basins are defined by the total recharge areas including all surface stream catchments that drain into the conduit system. Ground water basins evolve with time as the base level surface streams continue to downcut their channels. The evolutionary pattern has been interpreted in the Mammoth Cave area (QuiNLAN & EwERS, 1989). Some karst ground water basins are truly isolated so that all precipitation that falls within the basin ultimately appears at the spring. The boundaries "of these basins often show a good degree of correlation with the boundaries of overlying surface water basins. Others, however, are linked by either piracy routes or spillover routes. Conduits may develop across surface water divides and thereby transmit water to or from other nearby surface water basins. Piracy routes are common and result in ground water basins seriously out of register with overlying surface water basins. The term "spillover route" is used for abandoned conduits that lie just above the active conduit system. These transmit water only during high flow conditions. Thus a ground water basin may have one set of flow paths active during base flow conditions and a quite different set of flow paths during flood flow conditions. The boundaries of the ground water basins also depend on ground water stages and flow conditions. The greater the internal relief of the basin that is the head difference between the spring and the basin divides, the more localized the basin and the more stable the basin boundaries. Karst aquifers in the Appalachian Highlands of eastern United States are restricted because of the limited thickness of the carbonate rock units. The Mississippian limestones that underlie the Cumberland and Allegheny Plateaus have thicknesses of only a few hundred meters. The Ordovician carbonate rocks of the folded Appalachians range in thickness up to several thousand meters but consist of mixed limestone and dolomire sequences. As a result, most ground water basins span the entire saturated thickness of the aquifer. The entire aquifer must be interconnected by diffuse flow through the matrix and fracture permeability but the transmission of water

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12 through the conduit system is so much more efficient that the ground water basins account for nearly all ofthe water budget. The active conduit systems in the Appalachian ground water basins are generally shallow. Some can be explored under base flow conditions as open cave passages with free-surface streams. Often the conduit is an alternating sequence of op(m stream passage and sections that are completely flooded. Explorations by cave divers are revealing some of the characteristics of the flooded sections. Typically, these extend to depths on the order of tens of meters below base level. Much greater depths have been reached in other areas and much remains unknown concerning the extent of conduit development below local base levels. Evidence from diving exploration and from the vertical development of some dry caves shows that these depths can reach hundreds of meters. C onduit and P e rmeabil i ty Patterns The triple permeability model (or triple porosity model) contains three components: matrix permeability, fracture permeability, and conduit permeability Matrix permeability is the permeability of the bedrock itself-the interconnected pores, vugs, and 9ther void spaces on the scale of individual mineral grains Unconsolidated sand or gravel is an example of a medium with only matrix permeability. Fracture permeability is the result of mechanical rupturing of the rock, either joints, joint swarms, faults, or bedding plane partings. Brittle rocks are usually fractured In s ome rocks, such as fractured granites, fracture permeability is the only significant permeability Other rocks, such as massive sandstones, may contain both fracture and matrix permeability. Conduit permeability is provided by pipe-like openings created in such rocks as limestone, dolomite, and gypsum by the solvent action of circulating ground water. Although conduit permeability is usually confined to karstic rocks, it also occurs in some volcanic rock aquifers. There is a great diversity of karstic aquifers depending on the relative contributions of the three permeability types as illustrated schematically in Figure 2. Many of the karst aquifers it1 eastern United States have formed in Paleozoic limestones with a negligible matrix permeability and are dominated by conduit systems and by allogenic recharge from surface catchments. Fracture flow plays an important role in transmitting water from diffuse recharge on the land surface to the conduits and in transmitting water to wells drilled in these aquifers. Aquifers in dolomite tend to have more poorly developed conduit systems so that the ground water movement is dominated by fracture flow. Fractured dolomites tend to be more useful for water supplies because the water can be more readily accesse d by prop erl y located wells and because the supply is l ess threatened by surface contaminants derived from sinkholes and sinking streams. In contrast; young limestones such as those making up the Floridan aquifer are highly permeable so that much of the ground water is transported W.B. White & E.L White through the matrix. Concentrated flows produce large conduits within the permeable rock mass. Fractures are relatively less important. The Edwards Aquifer in Texas is an intermediate case involving all three types of permeability. Ground water velocity increases in a nonlinear fashion with the effective aperture of fractures and conduits, resulting in a concentration of flow along a few preferred pathways. Flow velocities in conduits are often sufficient to drive the system into a turbulent regime. The contrast in velocity between the least permeable and most permeable parts of the same aquifer is often six to ten orders of magnitude. It is a common fallacy to assume that if one scales over a sufficient volume of the aquifer, then the fractures and conduits will average out and the aquifer as a whole can again be characterized by a single hydraulic conductivity. This does not work. The in velocity and flow is too extreme. WORTHINGTON ( 1999) has calculated that more than 90% of the flow in a selection of karst aquifers is through what he calls the "channel" system The karstic characteristics of an aquifer can be evaluated in terms of the degree of development of the conduit system, the degree of coupling between the conduit permeability and the matrix and fracture permeabillty, and on the relative contribution of surface water The arrangements of the conduit system are reflected in resulting cave patterns. Some of the possibilities are sketched in Figure 3 in a manner similar to patterns proposed by PALMER (1991). The pattern in 3(A) shows a single, conduit cave with the stream from a surface catchment entering one end and the discharging through the other end The cave segment itself MOST PALEOZOIC KARST AQUIFERS Fracture Flow Surface Streams/ Conduit Flow FRACTURED FRACTURED FRACTURED GRANITES DOLOMITES SANDSTONES Matrix Flow GRAVEl. AQUIFERS Fig. 2. Contributions of the three components of the triple permeability model to various aquifers. Contributions des trois composantes du modele de La triple permeabilite pour differents aquifo res

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Conduit fragmentation, cave patterns and localization of karst ground water basins 13 Surface Water ..... '4t-------_...._ Ground Water D E \ I (/1 I I I ,f,fl": I I I I I if, I r 1 I \;""', .... / . ' If I F Allogenic Recharge Travel Time Fig. 3. Sequences along the continuum from a single conduit cave acting as an underground route for a surface stream to non-karstic fracture and porous media aquifers. Sequences le long d'une cavite quifonctionne comme voie souterraine d'un cours de surface vers des aquiforesfractures et poreux non karstiques. may either contain a free-surface stream or be located completely in the phreatic zone. There is little hydraulic coupling between the water stored in the surrounding bedrock and the surface water draining through the cave. The limit, as the length of the cave segment is made shorter and shorter, is the natural bridge. Many caves are found in many parts of the world that are essentially underground reaches of surface streams. The best known such cave in the Appalachians is the Sinks of Gandy (Fig. 4). Whether or not the water in such conduit segments should be considered ground water is a matter of semantics. The main catchment is a surface water basin with a well-defined divide. The pattern in 3(B) is that of a branchwork cave. There are multiple surface inputs both from sinking steams and from the drains of closed depressions. The underground pattern has many features in common with the headwaters regions of surface streams. The branchwork drains into a master trunk that ultimately leads to the spring. A cave fragment of the downstream trunk, of course, is not distinguishable from a trunk of type 3(A) except that its catchment is underground rather than on the surface. The branch work pattern is typical of many Appalachian ground water basins. What is usually observed are inlet caves at stream sinks or at sinkhole col lapses, outlet caves accessed through springs or paleosprings, and other bits of the collect
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14 SINKS OF GANDY CREEK JtANOOLPH COUNTY W.B. White & E.L. White Fig. 4. Map of the Sinks of Gandy, Randolph County, West Virginia. Topography from US Geological Survey Sinks of Gandy 7.5 minute Quadrangle Cave map from DAVIES (1958). A more detailed map appears in DASHER (2000). Carte de Sinks of Gandy, Randolph County, West Virginia. Topographie d'apres /'US Geological Survey Sinks of Gandy, rectangle de 7,5 minutes Carte de Ia grotte d'apres DAVIES ( 1958) Une carte plus detailtee a ete publiee par DASHER (2000) In the sequence of conduit permeabilities sketched in Figure 3, those on the left are dominated by surface water; those on the right by ground water. The fraction of allogenic recharge decreases from left to right. Travel times increase from left to right. The concept of a ground water basin is well defined for conduit systems of the left. Basin boundaries and indeed the very concept of a ground water basin becomes increasingly fuzzy and finally fades away completely from left to right. Parameters controlling the development of karst ground water basins There have been three broad approaches to the study of karst aquifers: (1) Calculations of the flow mechanisms in the conduits. (2) Geochemical/hydrodynamic modeling of the evolution offracture systems to maturely developed conduits. (3) Interpretation of cave patterns and drainage basin patterns based on the geologic setting in which the cave or basins are located. Calculations of type (1) have assumed various geologic frameworks but generally take the geologic framework as a given condition. Early speleogenetic research was largely intuitive and depended strongly on the geologic framework. As analysis of karst aquifers became more mathematically and geochemically sophisticated, the emphasis shifted to approaches (1) and (2). Recent work has been returning to the geologic framework. Our concern here is with the geologic boundary conditions that provide the limitations on how the ground water basins can develop. If we think-in a rather idealistic sense -of the process of conduit system development being guided by a

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Conduit fragmentation, cave patterns and localization of karst ground water basins 15 PERENNIAL SINI
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16 In the Appalachian Plateaus, the most important of-the focu sing agents is the precursor surface drainage. Base level streams determine the down-gradient end of the drainage sys tem. Preexisting tributary valleys on the clastic rocks overly ing the carbonate units determine the pattern of surface drain age. When these tributary streams downcut into the underly ing carbonate rocks, the gradient along the surface stream channel is sufficient to drive the development of a conduit system. The surface streams are eventually pirated under ground and become the master conduits for a ground water basin. Underground drainage in a very large number of the tributary valleys of the dissected Cumberland Plateau of Ten nessee and Alabama roughly parallel the surface drainage. The conduits are often offset from the valley thalweg and occur under the valley walls. The ground water basins with their allogenic surface catchments are well defined and are often almost coincident with the surface divides. An example is Sinking Cove located in the dissected southern margin of the Cumberland Plateau in Tennessee (Fig. 6). Ancestral Little Crow Creek drained from the clastic rocks of the Cumberland Plateau to the ancestral Tennessee River. The river breached the sandstone caprock along a northeast southwest trending anticline to form the Sequatchie Valley and rapidly downcut through the underlying carbonate rocks. Crow' Creek and its tributary Little Crow Creek cut head ward to the northwest gradually exposing carbonate rock along the tributary valley. Disruption of the surface drainage by underground piracies eventually produced large closed depressions along the valley floor known sequentially as Cave Cove, Farmers Cove and Wolf Cove and a 2 km-long dry valley at the bottom known as Sinking Cove. The surface Table I Factors serving to focus the development of conduit systems. Facteurs qui controlent La concentration dans le developpement des systemes de conduits. Precursor drainage Structural factors Large scale structures Small scale structures Fracture frequency Fracture homogeneity Stratigraphic factors Overall thickness of carbonate rocks above and below base level Hydrologic barriers Stratigraphic homogeneity W.B. White & E.L White stream from the Cumberland Plateau first sinks in the floor of Cave Cove, follows underground routes through Farmers Cove and Wolf Cove to appear at a spring at Sinking Cove Cave. The floor of Sinking Cove is supported by the 5 -7 m thick Hartselle Sandstone. The sandstone is breached and the drainage goes underground again to finally reappear at the head of the Little Crow Creek Valley. The master conduit' system has been fragmented but almost the entire conduit is accessible through Cave Cove Cave, Farmers Cove Cave and Sinking Cove Cave. In this example, the ground water basin is in close alignment with the surface water basin and the entire pattern of the conduit system, except for the deflecting influence of the Hartselle Sandstone, was dictated by the precursor surface drainage. Large scale structural features such as folds and faults have a major controlling influence on both surface and ground water basins. This is most evident in the Valley and Ridge and Great Valley Provinces of the Folded Appalachians. Here major northeast-southwest trending folds bring up Ordovician and Cambrian carbonate rocks along anticlinal valleys. Faulting is common and is mostly parallel to the regional northeast southwest structural trend. Here structural components completely dominate the development of ground water basins. The carbonate rocks are mixed sequences of limestones and dolomites. Because the carbonate rocks are in the lower part of the stratigraphic sequence, they tend to be exposed in the valley floors of breached anticlines. Allogenic recharge is collected from small basins on the synclinal ridges composed mainly of clastic rocks. The surface streams draining these catchments sink at the contact with the carbonate rocks. The underground drainage, however, tends to be parallel to the strike so the flow paths make a right angle turn and discharge at springs located where secondary valleys have cut across the regional structure. The surface catchments are defined by precursor drainage but the underground component is controlled largely by structure. Caves in steeply dipping rocks tend to extend primarily along strike as documented in central Pennsylvania by DEIKE (1969) and in many other examples in Virginia, West Virginia, and east Tennessee. Maze caves can form where dips are low on the crests of anticlines (WHITE, 1960; PALMER, 1975). Caves as conduit fragments are particularly helpful in identifying dominant structural controls on ground water flow systems. Small structures are mainly fractures: joints, joint swarms, and bedding plane partings. The important parameters are the density of fracturing, the initial apertures of the fractures, and the homogeneity of fracture apertures. The importance of frac ture density was recognized by FoRD & EwERS (1978) and used as the basis for their "four states" hypothesis for cave development. The higher the fracture density, the more read ily the ground water flow can follow paths dictated by hy draulic gradients alone and thus reflect the overlying surface water basin. Because flow through fractures increases with the cube of the fracture aperture, the heterogeneity of the frac ture sets is very important. Master fractures dominate the flow

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':;onduit fragmentation, cave patterns and localiwtion of karst ground water basins z Q 1-w .J w DISTANCE (km) 6 SINKING COVE MUD CREEK 17 E 400-z 0 w .J w PLATEAU SAND ----MOUNTAIN 500 ----l SEQUATCHIE I VALLEY E -I -a:: z I w 0 WOLF COVE I > 1-a: w I w > z w w w SINKING 0 a:: I w 300 ....J _J uw en COVE i= u en w w ww u I w _,a:: z z t-U ::J I z 1-J a:: w See detail above :J u I 1-200 10 25 30 35 Fig. 6. Longitudinal profile of Sinking Cove, southern Tennessee. The upper figure gives the detailed profile along the valley thalweg constructed from US Geological Survey 7.5 minute topographic quadrangle maps The maps used are given in the insert The lower figure shows a larger scale profile across the Cumberland Plateau. Proji//ongitudinal du Sinking Cove Tennessee du Sud. En haut, profit detailte le long du thalweg d'apres Ia carte de /'US Geological Suney, rectangle de 7,5 minutes. En vignette, les cartes utilisees En bas, profit a une echelle plus generate le long du plateau de Cumberland.

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18 1000 0 1000 2000 ...... ........ : ... /\. ttl'-/f 0 -, ....__...... .... 6000 1000 fEET eLaa:= EE353::::EE3::i.i5 :::EE3=:=:EE3=:::i0::=::=::=::=:==;::::=::=:===il CONTOUR INTERVAL 40 FEET NATIONAL GEODETIC VERTICAL DATUM OF 1929 W.B. White & E.L White Fig. 7. The Swage Creek Basin, Pocahontas County,West Virginia. Base map from US Geologi c al Survey Hillsboro 7.5 minute quadrangle. Superimposed cave maps adapted from STORRICK ( 1992). Overholt Blowing Cave follows the surfa c e route of Dry Creek The Swage -Carpente rs Cave System is guided by N60E master fractures. Le Bassin du Swago Creek, en Pocahontas County, West Virginia. Carte de base d'apres l'US Geological Survey Hillsboro, rectangle d e 7,5 minutes Cartes des grottes superimposees, adaptees d'apres SroRRICK ( 1992) La grotte d'Overholt Blowing suitle trajet de suiface du ruisseau de Dry Creek. Le systeme de Swago-Carpent ers est contr/Jle par des fractures majeures orientees N60E.

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Conduit fragmentation, cave patterns and localization of karst ground water basins 19 system The eventual development of a conduit system will trend along the path provided by the widest fractures even if such pathway is not along the maximum hydraulic gradient. Tension fractures parallel to anticlines may assist in control ling the strike-oriented drainage in folded rocks. Stress re lease fractures young geological features with wide apertures and so aie important in guiding conduit systems along tributary valley walls rather than down the thalweg as is observed in many Appalachian basins (SAsowsKY & WHITE, 1994). If fracture apertures are strongly heterogeneous, the large aperture master fractures can completely dominate the pattern of the conduit system. The ability of master fractures to override the inherited sur face drainage can be seen in the Swage-Carpenters Cave System in the Swago Creek Basin, Pocahontas County, West Virginia (Fig. 7). There are two active drainage lines in this valley each fed by surface catchments on overlying clastic rocks. Multiple small surface streams sink into the nearly flat-lying Mississippian Greenbrier Limestone. The Dry Creek sub-basin is underdrained by Overholt Blowing Cave which is parallel to the surface channel although offset from it under the valley wall. The Swage-Carpenters Cave System is one of the tributaries of the second sub-basin, with a more complicated drainage that ultimately discharges in Cave Creek Spring. The Swage-Carpenters System is developed along a N60E master fracture set which is oblique to the surface drainage. The master fracture has allowed drainage to be diverted from the Dry Creek sub-basin to the Cave Creek sub-basin. Lineaments are lines of structural weakness on a scale somewhat larger than that of master fractures. Lineaments often cross-cut local structures. The best West Virginia example of the influence of lineaments on drainage basin development is the Simmons-Mingo Cave System in Randolph County. The cave is developed along a major lineament and diverts dramage beneath a major topographic divide along a path oblique to the surface drainage lines (MEDVILLE, 1977). The presence of a lineament is apparently responsible for the exceptional depth development in Fern Cave, Alabama (WILSON, 1977) and for other cavern development is the southern Cumberland Plateau. Stratigraphic factors that guide the evolution of karst ground water include the overall thickness of carbonate rocks, interbedded shales, sandstones and other rocks that can act as hydrologic barriers, and the homogeneity of the carbonate rock units. Thickness of carbonate rocks is a self-evident factor, long recognized. Conduit drainage systems require a certain volume of rock in which to develop. The great karst regions of the world such as the Adriatic karst and the south China karst are devel-:_ oped on thousands of meters of carbonate rock. fluvial drainage systems have been lost long ago to predominantly karstic drainage systems. In moderate relief terrains such as the Appala chians, a few hundred meters of good limestone is sufficient for the development of large and complex karst ground water basins. Fifteen to 20 meters of Alderson Limestone in West Virginia allows the development of significant caves. The 6-7 meter thickness of the Van port Limestone in western Penn sylvania hosts large and complex maze caves such as Porters Cave, Brady's Bend Cave, and Harlensburg Cave (WHITE, 1976). An interesting question is whether there is a minimum thick ness for carbonate rock. It appears from observations on thin, but good quality limestones in western Pennsylvania that there is a minimum thickness and it is on the order of one to two meters. In the thin limestone units that occur in the Pennsyl vanian and Mississippian sequences of mainly clastic rocks, there are solutionally modified fractures, some of which would qualify as conduits in the sense that they exceed the 10 mm aperture required for the onset of karstic flow dynamics but they have not evolved into caves. There are, of course, other factors. Thin limestones sandwiched between impermeable shales may have no source of recharge. Hydraulic gradients are important and may be too low along the flat-lying thin limestone to initiate cave development. Hydrologic barriers are beds of shales, sandstones, and cherts that impede ground water flow. Such barriers are particularly important in the early stages of conduit development when the choice of flow path is very sensitive to the characteristics of the bedrock. (PALMER, 1991; SIEMERS & DREYBRODT, 1998). The role of hydrologic barriers has been examined in considerable detail by LoWE & GUNN (1997), LoWE (2000) & OsBORNE (1999) as part of the concept of "inception horizons". Thin layers of shale or shaly limestone can guide the initiation phase of cave development but these barriers are usually breached as the conduit enlarges. Thicker beds can function as hydrologic barriers guiding the overall development of the drainage basin. In the Mississippian Greenbrier Limestone of West Virginia are two such units: the Greenville Shale, 15-20 meters thick which separates the Alderson Limestone from the remainder of the carbonate units, and the Taggard Shale, a 7 m thick limey shale that occurs in about the middle of the carbonate section (Fig. 8A) (WHITE & WHITE, 1983). The Greenville Shale is sufficiently thick that the Alderson Limestone is hydrologically isolated from the other carbonates. Caves developed in the Alderson are not connected with caves in the remainder of the carbonate section. The Taggard some times limits vertical circulation in the limestones and some times is breached so that cave development crosses the Taggard. Underground crossings of the Taggard Shale occur mainly along major fractures. Passages take a canyon form in dicating that erosive underground streams may have been nec essary to cut through the shale. In the southern Appalachians, the Hartsellesandstone, a 5-7 meter-thick unit separates the Mississippian Monteagle and Bangor Limestones (Fig. 8B). Again, this unit serves to block vertical flow so that caves tend to develop either immediately above or immediately

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20 Ill 0: "' ... "' :1 ... '" '" ... MISSISSIPPIAN LIMESTONE LILlOALE SHALE (BASAL IAAUCH CHUNKI W.B. White & E.L White 300 ALDERSON LIMESTONE I I I \ GREENVILLE SHALE Thickness (m ) 250 200 150 100 50 0 A 'I I \1 \ \ ,. \ 1\\ ;.:.-:;: =. .., : -' ,, .' \ \' UNION LIMESTONE PICKAWA't LS. PATTON LS. :siNK S GROVE LS. LS. MONROE GREENBRIER POCOHANTAS COUNTY COUNTY COUNTY 7 5 80 40 3 0 8 LEGE!'IID EJ2 ........... ___________ Caprock Mtsstsstppllln "Bangor Ls. Hartselle F m. Ls. Lcll Riwr Ch11<1 St. Louis Ls. Warsaw Fm. Ft. Payne Fm. Fig. 8. Stratigraphic sections for (A) the Mississippian Greenbrier limestone of eastern West Virginia and (8) the Mississippian limestone sequence of the southern Cumberland Plateau showing the location of hydrologic barriers. Sections stratigraphiques par: (A) les calcaires du Mississippien de Greenbrier (est de La West Virginia) et (B) sequence des calcaires mississippiens du sud du Plateau de Cumberland avec La situation des barrieres hydrologiques. below the Hartselle Sandstone. Both Taggard shale and Hartselle sandstone act as inception horizons. In some cases caves are formed directly above these units because they perch the ground water flow. In other cases, the caves form directly below the shaley units which can also act as confin ing beds. Interbedded chert horizons can also interrupt ground water flow and can act as perching or confining horizons. Stratigraphic homogeneity is the variability in lithologic char acter along the stratigraphic sequence from one bed to an other. In a perfectly homogeneous carbonate sequence all beds would have the same chemical composition and all would consist of the same carbonate lithology. Such sequences are rare. Highly cavernous rock units often vary in lithologic char acter, e.g. micrites, sparites, oolitic limestones and others, without disrupting cave-forming processes. Alternating beds of pure limestone and shaley limestone or alternating beds of pure limestone and dolomite inhibit the cave-forming process : Ml;Jch depends on the scale of the interbedding. Alternating sequences of thin beds are most effective at inhibiting cave forming processes. Karstifiability "Karstifiability" is introduced as a term that describes the ease with which a particular rock unit yields to karst-forming proc esses. Karstifiability is related to the kinetics of carbonate rock dissolution but is more inclusive in that it also includes the paci fying effects of other components and the role of insoluble residues in blocking further dissolution of the primary bedrock. The main components of sedimentary rocks are sketched in Fig. 9. Within the Appalachians, the best developed conduit systems occur within the Mississippian Greenbrier, Bangor, Monteagle, and St Louis Limestones all of which are relatively pure limestones. Conduits do occur in the dolomites of the Valley are Ridge but are generally less well developed. Fracture aquifers are com mon in the dolomites. High concentrations of quartz sand do not seem to inhibit conduit development. The cavernous

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Conduit fragmentation, cave patterns and localization of karst ground water basins 21 Loyalhanna Limestone in western Pennsylvania contains about 50 percent quartz sand. In contrast. shaley limestones are cavernous. These rocks, in fact often act as aquicludes. Their presence disrupts the normal development of ground water basins. Although the role of lithology in determining the karstifiabil ity is well understood in qualitative terms, quantitative analy sis is much more difficult. A detailed comparison of cave volume with chemical, petrologic and mineralogic character istics of the carbonate rocks (RAUCH & WHITE, 1970) revealed subtle distinctions such as an inverse relationship between cave development and the aluminum content of the bedrock. A more important question is whether there is a threshold in the impurity content that would distinguish between karstifiable and non-karstifiable rock units. The existence of such a threshold would be important in assessing land use hazards in carbonate terrains As a proposal for quantitative assessment of karstifiability we can consider the bulk chemical composition of the rocks. The petrologic complexity of karstic rocks can be reduced to a set of chemical components [CaO], [MgO], [Si02], and [AlpJ. leaving aside the carbonate, [C02 ] component and also any other minor elements that may be present. The quantities in square brackets are in units of moles, derived from chemical analyses of the rock. These can be normalized as mole fractions The mole fraction of CaO, for example is defined as: ( ) [cao] N CaO = [CaO ]+ [MgO ]+ [SiO 2]+ [Al203] Lime-Cemented Dolomite Dolostone --z DOLOMITE CALCITE ,/ QUARTZ, Sandstone CLAY ',Shale und Siltstone Fig. 9 Composition tetrahedron for sedimentary rocks. Le tetraedre des composantes des roches sedimentaires. The mole fractions of MgO, A1p3 and Si02 are defined in the same manner as N(CaO). The sum of N(CaO) + N(MgO) can be used as a measure of total carbonate minerals. The dolomitic character of the rock can be represented by: N(dol) = (MgO] [cao ] + [MgO ] The composition of the rock can be represented as total carbon ates, clay minerals and free silica. Clay and related layer silicate minerals can be represented by kaolinite, Al4Sip10(0H)" Be cause AI and Si occur in a 1 : 1 ratio in kaolinite (or in a 1:2 ratio as the oxides, A1p3 and Si02), we can deduct the silica needed to produce clay minerals and then use the remaining silica as a plotting variable. The three plotting variables, which must be re-normalized to 100 percent, are {N(CaO) + N(MgO)} representing carbonates, { N(A1p3)} representing total clay minerals, and { N(Si02 ) -2N(Alp3)} representing free silica (quartz grains, silicified fossil fragments, or chert). These quantities can be used to plot the chemical composi tions of the rock on a triangular diagram in a way that relates composition to mineralogy. Attempts to use published rock analyses to map karstifiability are suggestive but inconclusive (Fig. 10) Three relatively pure limestones, the Pennsylvanian Vanport of western Pennsyl vania, the Mississippian Monteagle of central Tennessee, and the Ordovician Stones River of eastern West Virginia are all highly cavernous. The Devonian Tonoloway of Pennsylva nia and West Virginia is marginally cavernous The Missis sippian Warsaw of Tennessee is a shaley limestone that usually acts as an aquiclude. The problem is that published analyses are often from samples of unknown stratigraphic positions within a given formation. Further, most published analyses are for samples taken from rock quarries and thus represent the better quality limestone Analyses on impure limestones with limited cave development are sparse. Although carbon ate formations with limited cave development are known in the Appalachians, there are, at present, insufficient data on their chemical compositions to actually contour karstifiability on a diagram such as Figure I 0. Conclusions Conduit systems provide high efficiency pathways for the movement of ground water through carbonate aquifers. Because conduits act as drains of low hydt:aulic resistance, ground water flow becomes localized in ground water basins with well-defined drainage divides. Although entire conduit systems are rarely accessible to human inspection, many conduits can be reconstructed from survey and mapping of existing caves within the drainage basin. Factors that deter mine the pattern of the conduit system and the localization of

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22 [CaO] + (MgO] Stones River Monteagle Tonoloway the associated ground water basin are the hydraulic gradient, geologic factors that provide focus for the basin, and the karstifiability of the carbonate bedrock. Caves provide useful fragments of the conduit system. Inspec tion of cave patterns provides a useful assessment of the geo logic panimeters that have guided the development of the ground water basin. In particular, the competition between superimposed drainage and local hydraulic gradients and structural controls is often well displayed in the cave systems. References DASHER, G. R. (2000) The caves of Central West Virginia. West Virginia Speleological Survey Bulletin, 14, 296 p. DAVIES, W. E. (1958) Caverns of West Virginia., West Virginia Geologic and Economic Survey, XIX, A, 330 p. DAVIES, W. E., & LEGRAND, H. E. (1972) Karst of the United States. Chap. 15. In Karst: Important Karst Regions of the Northern Hemisphere (HERAK, M., & STRINGI'IELD V. T., Eds.), Elsevier, Amsterdam, pp. 467-505. DAVIES, W. E., SIMPSON, J. s .. OHI.MACHER, G. C., KIRK, w. s .. & NEWTON E. G. (1984) Engineering Aspects of Karst. US Geological Sun1e)' National Atlas of the United States of America, one sheet. DEIKE, R. G. ( 1969) Relations of jointing to orientation of solution cavities in limestones of central Pennsylvania. Am. J. of Science, 267,pp. 1230-1248. W.B. White & E.L White Fig. I 0. Triangular plot of carbonate rock composition in terms of the three components that represent carbonates, clays, and silica. Compositions are calculated from published rock analyses. Pennsylvania data (Vanport and Loyalhanna Limestones) from O'NEILL (1964). West Virginia data (Stones River and Tonoloway Limestones) from McCuE et at. ( 1939). Tennessee data (Monteagle and Warsaw Formations) from MAHER (1985) . Diagramme triangulaire de La composition des roches carbonatees enfonction de trois composantes representant les carbonates, l'argile et La silice. Compositions calcutees a partir des analyses publiees. Pour La Pennsylvania (Calcaires de Vanport et de Loyalhanna) les donnees d'apres 0 'Nw.1. ( 1964). Les donnees de West Virginia (Calcaires de Stones River ei de Tonoloway) d'apres McCuE et al.( 1939). Les donnees du Tennessee (Formations de fl!onteagle et de Warsaw) d'apres HERSHEY & MAHER ( 1985). Acknowledgements The work described in this paper draws on many earlier investigations and the graduate students who conducted them. The support of the Environmental Resources Research Institute is acknowledged. DoMENICO, P. A., & ScHWARTZ, F. W. (1990) Physical and Chemical Hydrogeology. Second Edition, John Wiley, New York, 506 p. DREYBRODT, W. ( 1992) Dynamics of karstification: A model applied to hydraulic structure in karst terranes. Applied Hydrogeology, 3, pp. 20-32. DREYBRODT, W. (1996) Principles of early development of karst conduits under natural and man-made conditions revealed by mathematical analysis of numerical models. Water Resources Research, 32, pp. 2923-2935. EwERs,R. 0., & QUINLAN, J. F. (1981) Cavern porosity development in limestone: A low dip model from Mammoth Cave, Kentucky. Proc. o/the Eighth International Congress of Speleology, Bowling Green, KY, pp. 727-731. FETTER, C. W. (1994) Applied Hydrogeology. Third Edition, Macmillan, New York, 691 p.

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Conduit fragmentation, cave patterns and localiZDtion of karst ground water basins 23 FoRD, D. C., & Ewr:Rs, R. 0. (1978) The development of limestone cave in the dimensions of length and depth. Canadian J. of Earth Sciences, 15, pp. 1783-1798. F01m. D. C., & Wti.J.IAMS, P. W (1989) Karst geomorphology and hydrology. Unwin Hyman, London, 602 p. FIHZr., R. A., & CHERRY, J. A. ( 1979) Groundwater. Prentice-Hall, Englewood Cliffs, NJ, 604 p. GROVES, C. G., & HowARD, A. D. (1994) Early development of karst systems. I. Preferential flow path enlargement under laminar flow. Water Resources Research, 30, pp. 2837-2846. HERSHEY, R. E., & MAHER, S. W. (1985) Limestone and dolomite resources of Tennessee. Tennessee Division of Geology Bulletin 65, 252 p. HowAtm, A. D., & GRoVES, C. G. (1995) Early development of karst systems. 2. Turbulent flow. Water Resources Research, 31, pp. 19-26. KAUFMANN, G., & BRAUN, J. (1999) Karst aquifer evolution in fractured rocks. Water Resources Research, 35, pp. 3223-3228. KAUfMANN, G., & BRAUN, J. (2000) Karst aquifer evolution in fractured porous rocks. Water Resources Research, 36, pp. 1381-1391. KuMCHOUK, A. B., FoRD, D. C PALMER, A. N., & DREYBRODT, W Eds. (2
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Abstract Theoretical and Karstology, 13-14 (2000-20<)1), pp. 25-32 U-Th TIMS chronology of two stalagmites from V11 Cave (Bihor Mountains, Romania) Tudor a & Christiane Causse2 I Quaternaty Research Group, Dept. of Mineralogy, Babes-Bolyai University, Kogatniceanu I and "Emil Racovi" Institute ofSpeleology, Clinicilor 5, 3400 Cluj-Napoca, Romania. -LSCE-J...aboratoire des Sciences du Climat et de l'Environnement, I2, Av. de La Terrasse, 91198 Gif sur Yvette, France. Two stalagmites (S22, S 117) from VII Cave (Bihar Mountains, Romania) were dated by thermal ionisation mass-spectrometry (TIMS). The 40 subsamples dated had uranium contents between 0 229 and 0 676 ppm, a 234U/231U ... I and generally low detrital contamination. Ages obtained range between 138.3 1.6 ka and 5.6 0 1 ka and are distributed in six growth periods separated by hiatuses. Growth rates calculated show that calcite deposition was slow in both stalagmites for most of the depositional periods recorded during oxygen isotope (OJ) stage 5 ( 1.3-3 mmlka), with the exception of the OI substage 5e, when S 117 experienced fast growth (50 mmlka). After an interruption of 22 ka, calcite deposition in S22 resumed during 01 stage 3 (2.5 mmlka). The age of 23.4 0.12 ka recorded in S 117 confirms previous evidence for a short depositional period during 01 stage 2. Termination I was determined in Sl 17 at 16.08 ka. The last growth interval during 01 stage I is marked by a strong increase in growth rates of both stalagmites, determined by warming and by a significant increase in precipitation. The presented dataset frames the main climatic events that occurred in the last 140 ka and brings a precise chronology in this time span, in good agreement with previous studies from Europe and NW Romania. Key words: U-Th TIMS dating, stalagmites, growth rates, climate, Bihar Mountains, Romania Resume Chronologie U-Th TIMS de deux stalagmites de Ia Grotte V11 (Monts de Bihor Roumanie) Deux slalagmites ( S22, S 117) provenant de La Grotte V 11 (Monts de Bihor, Roumanie) ont ete datees par spectrometrie de masse il ionisation thermique (TJMS). Les 40 echantillons dates ont eu des concentrations d'uranium comprises entre 0,229 et 0,676 ppm. un rapport m u;mu 1 s 1 et une faible contamination detritique. Les ages obtenus varient entre 138,3 1,6 ka et 5,6 0,1 ka et sont distribues e;r:tix intervalles de croissance, separes par plusieurs hiatus. Les taux de croissance calcutes montrent une precipitation lente dans les deux stalagmites durant le stade isotopique 5 ( 1,3-3 mm/ka), a l' exception du substade 5e, quand La slalagmite S/17 a marque une croissance rapide (50 mmlka). Dans le cas de La Stalagmite S22, ap_res une interruption de 22 ka, Ia precipitation de La calcite a ete reprise pendant le Stade isotopique 3 (2,5 mmlka). L'dgede 23,4 0,12 ka determine pour S 117 confirme les donnees obtenues pard' autres auteurs concernant l' existence d' une courte peri ode de depot au cours du stade isotopique 2. La terminaison 1 a ete datee dans La S117 a 16,08 ka. Le dernier intervalle de croissance enregistre couvre La plus grande partie du stade isotopique I; il se caracterise pour les deux stalagmites par une forte hausse des taux de croissance, due cll'eclzauffement general du climat et al'augmentation significative des precipitations atmospheriques. L'ensemble des donnees place les principaux evenements climatiques produits au cours des derniers 140 ka et offrent une chronologie precise de cet in tervalle de temps, en accord avec les etudes anterieures portant sur /'Europe et le Nord-Ouest de La Roumanie Mots-ctes: datation.r U-Th par TJMS, stalagmites, taux de croissance, climat, Monts de Bihor, Roumanie corresponding aulhur E-nwil address: ludort@bioge.ubbcluj.ro ID 2001, Edilura Acudemiei Romllne. All righls reserved.

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26 Introduction Calcium carbonate deposits from caves, such as stalagmites or flowstones, can provide information on the nature of the past environments. Changes of climatic conditions were proven to influence speleothem deposition (HENDY & WILsoN, 1968; ScHWARCZ, 1986; AYLIFF.E etal., 1998). Speleothem calcium carbonate is suitable for U-Th dating, thus making speleothems good repositories of palaeoenvironmental infor mation. U-Th dating of carbonates, such as coral or speleo them, by thermal ionisation mass-spectrometry (TIMS) pro vides an enhanced precision of results in terms of radiometric ages as well as sample stratigraphy (EDWARDs et al., 1986; LI et al., 1989; CHENG et al 2000). Dating of speleothem by TIMS proves a good absolute timescale and gives valuable information when correlated with other proxies such as B 180 and B 13C records (DORALE et al., 1998; FRUMKIN et al., 1999; McDERMOTI et al 1999; DESMARCHELIER et al., 2000). In Romania, U-Th ages obtained on speleothem, as well as B IKQ and B 13C analyses and correlations with other palaeo climatic proxies have been reported by LAuRmEN & ONAC (1995 ; 1999), 0NAC & LAURITZEN (1996), CONSTANTIN & LAURITZEN (1999), 0NAC et al. (1999), 0NAC (2000). Site description Vll Cave (The Cave from Varaoaia Glade) was discovered in 1990 in the southeastern part of Vadioaia Glade (Bihar Mountains) (Fig. 1), at an elevation of 1254 m. It is situated in an area with alpine climate, with a mean tempera ture of 4 C, precipitation reaching 1400 rrun/year and an average of 6 months snow. V11 Cave is carved in Anisian carbonate rocks: black limestones (Guttenitein facies) and grey dolostones. It has 1166 m of passages, and a maximum BULGARIA Fig. I Map of Romania with location of the V 11 Cave (black square) Localisation de Ia GrotteVII sur Ia carte de Ia Roumanie (rectangle nair) T. & C. Causse depth of 67 m (-37m; +30m) (Fig. 2a). It is a dendritic maze developed on four main karstification levels (DAMM, 1993). Two stalagmites (S22, S 117) were collected from a passage, 200m away from the cave entrance and s9me 60 m below the surface. The passage has no noticeable airflow and the humidity is close to 100 % 0 +3om Vll Cave (Pestera din Poiana Varasoaia) Survey: P. Damm, 1. Kiss, C. Pop, M. Botez, Sz. Szucs, Z. Kiss, H. Corbeanu, R. Pop, M. Hudrea (1990-1991). b --Fig. 2. a: Map-and cross section of V 11 Cave with location of stalagmites S22 and S 117; b : Cross section of passage with sampling point of S22. a a: Planet profit de Ia Grotte VII indiquant Ia localisation des stalagmites S22 et SI17; b: Coupe transversale de Ia galerie avec le point d'ei:hantillonnage de S22.

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U-Th T/MS chronology of two stalagmites from VJJ Cave Sample morphology S22 (Fig. 3a) is a 34 em-tall stalagmite formed on a limestone block fallen from the ceiling of the cave passage. The sample consists of low-Mg calcite and shows numerous growth levels, with colour variations from white to yellow -light brown (richer in organic substance). Calcite crystals are large pris matic, continuous from one growth level to another and ori ented oblique to the outer surface. On the first 8 em from the base one can observe an altemance of thin transparent and opaque levels, which ends with a well-marked hiatus. Growth seems continuous on the following 26 em to the top. In the interval 10.5 to 5.8 em from the top, there is an opaque level made up by calcite microcrystals with high porosity. S117 (Fig 3b) has a total length of 48 em (measured along the growth axes), and formed on the floor of the same pas sage, some 5 m away from S22. Its composition is similar to the sample previously described, but S117 has a more com plicated stratigraphy due to its repeated movement with respect to the feeding point. This displacement was probably produced by sliding over the clayey substratum. On the basis of macroscopic observations, we divided the sample in 4 zones: I. 0-9 em: from the base to a fracture line covered by sub sequent deposition (growth axes Al0-A8); thin growth levels, dark brown calcite with a slight porosity. II. 9-29.5 em (A7-A5). Light brown to white compact cal c ite; at 25 em there is a small hiatus, marked by a thin film of clay. This sequence ended when the stalagmite broke (not shown in Fig. 3b) III. 29.6-36.4 em (A4-A2); deposition resumed and new growth layers covered the fracture separating zones I and II. Yellowish white, transparent, non-porous calcite, al ternating with porous growth layers. At the base there appear two hiatuses, separating a thin growth layer. IV. 3 2 .5-48 em (A 1 ) The stalagmite slipped once more over the substratum and the younger growth layers partly cov ered zone III. Fig. 3 (a) Cross-sections through stalagmites S22 (scale bar= 2 em) and (b) S 117 (scale bar= I em) showing the positions and the ages of the dated S 117 : I -IV: growth zones; AI-AIO: g rowth axes The upper part of zone II of S 117 is not shown in the p i c ture Sectio n s l o ngitudinales d e s stalagmit e s S22 (a) ( eche ll e = 2 em) e l 5117 (b) (echelle = ]em) indiquant les positions et les ages des suus-echantillons dates. Sf 17: 1-/V: zones de croissance; Al-A/0: axes de croissance. La partie superieure de la zone 11 de Sf 17 n 'esc pas comprise dans la figure 27

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28 T. Tlimaj & C. Causse Chemical procedure fractions were dried, re-dissolved in 1M HN03 and then loaded in a graphite sandwich on single outgassed Re filaments. We selected for TIMS dating 40 subsamples (23 from S22 and 17 from S 117 ), 3 to 4 mm thick and weighing 1-2 grams. Chemical separations generally followed the procedure pre sented by TuRNEY et al. (2001). Subsamp1es were cut out of stratigraphically distinct layers using a steel dental disk. All visible impurities were mechanically removed. Further, subsample surfaces were cleaned in alternating acetone/dis tilled water ultrasonic baths, and then dissolved in HNOJ. Organics were destroyed using hydrogen peroxide, then a 229'fh-mu_2.16U spike (233UP36U -0.98) was added. ThiU ra tio in the spike was calibrated with respect to the HU-1 stan dard uraninite, considered in secular equilibrium (LuDWIG et al. 1992). U and Th were precipitated by Fe(OH) 3 at pH 7 .0, purified by anion exchange in 7M HN03 and then extracted with 8M HCl and Hp respectively. Radionuclide purified 234Uf-3sU, nsuf..36U, 233Uf236U, 229Thf-30"fh and 229Thf232Th ra tios were measured in peak jumping, ion counting mode on a Finnigan-MAT262 solid source mass spectrometer. The half lives used were from STEIGER et al. (1977) for 238U, respec tively 75.381 ka for 230Th and 244.600 ka for234U (LUDWIG et al., 1992). Results The uranium contents of the samples were between 0.229 and 0.676 ppm. As most subsamples showed a relatively high 2.10Th/232Th ratio, we did not apply corrections for detrital con taminations. Most subsamples dated have shown a 234U/ 238U actual s 1, characteristic for both speleothems. Such ratios Table I U-Th ages and isotope ratios obtained on the S22 stalagmite. Ages U-Th et rapports isotopiques obtenus pour La stalagmite S22. Sample d"'(cm) U(ppm) 234UPJ&ua 234uJ!l&ui 23DTbJ!34U Age (ka BP) 22top 33.7 0.407.(X)2 0.993.021 0.992.018 0.050.001 27.5 5.570 0.118 22A 30.2 0.446.000 0.970.003 0.969.003 0.068.001 189 7.628 0.106 22B 29.4 0.417.000 0.981.003 0.980.002 0.069.001 505 7.810 0.039 22C 28.5 0.371.000 1.001.002 1.000.002 0.077.001 282 8.724 0.041 22D 23.0 0.450.000 0.927.003 0.925.002 0.082.001 851 9.349 0.056 22E 21.8 0.440.000 0.927.003 0.925.002 0.083.002 371 9.480 0.157 22F 20.8 0.411.001 0.929.005 0.927.004 0.089.001 283 10.118 0.111 22G 19.8 0.344.000 0.930.002 0.928.002 0.092.001 779 10.536 0.141 22H 18.9 0.403.000 0.921.002 0.918.002 0.091.001 775 10.339 O.o74 22I 15.9 0.493.000 0.921.003 0.918.002 0.096.001 193 10.983 0.044 22J 12.0 0.549.000 0.905.002 0.901.002 0.102.001 263 11.753 0.046 22K 10.0 0.520.001 0.919.003 0.916.002 0.110.001 137 12.747 0.035 22L 8.4 0.609.000 0.885.002 0.880.001 0.125.001 100 14.526 0.090 22M 8.0 0.363.000 0.933.002 0.924.002 0.347.003 355 46.555 +0.408;-0.405 22N 6.0 0.356.000 0.953.003 0.946.002 0.382.003 172 52.602 +0.476;-0.473 220 5.3 0.492.000 0.901.002 0.884.002 0.404.003 71 56.953 +0.495;-0.492 22P 4.8 0.5 39.000 0.903.002 0.886.002 0.415.003 140 59.058 +0.418;-0.416 22Rt 4.4 0.321.000 0.998.002 0.998.002 0.526.004 419 sf.312 +0.717;-0.711 22R 4.2 0.296.001 1.006.008 1.008.008 0.5 32.006 284 82.396 +1.119;-1.116 22Rb 3.9 0.276.000 1.030.002 1.037.002 0.528.004 2675 81.336 +0.839;-0.832 22S 3.5 0.229.000 1.022.002 1.030.002 0.599.005 56 98.890 +1.053;-1.042 22T 2.7 0274.000 0.983.002 0.976.003 0.653.008 28 115.675 +2.290;-2.237 --22U 1.8 0.296.000 0.976.002 0.966.003 0.678.007 119 124.220 +2.090;-2.047 *d=distance from base

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U-Th TIMS chronology of two stalagmites from VII Cave are quite unusual in speleothems, and when occuring they generally indicate a preferential leaching of 134U from the sample, thus resulting in calculating ages greater then the real ones. Our samples show a relative constancy of the uranium content and of the 234UP38U along the growth intervals, sustaining that after deposition the stalagmites acted as a closed system with respect to uranium isotopes The unusual134U/ recorded in the speleothems might have their origin in the host rock above the cave. The ages obtained generally show a progressive decrease from 124 2 ka to 5.6 0.1 ka (Table 1), and 138 1.6 ka to 6.1 0.04 ka, respectively (Table 2). One age (subsample 220) was not concordant with the rest of the values obtained due to analytical errors and was rejected. The evolution of S22 and S 117 stalagmites from V11 Cave is shown in Figure 4. Stalagmite S22 begins with two growth episodes of short duration, at 124.2 2.0 ka and 115.7 2.2 ka, on which the growth rates could not be determined be cause of the thinness of the deposits. The next growth epi sode, between 98.9 1.0 ka and 81.3 0.7 ka, has an average growth rate of 1 .3 rrun/ka. After an interruption of some 22 ka, four ages (59.1 0.4 ka-46.5 0.4 ka) indicate another growth period with an average rate of 2.5 mmlka. The next interruption was determined at about 32 ka, but its precise duration was probably shorter. The hiatus line marking the 29 interruption has an irregular shape and crosses over several growth layers, probably due to the setting of conditions unfavourable for calcite deposition in S22 when drip water alimentation resumed (corrosive water which removed part of the material previously deposited) (Fig. 3). The last depo sitional episode recorded took place between 14 5 0.09 ka and 5.6 0.1 lea, the average growth rate being 30.5 mmlka. (Fig. 4). Sl17 started growing 138.3 1.6 ka B.P 138.3 1.6 ka and 128.2 0.9 ka (zone 1), calcite deposition was slow (circa 2 mmlka), after which follows a period marked by fast growth (50 mm/ka) unti1123 0.7 ka. After an inter ruption of 26.5 ka (upper part of zone II), deposition resumes at around 96 ka B.P. (average growth rate 3 mm/ka), until 86.4 0 8 ka. The next hiatus recorded in S 117 is very long (86.4 0 .84 to 23.4 0 .12 ka B.P.), but its extension is not controlled by climate oscillations, but by local causes (the break and displacement of zone II of the stalagmite). This assumption is supported both by our other dates in V11 Cave and by studies on speleothems from other caves in the Apuseni Mountains (ONAC & LAURriZEN, 1996; ONAC, 2000) Zone III in S 117 starts with a short growth period (3 mm-thick), with an age of 23.4 0.12 ka, followed by another hiatus. Growth respmed at 16.0 0 .09 ka and continued without interruption unti16.1 0 .04 ka, at an average growth rate of 13.5 mm/ka. Table 2. U-Th ages and isotope ratios obtained on Sll7 stalagmite. Ages U-Th et rappons isotopiques obtenus pour Ia stalagmite S/17. Sample d(cm) U(ppm) 134(Jf38Ua 134(Jf38Ui ZfhP"T h Age (ka BP) 117A1-1 47.8 0283.000 0.953.003 0.952.002 0.055.001 86 6.141 0.038 117A1-3 47.1 0.447.001 0.923.008 0.922.006 0.068.001 311 7.699 O.o67 117A1 6 44.5 0.446.000 0.904.002 0.901.002 0.082.001 429 9 .268 O.o69 117A1 4 41.4 0 333.000 0.930.003 0.928.003 0 091.001 838 10.347 0.()70 117A2-1 40. 8 0 345 .000 0.881 002 0.877.002 0.095 001 490 10.909 0.048 117A2-2 39.3 0.378.000 0.870.002 0.866.002 0.098.001 943 11.223 0.059 117A2 -3 38.0 0.655.001 0.882.002 0 878.002 0.105.001 1376 12.092 OJ29 117A3-2 35.9 0519.001 0.863.003 0 858.002 0 114.001 874 13.198 OJ35 117A4-1 35.5 0.467.000 0 867 002 0.862.002 O f17 001 650 13.525 0.097 117A4-2 34.6 05 13.000 0.8 19.002 0 810.001 0.137.001 29 16.()4.5 0.089 117A4-3 34.3 0522.001 0.838.002 0 827.002 0.192.001 49 23.365 0.120 1171R 33.8 0.355.000 0.954.003 0.942.003 0545.004 458 86.447 117A6 1 30. 9 0.651.001 0.949.002 0.933.002 0571.004 171 92.961 117A6-2 32.8 0.400.001 0.910.003 0 882 004 0581.003 770 96.513 0.645 117A6 4 31.5 0.676.001 0 918.003 0.883.003 I 0.668.003 2515 123.0ZO 117A9-1 4.0 0286.000 0.968.002 0.954.003 0.689.003 366 128238 +0.900;-0.895 117A9 2 02 0.654.001 0.923.003 0.886.004 0.709.005 38 138.274 +1.609;-1.605 *d=distance from base

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30 T. & C. Causse 50 40 ? E 30 u -Q) (/) c:tl ..c E 0 v; 20 '5 10 \ '$ ---9-0 0 20 40 60 80 100 120 140 age (ka) Fig. 4 Graph of S22 (open circles) and SII7 (solid circles) stalagmite ages vs. distance from base Growth intervals are marked with continuous lines. Error bars shown are 2a counting errors of age determinations (most age error bars arc smaller than data symbols). Diagramme des ages de S22 (cercles vides) et Sl 17 (cercles pleins) par rapport ala distance vers La base Les barres d'erreur repr e sentent 2a des determinations des ages (La plupart sont plus petites que les symboles) Discussion and conclusions The 40 samples dated from stalagmites S22 and S 117 in V 11 Cave cover a time span of nearly 140 ka (marine 01 stages 5 to 1), and are distributed in six g.rowth periods (Fig. 5d) Cal culated growth rates show that calcite deposition was slow in both stalagmites during most of the 01 stage 5. The first two short growth intervals in S22 correspond to 01 substadial 5e a nd with peak 13 and an unmarked intermediary peak of the NW European speleothem record (BAKER et al., 1993 ). S 117 starts growing at the end of 01 stage 6 (slow growth), then follows a fast-growth period marking 01 substadial 5e after Termination II. Isotope substage 5d was colder/dryer and cal cite deposition stopped in both stalagmites. The next depositional interval of S22 covers part of Or subs tadial5c, all of 5b and part of Sa. The upper growth limit in S22 for this interval is 81.3 ka, confirming the increased severity of climate at the transition Sa-4 and during or stage 4. Deposition in S22 during 01 substadial 5b is sustained by the growth interval in S 117, whose upper limit is determined by the sliding of the stalagmite over the clayey substratum and not by climate control. The growth determined on S22 between 59 ka and 46 ka corresponds to an amelioration of climatic conditions dur ing isotope stage 3 (substadials 3.31 and 3.3, respectively the F2 and F1 peaks of the NW Europe speleothem record), docu mented in Romanian speleothems from Sclir:ioara Glacier

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U-Th TIMS chronology of two stalagmites from V11 Cave Cave and Humpleu Cave System, Bihor Mountains (0NAC & LAURITZEN, 1996) and certifies the presence of a wann/wet event, followed by a cool/dry one. Calcite deposition in Vl1 speleothems was not resumed during substadial3.13, marked 11 >-37 5 1 (.) <= a.> ::::> o-125 30 40 50 60 10 60 90 1110 110 120 130 140 lO J 2 b "@'15 {)@. lij!j! ... 1.0 --G 0 0 10 20 30 40 50 60 10 60 90 1110 110 120 130 140 .0.5 2L 5? r.o "0 a.> "' E 0 c: .0.5 age (ky} Fig. 5. Growth intervals of S22 and S 117 (gray squares, 5d) compared with the Romanian speleothem record {ONAC & LAURITZEN, 1996-Sa), NW Europe speleothem record (BAKER et ul., 1993 -5b) and oxygen isotope chronology (MARTINSON et al., 198-7, events from PrsrAs et al., 1984-5c). Intervalles de croissance de S22 et S1 17 (rectangles gris, 5d) compares avec les donnees obtenues sur les speleothemes de Roumanie (ONAC & LAURITZEN, 1996-5a), les donnees de BAKER et al. (1993) pour les speleothemes de l'Europe de NO (5b) et La chronologie des isotopes de l' oxyge'ne (MARTINSON et al., 1987, evenements de PIS/AS et al., 1984-5c). 31 by well-defined peaks on both NW Europe and Romanian speleothem record. The difference from the Romanian speleothem record may be linked to an effect. as the U-Th dates covering that period come from caves situated nearly 600 m lower than our study area (ONAC & LAURI1ZEN, 1996). The situation may be similar for the peak at 76 ka on the Romanian speleothem record. The growth level at 23.4 0.12 ka recorded in S 117 points to a short depositional period during 01 stage 2. This uncorrelates both with the oxygen isotope record of MARTINSON et al. (1987) and with the NW speleothem record, where it is somewhat close to through B; it correlates however with U-Th dates recorded on speleothems from Sdirioara Glacier Cave, Bihor Mountains (0NAC & LAURTIZEN, 1996; ONAC, 2000) and might indicate a short climate improvement (wetter conditions?) occuring in this particular area. This depositional interval is missing from S22, however there is morphological evidence for the removal of a part of the calcite deposited prior to wa ter alimentation. Termination I was determined in S 117 at 16.08 ka and in S22 at 14.5 ka. The disagreement of these two values is due to the setting of conditions unfavourable for calcite deposition in S22. The last growth interval, during 01 stage 1 is marked in both stalagmites by a strong increase in growth rates deter mined by warming and by a significant increase in precipita tion. Acknowledgements We thank Emil Silvestru and Antoniu Bodnariuc for help in collecting the samples and Linda Ayliffe for invaluable help in laboratory analyses. We extend special thanks to our refer ees, Dr. Derek Ford and Dr. Stein-Erik Lauritzen, and to the editorial staff of Theoretical and Applied Karstology who gave helpful comments on an earlier draft of this manuscript. UTh datings were done at the Laboratoire des Sciences du Climat et de l'Environnement (LSCE), Gif-surYvette, France. This work was supported by the Ministere Frantrais de !'Education Nationale, de la Recherche et de la Technologie "Reseau Formation Recherche Pays Europe Centrale et Orientale Reseau Franco Roumain" (Contract 4778836 A), Coordinator Dr. Ch. Causse, and partly by the IGCP-379 to Dr. Yuan Daoxian and by the ANSTI B37/2000 project of the Romanian Agency for Science and Technology to Tudor This is the 7th contribution to the SPEP III program in Romania. References AYLIFFE, L. I(, M'ARIANELLI, P ., MoRIARTY, K. C., WEI.Ls, R. T., McCuuocH, M. T., MoRTIMER, G. E., & HELLSTROM, J. C. ( 1995) 500 ka precipitation record from southeastern Australia: Evi dence for interglacial relative aridity. Geology, 26, 2, pp. 147-150. 0

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32 BAKER, A., SMART, P L., & FoRD, D. C. (1993) Northwest European paleoclimate as indicated by growth frequency variations of sec ondary calcite deposits. Palaeogeography, Palaeoclimatology, Palaeoecology, 100, pp. 291-301. BAKER, A., SMART, P L. & EDWARDS, R L. ( 1995) Paleoclimate im plications of mass spectrometric dating of a British flowstone. Geology, 23, 4, pp. 309-312. CHENG, H., ADKINS, J EDWARDS, R L., & BoYLE, E A. (2000) U-Th dating of deep-sea corals. Geochimica et Cosmochim ica Acta, 64 14,pp. 2401-2416 CoNSTANTIN, S., & LAURilZEN, S.-E. (1999) Speleothem datings in Romania, I : Evidence for a continuous speleothem growth in during Oxygen Isotope stages 5-3 and its paleoclimatic significance Theor Appl. Karstology, 11-12, pp. 35-46 DAMM, P (1993) asupra sistemului carstic Boga (Muntii Bihar) An. $t. al So ciet ilfii Ardelene de Speologie, pp. 30-49. DEsMARCHEI.IER, J. M., GoEDE, A., A YI.IHli, L. K McCuLLOCH, M. C., & MoRIARTY, K (2000) Stable isotope record and its palaeo environmental interpretation for a late Middle Pleistocene s peleothem from Victoria Fossil Cave Naracoorte, South Aus tralia. Quaternary Scien ce Re v iews 19, pp. 763-774. DoRAI.E, J. A., EDWARDS, R L., ITO, E & GoNzALEZ, L.A. (1998) Climate and Vegetation History of the Midcontinent from 7S to 25 ka: A Speleothem Record from Crevice Cave, Missouri, USA. Science 282, pp. 1871-1874 EDWARDS, R. L., CHEN, J. H & WASSERDURG, G. J. (1986) 2liiU-234U-2]('Th-232Th systematics and the precise measurement of time over the past 500,000 years Earth and Planetary Science Letters, 81, pp 175-192. FRUMKIN, A FoRD, D. c .. & s cHWARCZ, H. P (1999) Continental Oxygen Isotopic Record of the Last 170,000 Years in Jerusa-lem. Quat e rnary Research, 51, pp. 317-327 HENDY, C H., & WILSON, A. T (1968) Palaeoclimatic Data from Speleothems Nature 219, pp 48-51. LAURITI.EN, S. E (1995) High resolution p a la eotempe r a ture proxy record for the last interglaciar based on Norwegian speleothems. Quaternar y Research, 43, pp 133-146 LAURIT/.EN, S -E., & ONAC, B P. (19 9 5) Uranium series dating of some speleothems from Romania Theor. Appl. Karstology, 8, pp. 2536 LAururt.EN, S. E., & 0NAC, B P. (1999) Isotopic stratig raphy of a Last Interglacial stalagmite from north west ern Romania : cor relation with the deep-sea record. J of Cave and Karst Studies 61, I pp. 22-30. Lr, W -X., LuNDBERG, J., DICKIN, A. P FoRD, D. C ., ScHWARCZ, H. P., McNuTT, R & WILI.IAMS, D (1989) High -precis ion mass-T. & C. Causse spectrometric uranium-series dating of cave deposits and implica tions for palaeoclimate studies Nature, 339, pp. 534-536 LUDWIG, K. R., SIMMONS, K. R., SZABO, B. J., WINOGRAD, I. J., LANDWEHR, J. M., RIGGS, A. C., & HoFFMAN, R. J. (1992) Mass spectrometric 23D'fh-234U-238U dating of the Devils Hole calcite vein. Science, 258, pp. 284-287 MARTINSON, D. G., P1s1AS, N G HAYS, J.D. IMBRIE, J., MooRE, T C., & SHACKLETON, N.J. ( 1987) Age dating and the orbital theory of the ice age: Development of a high-resolution 0 to 300,000. years chronostratigraphy. Quaternary Research 27, pp. 1-29 McDERMOTT, F ., FRISIA, S., HUANG, Y ., LDNGINELLI, A., SPIRO, B HEATON, T H. E., HAWKESWORTH, C J., BoRSATO, A., KEPPENS, E FAIRCHILD, I. J., v. D BORG, K., VERHEYDEN, S., & SELMO, E ( 1999) Holocene climate variability in Europe: Evidence from dd 110, textural and extension-rate variations in three speleothems Quaternary Science Reviews 18, pp. 1021-1038 0NAC, B. P (2000) Mineralogical and Uranium Series Dating Stud ies in Glacier Ca ve (Bihar Mountains Rom a nia) Theor. Appl. Karstology 13, pp. 33-38 ONAC, B P & LAURITZEN, S -E. (1996) The Climate of the Last 150,000 Years Recorded in Speleothems: Preliminary Results from North-Western Romania Theor. Appl. Karstology, 9 pp. 9-21. 0NAC, B. P ., CoNSTANTIN, S & LAURITZEN, S. E ( 1999) The palaeoclimate recorded in a Late Glacial to Holocene stalagmite from Ursilor Cave (Romania) : preliminary results. Lucr Simp. "Realizliri perspective In studiul Cuaternarului din Romdnia"April, 2000, Cluj-Napoca, Romania pp. 13-16. PISIAS, N G MARTINSON, D G., MOORE, J. T C. SHACKI..CION, N J., PRELL, W HAYS, J & BoDEN, G (1984) High resolution strati graphic correlation of benthic oxygen isotopi c records spanning the last 300,000 years Marine Geology, 56, pp. 119-136. SCHWARCZ, H. P. (1986) Geochronology and Isotopic Geochemistry of Speleothems In: Handbo o k of Environmental Isotope Geochem i stry (FRm, P & FoNTEs, J-Ch ., Eds) 2B, pp. 271-303 SHACKLETON, N J., & OPDYKE, N D (1973) Oxy ge n isotope and palaeomagnetic stratigraphy of Equatorial Pacific Core V28238 : oxygen isotope temperature and ice volumes on a I 05 year and 106 year scale Quaternary Resea rch, 3, pp. 39-55. STEIGER, R H & J.i.GER, E (1977 ) Subcomission on Geochronol ogy : Convention on the use of the decay constants in geoand cosmochronolo g y Earth and Planetary Scien ce Letters, 36, pp 359-362 TURNEY, C S. M., BIRD, M. 1., FIRELD, L K., RoBERTs, R G., SMITH, M ., DoRTCH, C. E., GRON, R., LAwsoN E., AYLII'FE, L. K., MIU.ER, G H., DoRTCH, J ., & CRESSWELL, R. G. (200 I) Early Human Oc cupation at Devil's Lair, Southw estern Australia 50,000 Years Ago. Quaternary Research, 55, pp 3 -13.

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Theoretical and Applied Karstology, 13-14 (2000-2001), pp. 33-38 Mineralogical studies and Uranium-series dating of speleothems from Scarioara Glacier. Cave {Bihor Mountains, Romania) Bogdan P. Onac Quaternary Research Group, Dept. of Mineralogy, "Babei-Bolyai" University,Kogalniceanu 1, and "Emil Institute ofSpeleology, Cluj Department, Clinicilor 5, 3400 Cluj, Romania. Abstract Recent mineralogical investigations carried out in Scarisoara Glacier Cave pointed out the presence of speleothems made up of monohydrocalcite and hydromagnesite. Although both minerals were documented earlier from other Romanian caves this is for the first time when a speleothem is described as being entirely composed of monohydrocalcite. Crocoite, a rare mineral was also identified; however, this is not a real cave mineral being transported into the cave by the percolating waters. UTh dating of some speleothems from Scarisoara Glacier Cave enabled us to draw some considerations concerning the palaeoclimate changes and the age of the cave. Key words: speleothems, cave mineralogy, U-Th dating, Scarisoara Glacier Cave;Bihor Mountains, Romania. Etudes minera/ogiques et datations U-Th des spe/eothemes de Ia Grotte-G/aciere de (Monts du Bihor Roumanie) Resume Les recherches mineralogiques recentes effectuees dans La Glaciere de ont mis en evidence La presence des speleothemes composes de monohyqrocalcite et d'hydromagnesite. Bien que ces deux dernieres aient ete deja decrites aussi d'autres grottes, c 'est pour La premiere fois que la monohydrocalcite constitue ici des speleothemes bien dis tincts. La crocoi"te, un mineral rare, a ere egalement identifiee, mais sa presence est tres probablement due a un transport depuis la surface par l'eau de percolation.Les datations par la methode U-Th de certains speleothemes de la Glaciere de nous ont permis egalement defaire quelques considerations concernant les changements paleoclimatiques et l'age de la grotte. Mots-cles: speleothemes, mineralogie des grottes, datation par Ia serie d'Uranium, Grotte Glaciere de Sclirioara, Monts du Bihor, Roumanie. Introduction Sclirioara Glacier Cave is located on the left bank of the Garda Seadi Valley, 5 km upstream from its confluence with Ordancua V atley, within the Ocoale-Scllrioara karst depres-sion (Rusu etal., 1970). The cave develops on thick-layered limestones of the Upper Jurassic (B ucuR & ONAC, 2000). The deposit forms a monocline dipping about 20 towards SW. *corresponding author. Email: bonac@bioge.ubbcluj.ro 200 I, Editunt Academiei Romll.ne. All rights reserVed. Further informations concerning Sclirioara Glacier Cave can be found in RACOVITA & 0NAC (2000). Morphology and mineralogy of speleothems Scllrioara Glacier Cave, the carbonate minerals calcite, aragonite, monohydrocalcite, and hydromagnesite are depos ited as variot1s from dripping, seeping, and pool ing water. Calcite composes the majority of the speleothems. The other three carbonate minerals occurred only in one or a maximum of two types of speleothems. TAMAS (pers. comm.)

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34 also identified a few phosphates, which will be presented in a forthcoming note. SclUiOara Glacier Cave contaitls a variety of calcite speleo thems Many of these decorate the passages and chambers located within the warm meroclimate zone of the cave. These include calcite clusterites, cave pearls corraloids, rimstone dams (gours) draperies (with or without odontolithes), rafts, stalactites, stalagmites, columns, boxwork, and impressive flows tones Among these, cave pearls are the more outstanding, due to their unusual mechanism of formation (VIEHMANN, 1963; 1967) VIEHMANN postulated that freezing of percolating water has caused the separation of dissolved substances (cal cite) in a cryptocrystalline form (lublinite). As the process continues, these cryptocrystals develop into micropearls Aragon ite is the second most common carbonate cave min eral after calcite. However, in Sc!rioara Cave it is not well represented; it is only found in some stalactites, clusterites, and cave pearls (B.i.o.i.u, 1984; BoDOLEA, 1992). In all of these occurrences, aragonite was identified by thin section examination using a polarizing microscope. Aragonite and calcite coexist as alternating layers in most of the speleothems analyzed. All these samples exhibit pseudo morphism of calcite after aragonite (the initial internal struc ture was changed while the external form was preserved) 0 Patches of micron or millimeter-thick coatings, composed of white finely crystalline material, were found covering the walls in a few of the sectors within the Rezervafia Midi (=Little Reserve) (Fig 1). X-ray diffraction and thin section examination showed these crusts to be composed of monohydrocalcite Under a polarizing microscope, monohydrocalcite B.P. Onac exhibits second to third order interference colors and moderate birefringence. In additi.on, when the crusts were stained with alizarid red-S (FRIEDMAN, 1959), the dark red color (a darker shade than that obtained when staining calcite or ara gonite) confirmed the presence of monohydrocalcite. To our knowledge this is for the first time when monohydrocalcite is found to be the only mineral component of a speleothem in a Romanian cave. Crusts composed of monohydrocalcite can only be found in a particular area of the periglacial sector of the cave where the temperature ranges from 0.3 to 3C. In this area, monohydrocalcite occurs in a zone where small water droplets hit the ice stalagmite heads, ejecting onto the walls, forming a fme mist (aerosol) environment. Although no water chemis try data is available for this cave passage, the appearance of hydromagnesite and monohydrocalcite speleothems deposited in the same area indicates the likely presence of magne sium-rich solutions. Worldwide, monohydrocalcite has been documented in rela tively few caves (HILL & FoRTI, 1997). In Romania, it has been reported in only two caves (Humpleu and Lucia Midi), being identified in the composition of moonmilk ( 0 NAC & GHERGARI, 1993). The only explanation we have found for the presence of monohydrocalcite in SclUioara Cave is the one proposed by F!SCHBECK (1976)'and FISCHBECK & MOLLER (1971). They assumed the following conditions for precipitation of mono hydrocalcite: Mg/Ca ratio in solution higher then 1 solution temperature to be lower than 20 C, and the presence of aero sols All these conditions are met in Sc!rioara Cave. In "Palatul Stinzienelor' (upper part of the 'Little Reserve'), patches of white mats of an earthy pasty mass (moonmilk-F i g. I Lon g profile through Sdirioar a Glaci e r Cave with the location of anlysed samples. Profillongitudinal parmi Ia Grott eGla c ere de Sciirioara e t Ia localisation des ec hantillons analysees. Little Reserve \Shaft/ Great Hall ) I Palatul Sanzienelor 0 SOm G rea t Reserve "The Cathedral" L warm lperiglacial...ll ____ glaciai------'L-----periglacial ____ _..... ___ w.arm ____ ...J meroclimate

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Mineralogical studies and Uranium-series datings in Scifrisoara Cave 35 Pb Sample #1342 Si Cr Pb 0 5 keV 10 15 Fig. 2 Energy dispersive X-ray spectra of crocoite. Spectre energetique en RX de La crocoi'te. . Table I. X-ray data for crocoite. like speleothems) were collected from a side passage (Fig. 1). The average size of these patches is about 1.5 em. X-ray Donnees de {'analyse RX pour La crotoi'te. diffraction analysis of the samples revealed the presence of d(A) hydromagnesite. lntensit;r hid 5.38 6 101 Hydromagnesite is a common carbonate cave mineral, and 5.01 8 110 its presence is not a surprise. However, currently it is the only 4.89 18 011 magnesium carbonate mineral found in Scarioara. We be-4.32 30 111 Iieve that hydromagnesite was precipitated from magnesium-3.71 8 111 rich percolating solutions due to the degassing of carbon di-3.67 8 020 oxide in passages located above the periglacial meroclimate zone. 3.44 48 200 3.24 100 120 Scattered within the same area where monohydrocalcite 3.20 8 021 speleothems were identified, bright yellow-greenish miner-3.11 8 210 als occurred as scaly crusts (see Fig. 1). Under binocular the 3.00 48 012 crystals were translucent and showed adamantine luster. 2.97 18 112 Chemical analysis of the mineral by energy dispersive sec-2.68 10 202 ondary X-ray (EDX) shows its composition to be dominated 257 10 112 by the elements Pb and Cr, and the remaining being a mix-2.52 10 212 ture of Ca, Si and AI (Fig. 2). 2.23 24 103 The powder diffraction data were collected using a Scintag 2.22 10 111 Pad V diffractometer operated at 45 kV and 40 rnA. The 2.13 2 131 instrument employs Cu-Ka radiation. The X-ray diffraction 2.07 16 212 (XRD) pattern is sharp and well resolved, indicating a well-1.98 8 231 crystallized material. The peak search revealed a good match 1.95 16 132 for most of 2-theta values for the crocoite (PbCr04 ) pattern, 1.94 10 320 whereas some of the peaks were assigned to calcite Table 1 displays the results. These values are almost identical to those 1.82 18 322 reported in the JCDD file of crocoite (08-209). Small sys-1.79 4 232 tematic shifts in the pattern may reflect either a slightly dif-1.77 6 140 ferent composition or an uncorrected calibration of the in-1.68 4 141 strument.

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36 Table 2. U-series dating results of speleothems from Sdirioara Cave. Resultats des datations des speleothemes de la Grotte de Sam.ple U(ppm) 23'Tbfllu 234U.P'U SC-1a 0.023 0.358.042 2.382.216 SC-1c 0.044 0.384.036 2.02.146 SC-3 (a) O.D35 0214.021 1.758.152 SC-3 (b) 0.029 0216.019 1.749.147 SC-4 base 0.039 0.129.015 2.404.13 SC-4 top 0.033 0.094.018 2.958.235 SC-5 base 0.102 0.612.007 0.976.002 SC-5 top 0.108 0.65.006 1.001.001 SC-6 base 0.133 0.617.007 0.917.002 SC-6 top 0.109 0.579.003 0.91.003 SC-7 0.055 1.164.079 1.78.095 SC-8 0.085 1.032.049 1299.072 SC-9 0.037 1.075.041 1.387.051 Refinement of the XRD data using POWDER 2.0 program produced the following monoclin unit-cell parameters: a = 7.02A ;h=7.32A ;c=6.71 A ,andp=l02.32A. Scanning electron microscope images of crocoite show slen der prismatic crystals. Crocoite is a rare mineral even for the surface environment. Its presence in Sclirioara Glacier Cave is enigmatic. In the natural environment, the mobile specie of chromium is the Cr1>+ ion. Under oxidizing conditions, Crl+ is the stable va lence state in equilibrium with the atmosphere, occurring ei ther as the HCr04 or CrO/" anion (DREYER, 1997). Because, within the cave environment, the pH is typically in the range of 7 to 8, and the redox potential in the range of +0.4 to 0.6 volts, the Cr3+ can not oxidizes to form CrM (chromate). The precipitation of crocoite in Scarioara Glacier Cave as a secondary mineral is hard to accept. Considering the remote location of the cave, and the fact that Pb and Cr ions are rare in the environment, a natural origin for this mineral is ex cluded. In addition, there are no ore deposits containing lead 1 The U-series alpha dating was done at the Departement of Geology, Bergen University, Norway. 2 TlMS dating was performed at the Geological Institute, University of Copenhagen, Denmark. B.P.'Onac Age (ka) Corrected age (ka) 18 46.01 (6.721-6.4) 43.00(7.11/-6.8) 12 50.41(6.06/-5 .79) 22 25.71(2.93/-2.81) 51 24.82(1.121-1.08) >1000 14.83(1.87/-1.85) >1000 10.69(2.17/-2.13) 215 126.3(0.89/-0.91) 850 1052(0.67/-0.63) 725 124.9(0.78/-0.781) 749 96.4(0.56/-0.055) 217 >350 >1000 >350 >1000 >350 and chromium within at least 250 km from Sclirioara. Hence, it cannot be considered a true cave mineral. The presence of crocoite raises the question of lead and chromium origin. The only explanation we can put forward is that the occurrence of crocoite in Sclirioara Glacier Cave has a human-induced origin. It is. known that various chromates are used for artificial dye preparation. Such dye could have been durp.ped in the close vicinity of the cave and then crocoite formed from its components was transported into the cave by the percolating waters. If so, crocoite would be the first mineral that can actually be considered a pollutant of the cave environment. Uranium-series dating of speleothems Speleothems provide a sensitive tool for studying past climatic changes. Their growth (deposition of calcite) coincides with relatively warm and humid episodes, while breaks in calcite deposition correspond to cool or dry phases. To study this process, eight speleothems (four stalagmites and four fragments offlowstone) were collected from 'The Cathedral', 'Great Reserve', and 'Little Reserve' in Scarioara Cave (Fig. 1 ). These samples were cut into thirteen sub-samples and dated by means of uranium-series dating (23Th/234U) using both alpha-particle' (0NAC & LAURITZEN, 1996) and thermal ionization mass-spectrometry (TIMS) techniques2

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Mineralogical studies and Uranium-series datings in SclJrisoara Cave The sample age can be determined by the activity ratio of !.14U to its decay product !30'fh, providing the speleothems contain no clay or other insoluble detritus. Clay and insoluble material are known to be carriers of detrital thorium. This ratio can be calculated using standard algorithms (IVANOVICH & HARMON, A sample (SC) was taken from a 15-cm thick layer of flow stone found under some breakdown blocks located at the edge o f the ice stalagmite field. Sample SC consists of yellowish brown,. porous, micro-crystalline calcite. Both sub-samples extracted off the speleothem (SC-la and SC-lc) gave dates of ca. 43 ka3 (top) and 50 ka (base) but with large standard errors (Table 2). Sample SC-3 is a 77 em-tall stalagmite, collected close to the entrance in the 'Galeria Coman'. The stalagmite consists of dense, medium to large crystalline, milky white, banded cal cite laminae. The sample was located on top of some collapse breakdown blocks and was actively growing at the time of sampling. For dating, two sub-samples were taken from its bottom. The resultant dates for both samples are reliable and reasonably precise at ca. 26 ka. Stalagmite SC-4 (25 em in height) was collected from ap proximately the same position and under the same settings as sample SC-3. The speleothem showed a pattern of thin gray opaque horizons separated by thick white opaque layers. Signs of corrosion (small pores) are evident in its central part. The base and top of the stalagmite gave reliable ages of -14.8 ka and -10.7 ka, respectively. Within the same area of 'The Cathedral' two other small sta lagmites (up to 15 em each) were sampled and analyzed by means of TIMS These two samples, SC-5 and SC-6, pro duced dates of high precision, showing that they grew en tirely during the oxygen isotope (01) stage 5 (Riss-Wtirm or Eemian interglacial) Growth of SC-5 commenced prior to 126.3 ka and halted after 105.2 ka. The age of the base of SC-6 was 124.9 ka, while the top of this stalagmite gave an age of 96.4 ka. Based on these ages the growth periods of the two speleothems can be p l aced within the sub-stages 5e and 5c, respectively Two fragments of flowstone (SC-7, 8) were detached from the upper part of the Little Reserve, and another (SC-9) from a small side passage within the Great Reserve. The ages of all three samples were beyond the limit of the alpha-particle counting method (350 ka). The results of the thirteen dates performed are shown in Table 2 Without exception all samples were low in uranium con tent, which was in part compensated for by using larger J I ka = 1000 years. 4 B" represents the ratio in the detritus. 37 samples and prolonged counting times (when using the al pha-spectrometry method). The levels of detrital !30'fh con tamination were acceptable, and only one date was corrected using B0= 1.5 in ScHWARCZ's (1980) equation With all these precautions, some of the dates still have large analytical er rors. The most prominent paleoclimatic results obtained when ana lyzing the collective properties of the dates are: an active speleothem growth period took place at sometime beyond 350 ka; there is an evidence for a gradual shift towards cooler or/and drier climate during sub-stages 5d and 5b when stalagmites SC-5 and SC-6 ceased their growth; the continuous growth of speleothems through the isotope stages 2 (Wtirm III or Late Weichselian) when the ice sheet was only 500 km away from Apuseni Mountains (LoWE & WALKER, 1997). This conimns that this area of the Bihor Mountains was neither covered by alpine glaciers nor experienced enough severe permafrost conditions to suppress wa ter percolation and hence speleothem growth. The two stalagmites found on top of the limestone break down and the flowstone fragments were dated to more than 350 ka. From these dates, we may estimate that Sclirioara Glacier Cave was formed during the Middle-or even Lower Pleistocene period. Acknowledgements I am deeply indebted to Joe Kearns for crocoite analysis Many thanks go to Dr. Lucretia Ghergari and Dr. William B. White for helpful comments on crocoite geochemistry. The field work for this study was fmancially supported through the CNCSIS grant No. 11/50 to Bogdan Onac. This is the 6th contribution to the SPEP III Program in Romania. References Bil.oil.u, A. (1984) Remarques sur Ia structure microscopique de certaines perles de caveme. Theor Appl. Karstology. 1, pp. 5157. BoooLEA, A. (1992) Mineralogia speleothemelorin pCteri din Muntii Bihar. Lucrare de licen, Facultatea de Biologie-Geologie, Universitatea Babes-Bolyai, 105 p BucuR, 1., & ONAC, B. P. (2000) New data concerning the age of Mesozoic limestone from (Bihar Mountains, Roma nia) Studia Univ. Babes-Bolyai, Geologia, XLV 2 pp. 13-20. DREVER, J. I. (1997) The geochemistry of natural waters. (3nl ed. ), Prentice Hall, New Jersey, 436 p.

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38 F ISCHllECK, R. ( 1976) Mineralogie und Geochimie Carbonatischer Ablagerungen in Europliischen Hohlen,ein Beitrag zur Bildung und Diagenese von Speleothemen. Neues Jahrbuch Miner. Abh., 126 : pp 269-291. FISCHllF.CK, R., & Mou.ER, G. (1976) Monohydrocalcite, hydro magnesite, nesquehonite, dolomite, aragonite and calcite in s peleothem s of the Frankische Schweiz, Western Germany Contr. Miner and Petrol. 33, pp 87-92. FRI E D M A N G. M ( 1959) Identification o f carbonate minerals by stain ing methods Jour Sed Petrology 29 I pp. 87-97. H11.1., C A & FoRTI, P Eds. (1997) Cave minerals of the world. 2d ed ., NSS, Huntsville Alabama, 464 p IVANOVICH, M & HARMON, R. S. (1992) Uranium-series disequilib rium. Applications to Earth, Marine, and Environmental Sci en c es ed Oxford University Press 910 p. LowE, J. i, & WALKE R M J. C ( 1997) Recons t ructing Quaternary Environments. 2 d ed., Longman, 466 p B.P. Onac ONAC, B P & GHERGARI, L ( 1993) Moonmilk mineralog y i n some Romanian and Norwegian caves. Cave Science 20, 3 pp. 107-111. ONAC, B. P., & LAURITZEN, S -E. (1996) The climate of the last 150,000 years recorded in speleothems: preliminary results from north-western Romania. Theor. Appl. Karstology 9, pp 9-21. RAcovrr.X., G & 0NAC, B P (2000) Scliriioara Glacier Ca ve. Mono graphic Study Carpatica, Cluj, 140 p. Rusu, T., RACOVITA, G., & COMAN, D (1970) Contributions a ) etude du complexe karstique de Scarisoara Ann Spe leol., 25 2, pp 383-408. ScHWARCZ, H. P. ( 1980) Absolute age determination of archaeological sites by uranium dating of travertines Archaeometry 22, I pp. 3-24. VIEHMANN, I (1963) Un nou proces de genez!i a perl elorde cavema. Lucr. Inst Speol. "E. Rac oviJa' ', I-ll, pp. 295-303 VtEHMANN, I. ( 1967) Noi contribut ii Ia geneza perlelo r de caverna din cu gheata Lucr Inst. Speol E Racovit a ", VI pp. 141-147.

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Theoretical and Applied Karstology, 13-14 (2000-2001), pp. 39-50 Karst evolution in the Danube Gorge from U-series dating of a cave-bear skull and calcite speleothems from Pe!}tera de Ia Gura Ponicovei (Romania) Silviu Constantin1* Stein-Erik Lauritzen2 Emanoil & Alexandru Petculescu1 I "Emil Racovifa" Institute of Speleology, str. Frumoasa 11, 78114 Bucureti, Romania 2Bergen University, Department of Geology, Allegaten 41, 5009 Bergen, Norway Abstract Two bone samples taken from a cave-bear skull discqvered in Pestera de Ia Gura Ponicovei (Danube Gorge, Romania) have been dated by U-series liquid-liquid extraction procedure. They allowed the determination of a minimum age of the cave as well as the minimum age of Danube's fourth terrace at c. 277 ka This age has been also used to ascertain the paleontologic determination of the bear species as Ursus deningeri v. Reichenau. Datings on speleothem calcite indicate that the minimum age of the active level of the cave is -30 ka and enabled rough estimations of the incision rate of the underground river and of the fluvial erosion rate of the Danube at 0.05 m/ka and 0.67 m/ka, respectively. Keywords: karst evolution, speleogenesis, paleogeography, cave bears, Ursus deningeri, Danube Gorge, Romania. Evolution du karst dans le Defile du Danube d'apres quelques datations par Ia serie de /'Uranium d'un crane d'ours de caverne et des quelques speleothemes de calcite de Ia Petera de Ia Gura Ponicovei (Roumanie) Resume Deux echantillons d'os pre/eves d'un crane d'ours de caverne decouvert dans Ia Petera de Ia Gura Ponicovei (Defile du Danube, Roumanie) ont ete dates par Ia methode de Ia serie del' Uranium, en appliquant Ia procedure d' extraction liquide-liquide. Les resultats ont permis de determiner l age minimum de Ia grotte ainsi que de Ia quatrieme terrasse du Danube, qui est d'environ 277 ka. Cet age a servia /'elimination des incertitudes de / analyse paleontologique classique, de meme que pour etablir qu'il s'agit d'un individu d'Ursus deningeri v. Reichenau. Les datations des quelques speteothemes de calcite ont indique que /'age minimum de Ia gaferie active de Ia grotte est d'environ 30 ka En outre, elles ont permis d etablir le taux d'approfondisse ment de Ia riviere souterraine a 0,05 mlka et celui d'erosion fluviale du Danube tout au plus a 0,67 mlka. Mots ctes: evolution du karst, speteogenese, paieogeographie, ours de cave me, Ursus deningeri, Defile du Danube, Roumanie. Introduction Cave deposits are well known as preserving important paleo climatic and paleogeographic information. Speleothems are now largely used for paleoclimatic reconstructions, mainly based on their isotopic record-which can be accurately dated by means of U-series methods (see, for example, FoRo, 1997 *corresponding author. E-mail address: Silviu.Constantin@geol.uib.no 200 I EdiiUf\1 Academiei Romllne All rights reserved. and references therein). Other cave deposits, such as the fossil remains of micromammals, may also bear important paleoclimatic significances (e.g. MEIN, 1976 or LowE & WALKER, 1997 and references), but they usually yield only a relative chronology being not suitable for absolute dating The use oflargp mammal fossils (such as cave-bear bones) for speleogenetic purposes is scarce. First, such remains cannot usually be associated with key-episodes within the lifespan of a cave; in general, their only significance is that they postdate the formation of the passage where found. Second, absolute

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40 dating "of such nemains is often impossible by means of the radiocarbon method (due to its low time-range) and it ha5 been problematic by the U-series method due to the high phos., phate content of the bones which impede both the extraction and the chemical separation of U and Th and usually cause low chemical yields. The new liquid-liquid separation method developed by LAURI1ZE N et al. (1997) at the U-series laboratory-Univer sity of Bergen allowed us to perform two successful dates of a cave bear skull from "Petera de la Gura Ponicovei" (Ro mania) Moreover since the recovered bone remains were not sufficient for a unique paleontological diagnosis, the ab solute dating has actually eliminated some alternatives and finally led to the species determination. The significance of the dating of the fossil remains, together with several con ventional alpha-spectrometric dates of speleothem calcite are further used to pinpoint some of the erosion phases of the evolution of the Danube Gorge during the Upper Quaternary. Mat e ria l an d me thods The Danube Gorge The "Danube Gorge" is Europe's longest defile stretching along some 135 km at the border between Romania and Yu go s l a via ( see F i g la). It includes four sectors of limestone gorges (SENCU, 1979) among which, the most spectacular and narrow i s the socalled 'Cazanele (=Giants' Pots) Duniirii', in Romanian and Djerdap (=rocky rims)-in Serbian. Within this sector the river flows between steep limestone cliffs for some 10 km; the gorge is interrupted for only 1 km (and only on the Romanian side) at Dubova where a small Miocene sedimentation basin may be found All along the gorge, the cross-profile of the riversides is asymmetrical: on the left (Romanian) side, the cliffs top at c. 320m asl., while on the right side they reach an average altitude of -700 m (Fig. 1) The g e n e sis o f the Danube Gorg e has made the subject of many theories since the beginning of the 20th Century. The principal hypotheses are those assuming either the a ntec e dence of the river that has cut the uplifting Carpathian r a nge, or the s tream piracy betwe e n tributaries of the Getic and Pannonian Basins, respectively. Regardless of any ge n etic theory, i t seem s quite clear that the genesis of the Danube Gorge e xtend s back in tim e until at least the Pliocene, since this is the age of the gravels covering the karst plateaus on the Romanian side (based on paleontological evidence, see V.A.LSAN, 1918 ). These karst plateaus se e m to correspond to the oldest terrace (the VIII-th) of the Danube(' der Pontischer Talhod e n of CvUJc 1908) with an absolute elevation of31 0-320 m. The re maining seven terraces o f the river are mostly pres e rved in the Romanian Plain (POSEA et al., 1969); within the Danube Gorge sector their distribution is limited to very s m all surfac e s and little i s known about the Quaternary his -S. Constantin et al. Fig. 1. Location of Ponicova Cave and the remnants of the VIIIth -+ terrace within the Cazane sector of the Danube Gorge a. General location of the Danube Gorge; b Cross-section through the gorge in the sector of Ponicova Cave showing the positions o f different surface and cave levels. Note the asymmetry of the Danube sides Vertical scale is 4x exaggerated Base map and profile after SENcu ( 1979) witlt modifications l. The limit of the Danube Valley at the end of the Pliocene; 2. Remnant surfaces of the VIIIth terrace; 3. Saddle ; 4. Elevation; 5. Limestone cliff; 6. Gorge; 7 Cave entrance; 8 D ir ec tion of the Ponicova Cave main passages ; 9. Ponicova Valley before the piracy Situation de la grotte de Ponicova et des surfaces de la terrasse dans le secteur de Cazane du Defi l e du Danube a Situation generate du Defile du Danube; b Coupe transversale du defile dans le secteur de la grotte, avec les positions des dijferents niveaux de surface et souterrains. A noter l'asymetrie des deux versants du Danube Carte de base et coupe d'apres Smcu (1979) modijiees 1. Limite de Ia vallee du Danube a Ia fin du Pliocene; 2 Surfaces de Ia V//l-eme terrasse du Danube; 3. Ensellement; 4. Cote; 5. Abrupt calcaire; 6. Gorge; 7 Entree de Ia grotte; 8 Direct ion des prin ci pales galeries de La grotte; 9 Dire c tion de la v allee d e Ponicova avant Ia capture souterraine tory of river's entrenchment. The most clearly recognizable terraces along the Danube Gorge are the terraces no. VII (250-300m), VI (170-200 m) and V (150-160 m); the later may be continuously followed downstream towards the Romanian Plain. Following the construction of the "Iron Gates" Dam, the last two terraces, with relative altitudes of 10-20 m (80-90 m asl.) and 6-8 m (-55 m asl.), respectively were totally inundated by the water within the entire Danube Gorge sec tor (POSEA eta[., 1976) Geological background The "Cazane" Gorge was formed at the northern end o f the karst plateau of Miroc, being mainly carved in massive reef limestones, Upper Jurassic to Lower Cretaceous in age. On the Romanian side these limestones hav e a spatial extension ofless then one kilometer and are overlied westwards by C r e taceous flysch sediments The gorge is divided into two sec tors by a small basin filled by Mioce ne sediments at Dubova. Detailed accounts of the geological structure of the Cazane' and Gorge region, may be. found, e.g. in MUTIHAC (1990), GRUBIC (1994), GRUBIC & B ERZA (1997). The karst plateau of Ciucarul Mare displays a large number of sink holes, accounting for almos t 39% of it s total surface (SENCU 1979). 1 Following the construction of the Iron Gates" Dam, in the late '60s the Danube's leve l rose w ith -3040 m within the Cazane sector. Since this paper is concerned with Danube's Quaternary evo lution, all relative altitudes are quoted with respec t t o the former Danube l evel. All absolute ( as !.) elev ations are quoted with respect to the Black Sea level.

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Karst evolution in the Danube Gorge I I -......... --r -I I I I 514 I I I; 1 I I I 1 I I I '\ I I I I I \ \ I : I 46() \ ..... -' ... , , , ; , 41 1.1_./1 3 .DIJ 4.EJ 6.b?:l 7.ITJ --,;;400C::==8\)0 m Stitbilfu/ Ma r e IOOL o 400m b.

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Bear skull-PGP1 ( 143 m a.s.l.) lower Pestera de Ia Gura Ponicovei !> (Danube Gorge, Almaj Mts Romania) PGP3 N s 25 a so m Fig. 2. Plan of Ponicova Cave with the location of the analyzed samples Base map after N EGREA & N EGREA (1979), simplified. Plan de La grotte de Ponicov a avec La localisation des echantillons anal yses. Releve de base d 'ap res NEGREA & NeoREA ( 1979 ) simplijie .l>o N s i! s 1:> ,.....

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Karst t:l'olution in the Danube Gorge de la Gura Ponicovei de la Gura Ponicovei (hereafter named Ponicova Cave for simplicity) is the most important cave in the Cazane Gorge. It is a tiered, through-cave, centered along the small Ponicova Brook. This river collects its waters from the crystalline schists of the basement and the impervious flysch deposits then, shortly after reaching the Jurassic limestones enters into the cave through a majestic porch, over 25m-high (98 m asl.). In the underground, the stream flows through a 400 m-long passage with heights of more than 25 m and a canyon-shape; eventually it reaches the "Iron-Gates" dam lake through an other, smaller, porch (Fig. 2). Two other systems of passages are worth-noticing: on the southern side of the Stream way Passage, at a height of 15-20 m, the Bats Passage has hs distinct entrance suspended above the main one (altitude: 116m). This is an inactive pas sage that includes a large collapse chamber (The Big Chamber) and a secondary system of narrow, muddy, ascending passages on its eastern end. Bats Passage communicates with the Streamway Passage through a descending gallery (lAd ders' Passage) which ends with a 20m drop abo':'e the un derground river. From this intersection, a third large, ascending, passage may be followed towards the NW. This is known as Speleothems Passage, although only the most massive speleothems are still preserved, such as large stalagmites and pillars, a thick flow stone pavement and large-size anemolites. This sector includes several small side passages and finally comes to a dead-end at an altitude of 143 m (81 m above the lowest entrance). Gravel elements of metamorphic rocks may be noticed on the floor and, in some sectors, also on the ceiling of this passage; together with the presence of the anemolites, they indicate that this passage has acted as a former paleo-Ponicova subterranean drain (NEGREA & NEGREA, 1979). Ponicova Cave has been studied by many researchers, includ ing JEANNEL & RACOVITA. (1929), ScHMIDT et al. (1968), BOTOSENEANU et al. (1967), SENCU (1979), etc. The last author has analyzed the genesis of the cave establishing four genetic stages (see Fig. 5). During the frrst stage Ponicova was flowing directly into the Danube along the sou!1westem margin of the limestone area In stage two, the river has been captured somewhere at the level of the Speleothems Passage. A relict saddle ("Poiana Popii") has been preserved at the altitude of 184 m. In the third stage, a second capture has occurred, this time in the right bank of the river, at the level of the Bats Passage (the upper entrance). Eventually, in the final stage, the river has adopted the actual level of the Streamway Passage A small natural bridge some 100 m upstream the main entrance suggests that the capture points in stages 3 and 4 were actually located further upstream and that part of the former cave passages were subsequently de stroyed by collapses. 43 Ponicova is generally a well-ventilated cave, strongly influ enced by the temperature variations at the surface, ex cept for the deeper sectors of Speleothems Passage and The Muddy Passage. The temperature may vary, according to the sea sons, between 9 oc and 22 C in the well-ventilated passages (average humidity: 60-78%), while the deep parts of Speleothems Passage benefits of a fairly constant tempera ture of 11-11.5 oc and a high humidity (-95%). Samples BarosENEANU et al. (1967) made the frrst mention on cave bear (U. spelaeus) bones that have been found in Ponicova Cave. However, these bones were not collected, apparently due to their serious degradation, which would have prevented any diagnosis. During a reconnaissance trip in 1998, we dis covered a skull cemented into a hardened clayey matrix, into the ceiling, at the very dead-end of the Speleothems Passage (see Fig. 2 and Fig 3). Several small fragments (samples PGP1) of this skull were collected at that time but most of it was carefully removed during a subse quent visit in 1999. The fragments collected allowed the partial reconstruction of the skull at the Laboratory of Paleontology "Emil Racovita" Institute of Speleology. This part consists of the left parietal, and the posterior orbital bone of a bear skull. Dimensionally it fits well within the variation range of a ju venile Ursus spelaeus or of a young adult of U. deningeri. Several remains of rodents have been also collected but they definitely belong to much younger (Holocene) specimens Four calcite samples were also collected. Sample PGP2 was the 'root' of a broken stalagmite and sample PGP3 was a30 em-tall stalagmite, both from Speleothems Passage. In longi tudinal section, sample PGP3 show a fine lamination with an alternation of white opaque and dusty-gray laminae. This appearance may be considered as indicative for a predomi nantly evaporative regime of precipitation. Samples PGP4 and 5 were fragments of flows tone taken from the base and the top of the Laders' Passage, respectively (see Fig. 2). PGP4 was part of a more massive, tufa-like deposit located 1.5 m above the base of the passage; PGP5 has a more compact appearance and was deposited on the pas sage floor. The morphology of these samples differs very much from that of a regular cave flowstone (Fig. 4 ). Sample PGP4 shows a very porous structure, which resembles to that of a tufa; in case of sample PGP5, the pores are replaced by shrinkage cracks, suggesting that the calcite precipitation took place under freeze-thaw conditions. Dating methods AI samples have been dated by alpha-spectrometry at the U-series laboratory in Bergen University, Norway. For the calcite samples we used the standard procedure described,

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44 S. Constantin et al. Fig. 3. The skull of Ursus deningeri, in situ. The surrounding matrix is a hardened, red, clay Le crane d'Ursus deningeri in situ englobe dans une matrice consolidee d'argile rouge. Fig. 4. Sections through the samples PGP4 (down) and PGP5 (up). Note the tufa-like structure of sample PGP4 and the 'shrinking' cracks of PGP5 See text for further comments Sections a travers les echantil/ons PGP4 (en bas) et PGP5 (en haut) A noter La structure tufiere de l'echantillon PGP4 et lesfissures de contraction du PGP5. Voir le texte pour details supptementaires.

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Karst evolution in the Danube Gorge for example, in LAURITZEN & 0NAC (1999). One date was per formed on each sample, except for PGP3 where we have at tempted to date both base and top of the stalagmite. The samples (20-40 g) were digested in HN03 spiked with a commercial 228Thf-32U tracer and the solution was equilibrated by H O, oxidation and repeated boiling. U and Th were p(e concentrated by scavenger precipitation on Fe(OH) 3 then the iron was removed by ether extraction in 9M HCI. U and Th were separated by ion exchange chromatography, then the fractions were purified and electroplated on steel discs. The boi:Je fragments require a modified chemical procedure in order to extract the U and Th from phosphate matrix. This procedure has been thoroughly discussed by LAURITZEN et al. ( 1997) and it is based on the liquid-liquid extraction (LLE) of U and Th by tri-n-octyl-methyl-ammonium chloride and nitrate (n-TOMA) (Aliquat 336, Auka art. no. 91042) from hydrochloric and nitric acid solutions Since U content in bones is usually high, samples of only 2-3 g are sufficient. Two small fragments of the skull were carefully cleaned, then incinerated at 500 oc for c. 6 h. The samples were digested in 9M HCl; FeC13 carrier and 228Th/232U spike were added. After oxidation, the iron was removed by ether extraction and the concentration of the Fe-free solution was adjusted at 6M HCI. U and Th were separated by liquid-liquid extraction with n-TOMA. U was first extracted in the organic phase using a solution of 0.1 M n-TOMA in xylene, then back-extracted ('stripped') into O.lM HCI. The Th fraction, rernining in 6M HCl, was evaporated to dryness and redissolved in 6M HN03 then extracted into 0.5M n-TOMA and, further on, back-extracted into 0 1M HCI. The purified U and Th fractions were oxidized and electroplated onto steel discs For both methods, the alpha particle activity was counted for 2-4 days using an Ortec Octete unit with silicon surface barrier -45 detectors. Finally, each spectrum was corrected for back ground and delay since separation and the ages were calcu lated using standard algorithms (LAURI1ZEN, 1993). All errors reported in this paper are 1 0 Results . The results of speleothem and bone fragments datings are shown in Table 1. One of the calcite samples (top of stalag-.-'. mite PGP3) has been rejected due to the very higl\ detrital Tii content (!30'fhi232Th < 1) and it is not presented here. Theremaining four samples also show high detrital contamination, the 230'fhi232Th ratio varying between 2.7 and 14.5. Conse quently, the corrected ages of samples PGP2 and PGP3 should tJe considered with caution, and only viewed as minimum ages. The flowstone samples PGP4 and PGP5 show a lower con tamination with detrital Th and their corrected ages may be considered as reliable. All samples showed low U-contents (between -0.04 and 0.1 ppm), which in turn results in quite high statistical errors of -10% for the non-corrected ages. Dating of the two bone fragments was considerably more successful. Since U-series dating of bones is generally con sidered problematic (see ScHWARCZ & BLACWELL, 1992 or BLACWELL & ScHWARCZ, 1995) we made two dating attempts to test for reproducibility The first sample (PGPla) was a small fragment of porous bone, while the second (PGPlb) was a thinner and smoother fragment of the parietal bone The measured activity ratios and the ages calculated accord ingly for the two samples are in very good agreement within the range of 1 a errors The high U-content, good chemical yields, and the absence of detrital Th allowed the calculation of ages that are statistically identical. The only noticeable dif ference is the U content, which is slightly (<10%) higher for Tab l e I The of the speleothem and bone datings by U -se ries alpha spectrometry First four dates were performed on calcite samples, and last two dates on bone samples Ages written in bold were used in this paper. All errors are I cr Re. wltats des datations en spectrometrie alpha des speleothemes et de l'os. Les quatre premieres datations ont ete e.ffectuees sur des e clumtillons de calcite et les deux dernieres sur des echantillons d os. Les datations en caracteres gras ont ete utilisees dans ce travail. Dans tousles cas l'erreur est de 1 a Lab. No. Ucort. :ZWUF2U Age (b.) -ten: Carr. age -ten: !PPID) -err -err PGP2 1872 Stalagmite 'root' o.cm 1526 0.064 2.1 7 .15 ..0.75 3.19 +1.16 .004 .105 .007 -0.75 -1.16 PGP3 1873 Base sta1agmite 0.041 2.858 0.063 3.4 6 98 +1.06 4.00 +1.52 .004 .339 .009 -1.06 -1.51 PGP4 1811 Streamway 0 .019 1576 0265 145 32.81 +2.15 29.89 +2!J7 Pass. .003 .066 .019 -2.69 -2.91 PGPS 1812 ladder 0 .096 1.185 0.081 10.3 9 19 +0.97 8.42 +1.11 Passage .003 .057 .008 I -0.97 -1.10 PGP1a 2119 -Bone fragment 19.814 15016 1.0175 1CXXD 282.03 +39.81 (porous) .447 .027 .0329 -30.42 PGP1b 2120 Bone fmgrrent 11.403 1.4643 1.0083 1CXXD 277.32 +28.28 .020 .025 -23.17

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46 the porous bone, suggesting that the U-uptake was by its structure. Discussion The results of the datings of samples from Ponicova Cave will be first discussed from a paleontological perspective; further on, we will discuss their relevance for the karst evolu tion within the Danube Gorge area. Paleontologic aspects As mentioned before, the paleontological analyses of the skull did not allow a determination of the bear species beyond any doubt. In the absence of any teeth remains, the morphologic and morphometric observations have only permitted the rec ognition of the genus. It is generally admitted that Ursus etruscus of the Villafran chian is the ascendant of the cave bear. The specimens of U. etruscus from Val d' Arno and Olivola, considered as typical for the Villafranchian of Italy proved to be constantly en countered in Lower Quaternary deposits throughout Europe (NEWTON, 1913; BERNSON, 1931; ScHREUDER, 1945; SAMSON & RADULESCU, 1963). Some rare bear remains have been signaled as occupying an intermediate position between U. etruscus and U. deningeri. Among these, the ones described from Jockgrim and Eberbach (HELLER, 1939) are debatable, being morphologically closer to U. etruscus than to U. spelae us. SoRGE L (1926) and KosY (1952) have noticed some distinct archaic features of the remains of U. deningeri from Stissenborn, which was considered by ZAPFE (1946) as a sub species (U. deningeri siissenbornensis) Other intermediate bear remains, such as U. saklillingensis Heller, 1956, show a morphology which is closer to U. deningeri than to U. etruscus. A posterior skull fragment, together with some other bone remains was described by BoNIFAY (1971) from the cave 'of LunelViel as U cf. deningeri; its age is considered to belong to the Mindel Riss interglacial. The transversal width of tlp.s skull is 148 mm, which is comparable to that of the skull discovered in Ponicova Cave as well as to the skull described from Masbach (150 mm in both cases). Thus, by taking into account both the dimensional and struc tural features of the skull and the calculated age of the bone fragments at -277.32 (+28.3; -23.2) ka, the uncertainty has considerably narrowed and the skull fragment was assigned to the species Ursus deningeri v. Reichenau. Any other alter natives (e .g. juvenile U. speleus) have been rejected. The morpho-structural analysis of the skull suggests a mature } ndividual; its small dimensions may be considered as a S. Constqntin e( al. manifestation of the sexual dimorphism (KURTEN, 1955; 1958) and are indicative for a young specimen. In general, U. deningeri is considered as a transition species with a rapid evolution. To our knowledge, our datings consti tute the first absolute age determination of bone remains for this species According to the determined age, the speci men of U. deningeri discovered in Ponicova cave lived dur ing the cold (glacial) period corresponding to the marine iso tope stage (MIS) 8 Paleogeographic interpretation As a typical multi-level cave, Ponicova has attracted the at tention of many researchers studying the evolution of the Danube within its gorge sector (e.g. SENcu, 1979; ScHMIDT et al., 1968). Its well-defmed passage levels, as well as the relict saddle of Poiana Popii may be correlated with correspondent terraces of the river (Table 2). However, this is the first at tempt to establish an absolute chronology for the incision rate of Danube during the Quaternary. Two out of the five calculated ages are rele':ant for recon structing the regional geomorphic evolution: that of the bearskull (PGP1a,b) which postd ates the formation of Speleothems Passage, and the PGP4 flows tone-which postdates the formation of the Streamway Passage. The remaining three sainples have lesser significance due to their young age and to the lower precision of age determinations. They only ac count for a massive calcite precipitation in SW Romania dur ing the Holocene warming, which may be well traced in many caves and travertine deposits of the region (see CoNSTANTIN & LAURTIZEN, 1999; CoNSTANTIN et al., 2001; also Constantin S unpublished data) The age obtained for the PGP4 flowstone (c. 30 ka) is more relevant since this sample is clearly a vadose deposit that was located only 1.5 m above the subterranean river, within the Streamway Passage. Thus, it enables the estimate of a minimum age for the creation of this large, canyon-shaped pas sage and, accordingly, a minimum age of the corresponding second terrace of Danube. Table 2. Correlation between the different geomorphic and cave levels and Danube's terraces within the gorge sector.. Correlation entre les differents niveaux de surfa ce et sout e rrains, d'un part, et les terrasses du Danube dans le defile d'autre part Cave level Elevation Terrace Age (mas!.) (elevation mas!.) (ka) Poiana Popii saaole 184 v (150-160) Speleothems Passage 143-112 IV (120-130) >277 Bats Passage 116 III (100-117) Streamway Passage 80-65 II (80) >30

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Karst evolution in the Danube Gorge a. c. 1 .c::.:=J 2.t....:..:..:.:: 3.1 'WI# I 4 1 'WI# 1 - 318 >280 ka Poiana Popii 100 200m Fig 5. Evolution of the Ponicova cave system (after SENcu, 1979, with modifications) Stages: (a) surface drainage over Poiana Popii; (b) underground capture through the Speleothems Passage (before 277 ka); (c) second capture at the level of Bats Passage (note that the passage extends upstream the current entrance); (d) modern phase: third capture at the Streamway level and direct drainage to the Danube. The natural bridge is a remnant of the former, collapsed, passages. The two shades of Danube designate the situation before and after the creation of artificial Iron Gates Lake. I Karstic spring; 2. Inferred underground drainage ; 3 River (active) passages; 4. Dry (fossil) passages; 5. a. Inferred position of former cave passages; b. Natural bridge ; 6. Gorge. Evolution de Ia grotte de Ponicova (d'apres SENCU, 1979. inodijiee). Etapes (a) drainage de surface a travers Ia Poiana Popii; (b) capture souterraine a travers Ia Galerie des Concretions (avant 277 lea); (c) seconde capture au niveau de Ia galerie des Chauves-Souris (a noter que Ia galerie se prolonge aussi bine en a mont de I' entree actuelle; (d) phase mode me: Ia troisieme capture au niveau de Ia Qalerie Active et drainage direct vers le Danube. Le pont nature/ reste comme un temoin des galeries detruites Jo amont. Les deux nuances de gris du Danube signifient le niveau de l'eau avant et apres lafonnation dulac artijiciel des Portes de Fer I. Source karstique; 2. Drainage souterrain suppose; 3. Galeries actives; 4. Galeriesfossiles; 5 a. Position supposee des galeries actuellement detruites; b. Pont nature/; 6. Gorge. 47

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Similarly, we may assume that the upper cave level (Speleo thems Passage) is older than -277 ka, which is the age of U. deningeri skull. This figure may be thus taken as the lower limit for the formation of Danube's fourth terrace (120-130 m asl.). The evolution of Ponicova cave system (Fig. 5) as inferred by the results of this work includes the initial underground capture of the river, through the Speleothems Passage, at some point in time well beyond 277 000 years ago. It seems rea sonable to assume this value as a minimul? age of the IVth terrace of the Danube as well. Dating by means of cosmogenic isotopes of the relict pebbles found into the upper sector of this passage might extend this figure considerably, but this will be the subject of further research. It will be hazardous to make any further assumptions con cerning the timing of formation of the other cave levels. Nev ertheless, it seems very clear that the lower (active) level shall be older than -30 000 years, the age of PGP4 flowstone. A tentative calculation of the subterranean river incision rate, based on the position of the sample at -1.5 m above the stream will yield a maximum value of -0.05 m/ka. This figure is one order of magnitude lower than the erosion rate value of 0.4-0.5 m/ka calculated for Crisul Repede river basin (LAURITZEN & ONAC, 1995) but this may be considered as normal taking into account only the large difference between the flow rates of the two rivers. Moreover, if we try to estimate Danube's incision rate based on the position of the second terrace (-20 m relative altitude), which may be considered as a base-level for the Stream way Passage, the maximum fluvial incision rate would be of -0.67 m/ka, in accordance with the work cited. The presence of small marrimals remains in the terminal sector of Speleothems Passage is indicative for the existence of an other cave entrance, located in the close vicinily, during the Holocene, since these species never live in the deep sectors of a cave. If we add to this: (i) the presence of anemolites, suggest ing a strong air current and (ii) the observations on the structure of PGP3 stalagmite indicating evaporative conditions of pre cipitation, we may conclude that the total clogging of the Speleothems Passage took place only in the recent past, less than -3 000 years ago. The stable meroclimate of this part of the cave is therefore only recent and the premises for further speleothem dating work in search for older specimens do not seem very promising. S. Constantin et al. Conclusions The successful dating by U-series LLE method of two frag ments of the same cave-bear skull from Ponicova cave yielded activity ratios and ages that are in very good agreement within the lcr errors range. The LLE method proved to be very use ful in dealing with bone samples and the close replkates of the two coeval samples is encouraging. The ages obtained not only allowed the dating of the skull at -277 (+28; -23) ka but were also crucial for the paleontological diagnosis. According to this, the skull belonged to a mature individual of U. deningeri v. Reichenau. This is also the first absolute dat ing of fossil remains for this species. The determined age offers a first estimate on the antiquity of the Ponicova cave system and a minimum estimate for the age of the fourth terrace of the Danube, which is considered to represent its first base level. U-series dating of PGP3 calcite sample allowed a second es timation for the minimum age of the lower cave level (the Stream way Passage) as of minimum 30 ka. This may be also considered as a minimal age for the second terrace of the Danube. Rough calculations yielded maximal incision rates of 0.05 m/ka for the cave passage and of 0.67 m/ka for the fluvial erosion rate of the Danube. These figures must be considered only as preliminary, and further work is required. Finally, the morphology and structure of the speleothems from the topmost sector of the cave, together with the discovery of recent micro-mammals remains indicate that another cave entrance located in this zone may have been clogged not ear lier than -3 000 years ago. Acknowledgements All datings were performed in the U-series Laboratory, Bergen University. All paleontological work was done in the spe cialized laboratory of the "Emil Racovita" Institute of Spele ology. Part of this work has benefited of the support for S. Constantin and A. Petculescu by the grant 5235 of Romanian Agency for Science, Technology and Innovation (ANSTI). We also thank Angela Teodorescu for help in the field and for drawing some of the figures. This is the 8th contribution to the Speleothem Pole-Equator-Pole (SPEP) III in Romania.

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Karst evolution in the Danube Gorge References BERNSEN, J. J. A. (1931) Eine revision derfossilien Siiugetierfauna und den Tonen von Tegelen. III. Naturhist. Maandblad, 5. BLACKWELL, B . & ScHWARCZ, H. P. (1995) The Uraniu{ll series dis equilibrium dating methods. ln: Dating methods for Quaternary deposits (RuTIER, N. W., & CArro, N. R., Eds.), Geological Ass. of Canada, St. John's, Newfoundland, pp. 167-208. BoNirAY, M.-F. (1971) Carnivores quaternaries du Sud-Est de la France. Mem. Mus. Nat. Hist. Nat., C, XXI, pp. 43-377. BoTosENEANU, L., NEGREA, A., & NEGREA, S. (1967) Grottes du Banat explorees de 1960 a 1962. In: Recherches sur les grottes du Banat et d'Oltenie (Roumanie, 1959-1962), Ed. CNRS, Paris, pp. 25-226. CoNSTANTIN, S., & LAURITLEN, S-E. (1999) Speleothem datings in SW Romania. Part I : Evidence for a continuous speleothem growth in Pestera 'during Oxygen Isotope stages 5-3 and paleoclimatic significance. Theor. Appl. Karstology, 11-12, pp. 35-46. CoNSTANTIN, S., ONAC, B. P., FI.EITMAN, D., & TAMAS, T. (2001) Past vegetation changes in karst areas as revealed by a comparative isotopic study of two Holocene speleothems from Romania. IGCP 448 Newsletter, Karst Dynamics Lab., Guilin, China, pp. 67-73. CviJic, J. (1908) Entwicklungsgeschichte des Eisernes Tares. Pettermans Geogr. Mitteilungen, Ergiinzungsheft 160, Gotha. FoRD, D. (1997) Dating and paleo-environmental studies of speleothems. In: Cave minerals of the world (HILL, C. & FoRTI, P. Eds.); NSS, Huntsville, pp. 271-284. GRUBIC, A ( 1994) Geological features of Carpatho-Balkanides mountain system. In: Ground waters in carbonate rocks of the Carpathian-Balkan mountain range. (Stevanovic, Z. & Filipovic, B. Eds.), Carpathian-Balkan Geological Ass., Belgrade, pp. 9-34. GIWBic, A & BERZA, T. Eds. (1997) Geology of Djerdap area. Inti. Symp. "Geology in the Danube Gorges", 23-26.09.1997, Geoinstitut, Spec. Publ. 25, Belgrade, 306 p. HELLER, D. P. ( 1939) Die Barenzahne aus den Ablagerungen der ehemaligen Neckarsschlinge bei Eberbach im Odenwald. Sitzungberic:hte der Heidelberger Akad. zu Wiss.math-naturw. Kl,7. HELLER, D.P. ( 1949) Ursus (Plionarctos) stehlini Kretzoi, der Kleine Bar aus den altdeluvialen Sanden von Mauer-Bammental und Mainz-Wiesbaden. S. Ber. Heidelberg Akad. Wiss. MathNaturw. Kl., 11, pp. 1-60. 1EANNF.L, R., & RACOVITA, E. ( 1929) Enumeration des grottes visitees. Arch. Zool. Exper. Gener 68, pp. 293-608. KURTION, B. ( 1955) Sex dimorphism and size trends in the cave bear Ursus spelaeus RosenmUller & Heinroth. Acta Zoot. Fenn., 90, pp. 1-48. KuRrtN, B (1958) Life and death of the Pleistocene cave bear. Acta Zoot. Fenn., 95, pp. 1-95. 49 LAURnZEN, S.-E. (1993) "Age4U2U". Program for reading ADCAM energy spectra, integration, peak-co"ection and calculation of 230Th/234U ages. Department of Geology, Bergen Univ., 5000 -LAURITZEN, S.-E., & ONAC, B. P (1995) Uranium-series dating of some speleothems from Romania. Theor. Appl. Karstology, 8. pp. 25-36. LAURITZEN, S.-E., & ONAC, B. P. (1999) Isotopic stratigraphy of a last interglacial stalagmite from Northwestern Romania: corre lation with deep-sea record and northern latitude speleothem. J. Caves Karst Studies, 61, 1, pp. 22-30. LAURITZEN, S.-E., HuRUM, J. & ALSTAD, J. (1997) Simple liquid-Jiq. uid extraction of U and Th in tracer amounts from phosphate matrix for dating purposes. Chemical Geology incl. Isotope Geoscience, 137, pp. 265-271. Kosv, F. E. (1952) Note sur main de I 'Urside de SUssenbom, Eclogae Helvetiae, 45, 2. LoWE, J. J. & WALKER, M., J. ( 1997) Reconstructing quaternary environments. 2"" Ed., Longman Asia Ltd., Hong Kong, 446 p. MEJN, (1976) Resultats du groupe de travail des vertebres. Biozonation du Neogene mediteranneen a partir des Mammireres. In Report on Activity ofRCMNS Working Group (SENES, J. Ed.), pp. 78-81. M UTIHAC, V. (1990) Structura geologica a teritoriului Romaniei. Ed. Tehnica, Bucuresti, 420 p. NEGREA, A., & NEGREA, S. (1979) din Defileul Dunarii fauna terestra. In : Speologia. Gr. Cere. Com pl. "Portile deFier" Seria Monografica. (ORGHIDA.III, T. & NEaREA, S. Eds .), Ed. Academiei RSR, Bucuresti, pp. 30--75. NEWTON, E., T. (1913) On the remains of Ursus etruscus (=Ursus arvernensis) from the Pliocene deposits ofTegelen sur Meuse. Verhandlingen van het geologischming bonwunding genoot shap., Woord Nederland en Kolonien. Geolog. Serle, Deeb, I PosEA, G., luE, I., GRIGORE, M., & PoPF.scu, N. (1969) Defileul dunarean al Poqilor de Fier. Caracterizarea reliefului Diviziunile morfologice. In: Geografia viiii Dunilrii romlineiti. (NICULESCU, G. et al., Eds.), Ed. Academiei RSR, Bucuresti, pp. 271-277. PosEA, G., GRIGORE, M. & PoPESCU, N. ( 1976) Treptele morfogenetice din zona Defileului Dunarii. In: Geograjia. Gr. Cere. Campi. "Portile de Fier". Seria Monografica (IANCU, M. Ed.), Ed. Academiei RSR, Bucuresti, pp. 60-66. SAMSON, P., M., & RADULESCU, C. ( 1963) Les faunes mammalogiques du Pleistocene inferieur et moyen de Roumanie. C.R. A cad. Sci. Paris, 257, pp. 1122-1124. ScHMIDT, N, PovARA, I., & PETcu, A. (1968) Aspecte ale reliefului calcaros din sectorul Cazanelor Marl. Comunicilri de Geografie, Soc. St. Geogr R.S.R. VI, pp. 27-35. ScHREUDER, A. ( 1945) The Tegelen fauna, with a description of new remains of its rare components. pp. 133-204. I ScHwARcz, H. P., & BLACWELL, B. A. (1992) Archaeological applications. In: Uranium-series disequilibrium: Applications to Earth, Marine and Environmental Sciences. (lvANOVICH, M., & HARMON, R. S., Eds.), Clarendon Press, Oxford, pp. 513-552.

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so SENCU, Y ( 1979) Carstu1 din Defileul Dunarii. In : Speologia Gr. Cere Campi. Portile deFier". Seria Monografica. (ORGHIDAN, T. & NEGREA, S Eds.), Ed. Academiei RSR, Bucuresti, pp. 11-29. SORGI'J., W ( 1926) Der "Ba-r von SUssenborn N Jahrbuch for Mineralogie, Beihige Band, LIV B. S. Constantin et al Y.i.LSAN, G (1918) Asupra trecerii Dunarii prin Pof\ile deFier. Stu diu de geografie critidi. But. S.R .G., XXXVII, pp 133-152 ZAPFE, H (1946) Die altpleistozli.nen Bli.ren von Hundsheim in Niederosterreich. Jahrbuch der Geologischen Bundesanstalt, XLI, 3-4.

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Abstract Theoretical and Applied Karstology, 13-14 (2000-2001), pp. 51-56 The Carbonate Island Karst Model applied to Guam John Mylroie 1 & John Jenson2 Department of Geosciences, Mississippi State University, Mississippi State, MS 39762, USA. 2 Water & Environmental Research Institute of the Western Pacific, University of Guam, Mangilao, Guam 96923, USA. The karst of tropical carbonate islands is unique because: 1) fresh water-salt water mixing occurs at the base and margin of the fresh-water lens; 2) glacioeustasy has moved the freshwater lens up and down through a vertical range of over 100m; and 3) the karst is eo genetic, i.e., it has developed in young carbonate rocks that have never been buried beyond the range of meteoric diagenesis. Carbonate islands can be divided into three categories based on basement-sea level relationships: simple carbonate islands (no non-carbonate rocks), carbonate cover islands (non-carbonate rocks beneath a carbonate veneer), an d composite islands (carbonate and non-carbonate rocks exposed on the surface). These ideas form the Carbonate Island Karst Model (CIKM) which can be visualized in terms of a three-dimensional framework, with island size on the x-axis, sea-level change on they-axis, and bedrock relationships on the z-axis. On Guam, tectonic uplift and glacio eustatic sea level change have produced a complex history on this composite island. The aquifer is partitioned in the subsurface by the antecedent topography of the volcanic core of the island, and lens discharge is both diffuse and conduit controlled. Keywords: carbonate island karst, karst model, Guam. Le modele karstique d'une ile carbonatee applique au Guam Resume Le karst des fles tropicales carbonatees unique parce que: (1) une zone de melange d'eaux douces et salines se trouve a Ia base et aux bords de Ia zone lenticulaire d'eau douce; (2) Ia glacio-eustasie a provoque une migration verticale de la lentille d'eau douce avec un ecart de plus de 100m et (3) le karst est eo-genetique, c'est-a-dire developpe dans des roches carbonatees jeunes, qui n. ont jamais ete enterrees en dessous de la zone de diagenese meteorique. Les fles carbonatees peuvent etre divisees en trois categories par rapport aux relations entre le soubassement et le niveau de la mer: fles carbonatees simples (pas de roches non-carbonatees), fles a couverture carbonatee (il y a des roches non-carbonatees en dessous d'une couverture carbonatee superficielle) et fles composites (des roches carbonatees et apparaissent en surface). Ces idees forment le Modele Karstique d'lle Carbonatee qui peut etre visualisee dans un modele tridimensionnel comprenant les dimensions de l'fle sur l' axe x, les variations du niveau de lamer sur /'axe yet les relations avec le soubasement sur l'axe z. Dans le Guam, le soulevement tectonique et la variation glacio-eustatique du niveau de Ia mer sont les causes d'une histoire complexe de cette tie composite. L'aquijere est partage en souterrain par la topographie du noyau volcanique de l'fle et sa decharge se fait tant de maniere diffitse que par des conduites. Mots ctes: modele d 'tie carbonatee, modele karstique, Guam. *corresponding author. E-mail address: Mylroie@DeanAS.MsState.Edu 200'1, Editura Academiei Romane. All rights reserved.

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52 Karst in carbonate islands Tropical carbonate islands are a unique karst environment that differs significantly from that found in temperate conti nental interiors, where most cave and karst research has been done. The differences center on three factors (MYLROIE & VACHER, 1999): I) freshwater/saltwater mixing occurs within the island freshwater lens; 2) glacioeustasy has moved the freshwater lens up and down through a vertical range of over 100m; and 3) the karst is eogenetic i.e., it has developed in carbonate rocks that are young and have never been buried beyond the range of meteoric diagen&sis. The outcome of the first factor is that enhanced dissolution by the mixed wa ters at the base and margin of the lens augments the enhanced dissolution at the lens surface by mixing of vadose and phreatic A B c CAR!JONATE ROCK SIMPLE CARBONATE ISLAND AUTOGENIC RECHARGE CARBONATE-COVER ISLAND AUTOGENIC RECHARGE + + + COMPOSITE ISLAND ALLOGENIC RECHARGE J. Mylroie & J. Jenson waters to modify the shape of the lens over time. The conse quent increase in hydraulic conductivity in the rock perme ated by the lens eventually results in a thinner lens. The second factor, glacio-eustatic variation of the lens position-and .variation in the time during which the lens occupies any given position in the section-results in a complex variation of po rosity and hydraulic conductivity over the section of carbon ate bedrock. If later carbonates are added above or adjacent to the original units, the lens will be thicker in the younger carbonates than in the older ones, creating a significant de parture from an idealized lens shape (VACHER, 1988). Along the margin of the lens, flow velocity increases and the mix ing zones at the top and bottom of the lens converge to form flank margin caves, typically the largest voids observed on small carbonate islands (MYLROIE & CAREW, 1995) Flank margin caves are not true conduits, but mixing chambers AUToaNIC RE:OiAROE Fig. I. Sea level and basement relation ships for carbonate islands A The simple carbonate islands, with no non-carbonate rock within the region of the fresh water lens. B. The carbonate-cover island, where non-carbonate rock at depth can deflect vadose flow and distort the freshwater lens. C Composite island, where non carbonate rock influences both surface and subsurface flow Relations entre le niveau de La mer et le fondement des ties carbonates. A lie simple carbonatee, pas de roches non-carbonatees dans La zone de La lentille d'eau douce. B. lie a couverture carbonatee; les roches non carbonatees dufondement peuvent devier l' ecoulement vadeux et deformer La lentille d'eau douce. C. lie composite, dont les roches non carbonatees influencent rant l'ecoule ment de surface que l'ecoulement souterrain

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The Cc1rbonate Island Karst Model applied to Guam Their position with respect to the margin indicates former sea-level stillstands, and their size and spacing along the is land margin are indicators of past flow conditions within the associated paleo-lens. The main consequence of the third factor i.e. that the karst is eogenetic, is that progressive diagen esis everywhere throughout the young, highly porous carbonate results in a re-ordei:ing of the host rock porosity. While the porosity remains constant or declines, it is rear ranged into selected pathways that result in a much higher hydraulic conductivity (MYLROIE &VACHER, 1999). Karst development can also be influenced by the nature of the depo sitional environment of the carbonate rock, which can vary from eolian to lagoonal, shoal or reef. Variations in island size create differences in catchment and lens volume/island perimeter ratios that appear to inhibit conduit development in small carbonate islands but favor it in larger ones (M YLROIE & VACHER, 1999). As a result of these differences, plus the effects of salt water-fresh water mixing, sea level change, and eogenetic evolution of the karst, carbonate islands contain karst features and caves remarkably different from the ty'pi cal fluvial karst formed in dense Paleozoic and Mesozoic car bonates of continental interiors. Sea level-basement relationships The three factors cited above are common to all carbonate islands, and produce karst features exhibited by all of them. Carbonate islands can be subdivided into three categories (Fig 1) based on the relationship between the sea level and the carbonate-basement contact (MYLROIE & CAREW, 1997; 2000, M YLROIE & VACHER, 1999). The sea level-basement re lationship has profound implications for the evolution of karst features. Simple carbonate islands have no non-carbonate rocks exposed at the surface or stratigraphically positioned within the range of glacioeustasy. Carbonate cover islands have non-carbonate rocks beneath a carbonate veneer, and the contact between them is within the position of the fresh water lens for all or part of a glacioeustatic cycle. Composite islands (VACHER, 1997) contain carbonate and non-carbonate rocks exposed on the surface. In carbonate cover islands, va dose waters infiltrating downward are shunted along the car bonate-basement contact, producing stream caves that carry water to the lens and/or sea level. In composite islands, this process is augmented by the development of sinks and insur gences at the surface expression of the carbonate-basement c ontact, which capture surface waters as well. In the phreatic zone of carbonate cover and composite islands, the lens can be subdivided into the basal zone, where the base of the fresh water forms the transition zone to the underlying marine water, and the parabasal zone, where the base of the fresh water rests on basement rock (MINK & VACHER, 1997). The parabasal zone is the zone of choice for groundwater development on carbonate islands because wells placed in the parabasal zone are relatively immune to lateral intrusion or upconing of ma rine waters. 53 Surface features The surface of carbonate islands contains a-characteristic epikarst, which differs from that in typical continental set tings mostly as a result of the youthful age of the carbonates and the pervasive presence of salt spray, which collects on the rock surfaces and mixes with meteoric water to create a distinctive etching pattern. In the absence of allogenic catchments on adjacent non-carbonate terrain, sinking streams, blind valleys, and springs are rarely found. Closed depres sions are common, but many represent constructional fea tures by initial depositional variation, or subsequent tectonics. In such cases, the depressions, while internally drained by dissolution pathways, have not had the majority of their volume created by dissolutional excavation. Vadose flow along the contact between the carbonate and non-car. bonate base on carbonate cover and composite islands, how ever, can undercut the overlying carbonate, producing large collapse voids that may prograde to the surface, as observed on Bermuda (MYLRoiE et al., 1995). The Carbonate Island Karst Model The variability of the initial carbonate depositional environ ment (e.g. reef, shoal, lagoon), the differential dissolution and diagenesis these rocks have undergone, and the relationship between carbonate and non-carbonate rocks thus combine to profoundly modify the classic Ghyben-Herzberg-Dupuit model of the freshwater lens of ideal islands. To provide an appropriate systematic geologic model, we seek to synthe size these characteristic features into a coherent framework, which we have labeled the Carbonate Island Karst Model (CIKM) (MYLROIE et al 2001). The model is summarized schematically in Figure 2. It provides the basis for accurate aquifer conceptual models for hydrologists working on wa ter resource development, or for other engineering applica tions on carbonate islands. The initial research for the CIKM began in the Bahamas and Bermuda, simplistic carbonate and carbonate cover islands, respectively, in tectonically stable settings. Work progressed to Isla de Mona, Puerto Rico, a simple carbonate island that has been tectonically uplifted. The research has been extended to the island of Guam, a com posite island in the western Pacific with a complex tectonic history. It is important to recognize that carbonate islands do not always fall into distinct categories, but may contain a range of characteristics that blend many island conditions, as shown below. Guam and the Carbonate Island Karst, M9del Guiun was selected to apply insights gained in the Atlantic Caribbean province to a Pacific location, while also incorpo rating the additional complexity of the island to extend and

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54 A. B. Schematic of Carbonate Island Karst Aquifer Concept ,. .. Mlxrd carbqnate and noD=Sj!rbonalt lcmln Basement relationships to sealevel and surface lncrmlng pro"":',::: 1 ouemenlabo.eaa// Busmenr t &r.semont be/owftu/1 wtdtlens aurflce lnundaUon & depo51Uon / I -r INhlmu / /?"7TTT77"7? t--""':""' _.__, .J --... ---__,-. / J. Mylroie & J Jenson deptenlon ...,., tacaoruc uplift Composite Islands basement elCPOsed at surface stream conduits at contact sinkhote-dmlned catchments Carbonate Cover Islands basement In contact with tens conduits develop along contact Common Characteristics Simple Carbonate Islands Freshwater lens basement below len!. dilluse matrtx now Glacio-eustatic movement of lens Eogenetic karst Composite Islands ...tream. ccndub I b1aernnt aurl'ac. contam ahkhole-drJintd c::atdunenla Carbonate Cover Islands c:o!Dtits devebp along bawmtNtensco"ntlel Defining Characteristics Freshwater lens Simple Carbonate Islands diffuse malri:w: flow Island shce Small Glacio-eustatic movement of lens Eogenetic karst Fig. 2. A. Schematic diagram of the Carbonate Island Karst Model (CIKM) Any island karst should fall somewhere in the three-dimen siona l field presented here See text for a discussion of terins and concepts shown in the schematic. B. Placem ent of sample islands within the field of the ClKM demonstr ates how chan ges in island size, lens discharge, and island category occur wh en sea lev e l varies. A. Diagramme schematise du Modele Karstique d'une lie Carbonatee (CIKM). Toute fie karstique doit se retrou ve r dans Ia representation tridimensionnelle presentee. Voir le texte pour une discussion sur les termes etles concepts presentes. B. Les positions des quelques fles dans l e cadre du modele CIKM demontrentl es changements de Ia dimension de l'fle, de Ia decharge de Ia l entille d'eau douce et de Ia categorie de l'fle par suite de s oscillations du niveau de Ia mer

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The Carbonate Island Karst Model applied to Guam refine the CIKM. Guam is a dual island-the southern half is volcanic with a few carbonate outliers, the northern half is carbonate with a few volcanic inliers. The carbonates are young, ranging in age from Miocene to Holocene. Tectonic uplift has been continuous in the Quaternary, overprinting the glacioeustatic sea level record and imposing a complex structural grain (joint and fault orientations) on the limestone units. Guam displays features from each of the three subdivisions of carbonate islands described in the previous section. The northern half is mostly carbonate, with attributes of a simple carbonate island over about 80% of its surface area, where the limestone bedrock extends down to well below sea level. Beneath the other 20% of the surface, however, the volcanic basement. lies well above sea level, as in the carbonate cover model. At two locations the basement extends to the surface, rising above the northern Plateau to give it attributes of a com posite island. The southern half of Guam is uplifted volcanic terrain upon which lies remnants of once extensive reef-la goonal limestones and occasional fragments of older shal low-water carbonate deposits that were incorporated into the younger volcaruc. units (TRACEY et al ., 1964). In all cases except a few on the eastern coast, the base of the southern carbonate rocks is elevated above modem sea level. Such a position removes them from the influence of glacio eustacy, and from the dissolution effects of fresh and marine water mixing. The karst of southern Guam is thus more analogous to larger islands such as Puerto Rico and Jamaica, where the interior carbonates produce caves and karst landforms similar to those in tropical continental settings. The diversity References JENSON, J. W JocsoN, J. M U., & SIEGRIST, H G. (1997) Ground water discharge styles from an uplifted Pleistocene island karst aquif er, Guam, Mariana Islands In: The Engineering Geology and Hydrology of Karst Terranes (BEcK, B F., & STEPHENSON, J. B., Eds.), Balkema, Springfield, Missouri, pp. 1519. MINK, J. F & VACHER, H L (1997) Hydrogeology of northern Guam. In: Geolog y and Hydrogeology of Carbonate Islands. Developments in Sedimentology 54 (VACHER, H. L., & QuiNN, T., Eds.), Elsevier Science, Amsterdam, pp. 743-761. M YI.ROIE, J. E & CAREW, J. L. (1995) Chapter 3: Karst development on carbonate islands. In : Unconformities and Porosity in Carbonate Strata (BUDD, D. A., HARRIS, P.M., & SALLER, A., Eds.), Vol. Melli 63, Am. Ass. of Petroleum Geologists, pp. SS-76 M YLROJE, J. E. & CAREW, J. L ( 1997) Land use and carbonate island karst. In: The Geology and Hydrogeology of Karst Terranes (BECK, B. F & STh1'HENSON, J. B Eds .), BaJkema, Rotterdam, pp. 3-12. ss of karst environments on Guam has thus produced an espe cially wide variety of karst landforms and cave gevelopment, ran gin,& from features characteristic of the simplest islands to features resembling continental landforms. Lens discharge is mainly by diffuse flow, modified by poros ity re-arrangement as diagenesis creates high-conductivity pathways in the rock occupied by the lens. Joints and faults appear important in developing these high-conductivity path ways (JENSON et al., 1997). Given that glacio-eustatic lowstands have occurred several times during the Pleistocene and that the entire Pleistocene section has been raised above sea level on northern Guam, it is likely that a considerable span of the carbonate section now below sea level was in the vadose zone long enough for stream caves to have developed along the carbonate-basement contact. The hydrological implications of the vadose flow paths that formed during sea level lowstands, and which now are partially embedded in the lens of the parabasal zo'ne, are uncertain at this point. Several levels of terraces and horizontal grooves in the cliff faces indicate episodes of relative sea-level stillstands in the exposed subaereal section. In recent field work, we have observed that these horizons also exhibit widespread devel opment of moderate-sized flank margin caves. The caves show clear evidence of re-invasion by chemically aggressive waters, another result of lens migration and overprinting fol lowing the interplay of tectonics and glacio-eustasy. Guam contains a bewildering variety of caves, karst features, and water flow pathways that defy existing simple island or con tinental models (M YLROIE et al., 2001 ). The CIKM, however, provides a common framework for uniting the geology and hydrology of this island into a single picture. M YLROIE, J. E & VACHER, H. L. ( 1999) A conceptual view of car bonate island karst. In: Karst Modeling Symposium: Charlottesville, VA (PALMER, A. N ., PALMER, M. V & SAsowsKY, I. D., Eds.) p. 48 58 MYLROIE, J. E & CAREW, J. L. (2000) Speleogenesis in young lime stones in coastal and oceanic settings In: Speleogen esis : Evolu tion of Karst Aquife rs (KI..IMCHOUK, A. B., FORD, D. C., PALMER, A. N & DREYBRoor, W., Eds.), NSS, Huntsville, AL, pp 226-233. MYLROIE, J. E CAREw, J. L., & VACHER, H. L (1995) Karst dev el opment in the Bahamas and Bermuda. In: Terrestrial and Shallow Marine Geology of the Bahamas and Bermuda (CURRAN, H A., & WHITE, B ., Eds.) Vol. Geol. Soc. of America Special Paper300,gp.251267 MYLROIE,J. E., JENsoN,J. W JocsoN,J. M. U., & LANDER, M (1999) Karst Geology and Hydrology of Guam : A Preliminary Report: Mangilao. Water & Environmental Research Inst it ute of th e Western Pacific, University of Gu am, Tec hnical R epo n No 89, 32 p.'

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56 MYLROIE, J. E., JENsoN, J. W., TAilOROSI, D., JocsoN, J: M. U., V ANN, D. T., & WEXEL, C. (200 I) Karst features in Guam in terms of a general model of carbonate island karst. J. of Caves and Karst Studies, 63, I, pp. 9-22. TRACEY, J., 1., Jr., ScHLANGER, S., 0., STARK, J., T., DoAN, D., MAY, H., G. (1964) General Geology of Guam. U.S. Geological Survey Professional Paper 403-A, US Government Printing Office, Washington, D.C., 104 p. J. Mylroie & J. Jenson VACHER, H. L. (1988) Dupuit-Ghyben-Herzberg analysis of strip island lenses. Geological Society of America Bulletin, 100, pp. 850-591. VACHER, H. L. (1997) Introduction: Varieties of carbonate islands and a historical perspective. In: Geology and hydrogeology of carbonate islands (VACHER, H. L., & QuiNN, T. M., Eds.), Volume Developments in Sedimentology 54, Elsevier, pp. 1-33.

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Theoretical and Applied Karstology, 13-14 (2000-2001), pp. 57-65 Karst genetic model for the French Bay Breccia deposits, San Salvador, Bahamas Lee Florea 1* John Mylroie2 & Jim Carew3 1 Kentucky Cabmetfor Natural Resources, Frankfort, KY 40601 USA 2 Department of Geosciences Mississippi State University, Mississippi State, MS 39762, USA 3 Department of Geology, University of Charleston Charleston, SC 29424, USA Abstrac t On the island of San Salvador in the Bahama archipelago 30 breccia deposits can be found along the French Bay sea cliffs on the southeastern coast of the island Breccia deposits of this type have not been observed on any other location on the is land These deposits have traditionally been interpreted as paleo-talus deposits from an eroding sea cliff formed on a transgressive eolianite deposited at the start of the oxygen isotope substage 5e sea-level highstand (ca. 125,000 years before present). New evidence supports a karst genesis A survey of several deposits revealed a vertical restriction of +2 to +7 meters above sea level consistent with flank margin caves developed during the substage 5e still-stand. The morphologies of the features were found to be globular and contain distinct caliche boundaries, overhung lips, and smooth undulating bases. Petrographic results support a model in which voids are created and then infilled with a soil breccia. It can be concl uded from these results that the deposits reflect qualities of a lithified soil breccia filling in breached flank margin caves. Keywords : karst breccia, paleokarst, San Salvador Modele gemitique karstique des depots de French Bay San Bahamas Resume Sur /'ile de San Salvador de Bahamas) on a trouve 30 depots de breches situ es le long de La cote de French Bay dans Ia partie sud de l 'fle. Ces depots ant ete traditionnellement interpretes comme des depots de paleo-talus d 'un e ancienne falaise marine, formes sur des eolianites transgressives qui ant ete depos ee s au debut du stage i sotopique 5-e (haute mer). Les nouvelles donnees indiquent une genese karstique. L 'et ude de quelques depots a revete une disposition verticale restreinte de +2 jusqu 'a +7 m au-dessus du niveau de La mer, correspondant aux grottes de flanc marginal developpees durant le stage 5-e La morpho lugie des formations est globulaire et inclut des horizons de caliches et des bases Legerement ondulees. L 'anal yse petrographique mggere que les cavites ant ete remplies d'une breche terrigene On conclut que ces depots repr esentent une breche terrigene lith(fiee qui a rempli des cavites de flanc marginal. Mots-ctes: breche karstique, paleokarst, San Salvador. Introduction San Salvador Island is located in the eastern portion of the 1000 km Bahamian Archipelago (Fig 1). The size of the is land is re lativ ely small: roughly 12 km wide by 19 km long ( F ig. 2). All rocks exposed on San Salvador are Pleistocene and Holocene carbonates : The geologic record is dominated *correspo nding author E -mail address: mr_ chaos@hotmail.com 2001, Editura Academiei Romline. All rights reserved by subtidal facies at low elevations, and eolianites at higher elevations; the result of cyclic changes in the glacio-eu static sea level. This produced cycles of carbonate deposition, during sea level high stands, and erosion, during sea level lowstands, Several of these sequences are apparent on the island, buf only the sea level associated with the oxygen iso tope substage Se still-stand (125,000 BP) was high enough for marine facies to remain subarea! in modern sea level con ditions {CAREW & MYLROIE, 1994; 1997)

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58 L Florea et a/. \ Plat.ea.u N KEY ......... I 0 ISLAND ,.-/\ 20 meter contour . 2000 m contour 0 100 zoo ktns Marks tho boundary between _,. the Nonh ...,.,rlcan Plata 0 60 100 ntltes and the Caribbean Plat ISLAND r, THE BAHAMA ISLANDS ATLANTIC OCEAN CAY).I.ANS : :'_ --....... ---.... -, -b;' ... "' Jl' # '-,, --... I . -HISPANIOLA -. Fig I. The Bahama Islands (from CAREW & MYLROIE, 1994). Les fles Bahamas (d'apres CAREW & MYLROIE, 1994) The island is highly karstified with several morphologic mani festations of karst features. Inland pits, blue holes, karren of various forms, and caves are several types of karst features identified. Paleo-karst features are also present on the island in the form of infilled dissolution pockets, "palmetto stumps" (CAREW & MYLROIE, 1994), notches (MYLROIE & CAREW, 1991; REECE et at., 2000), and breccia deposits (MARSHALL, et at., 1984; FLOREA et al., 2000). On San Salvador, 30 breccia deposits can be found along more than lkm length of sea cliffs in French Bay (Fig. 2 and 3). Breccia deposits of this type have not been observed at any other location on the island. Similar breccia facies have been recognized within caves on other carbonate islands such as the Cayman Islands (JoNES & SMITH, 1988), Isla de Mona (MvLROIE & CAREW 1995), and New Providence Island in the Bahamas (MYLROIE et at., 1991). The deposits on San Salva dor occur in Late Pleistocene carbonates of the French Bay Member of the Grotto Beach Formation. The breccia deposits in French Bay consist of angular blocks of laminar-bedded oosparites ranging from 1 em to more than 1 min size within a red micritic matrix This description indicates the deposits are soil breccias and distinguishes them from coastal breccias or back-beach rubble. Coastal breccia facies contain more rounded clasts as a result of continuous wave attack and contain a white sand matrix as opposed to a red (paleosol) matrix. The French Bay breccia deposits range from matrix to clast supported, and occur as promontories due to the more resistant nature of the paleosol matrix. These deposits have traditionally been interpreted as paleo talus deposits from an eroding sea cliff of oxygen isotope substage 5e transgressive dune deposits ca. 125,000 years ago (French Bay Member of CAREW & MYLROIE, 1985). In this theory a substage 5e transgressive dune was eroded to pro duce sea cliffs during the substage 5e sea level maximum. When sea level fell at the end of the 5e substage, the sea cliff became an inland scarp; the resulting inland scarp underwent erosion and collapse producing cliff-base talus slope. Over time this talus lithified to produce a paleo tal us associated with the surrounding solution pockets and paleosol. Recent rise in sea level has renewed coastal erosion on these paleotalus de posits producing the modern day distribution and location of this facies.

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K,mr mode/for the French Bay Breccia deposits 59 0 1 2 Kilometers N Geology Cockburn Town Member French BayMember Hanna Bay Member D North Point Member EJ Owl's Hole Formation Undiff. Grotto Beach Fm. CJ Undifferentiated Pleistocene -Unlithified Holocene Fig. 2 Map of San Salvador with location of study area (data from RoBINSON l}c DAvis, 1999). Carre de San Salvador avec Ia situation de Ia zone etudiee (donnees extraites de RoBINSON & DAvis, 1999)

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60 Fig. 3. Breccia deposit on French Bay sea cliff. Depots de hreche de lafalaise de French Bay. An alternative explanation for the development and distribu tion of the breccia deposits can be derived from the theoi:y of flank margin cave development. Fresh water entering the groundwater system through precipitation floats on the salt water as a lens thinnest near the discharge at the margins of the island and thickest where the recharge is maximum. Both the fresh and the saline water quickly become saturated with respect to calcite in a carbonate island environment. Mixing of fresh and saline water along the base of this lens produces a solution with renewed dissolution capabilities (PLUMMER, 1975). Thus, karst features tend to develop along this inter face. The thinning of the fresh-water lens near the discharge at the island margins increases the velocity of water due to a reduc tion in cross-sectional area. This increase in velocity com bined with the intersection of the upper and lower mixing surfaces of the lens promote maximum dissolution potential (SANFORD &KONIKOW, 1989; MYLROIE & CAREW, 1988; 1990). In the Bahamas, the freshwater lens tends to be thickest in eolianite ridges and discharges along the flanks of these ridges. The caves _associated with this dissolution process have been termed flank margin caves (M YLROIE & CAREW, 1990). L. Florea et al. The morphology of flank margin caves reflects the manner in which they were formed. These caves are mixing chambers not conduits; therefore are formed independent of surface conditions, or hypo genic (PALME.R, 1991 ). They contain large globular chambers with concave dissolution surfaces con nected to others by narrow windows or not connected at all, have undulating ceilings and floors, and are vertically re stricted. Because these voids form along the flanks of eolianite dunes, they tend to be clustered like "beads on a string" (VoGEL et al., 1990). If the Bay breccia deposits were indeed the result of karst processes, several indicators would be present. The de posits would be distributed along a linear trend parallel to the paleocoastline. The deposit morphologies would reflect a void history by being globular with undulating bases and over hung lips. The deposits would appear as a sequence similar to "beads on a string." The boundary between the country rock and the breccia would be distinct and could include altered wall rock or stalagmitic material (flowstone). The intent of this study was to characterize several of the deposits with field reconnaissance, accurate survey and mor phology, photographic documentation, and petrographic analysis. From this, a conclusion of non-karstic or karstic genesis would be made. Finally, a new sequence of forma tion would be developed based on the results obtained. Methods A January 2000 survey was conducted of seven breccia de posits along the northeast section of the French Bay sea cliffs using fiberglass tape and Suunto compass and inclinometer (Fig. 3). Several survey transects were run across each of these seven breccia deposits and all seven deposits were linked by survey. On larger deposits, profile transects were taken to help in the characterization. Solution pockets and other fea tures of interest proximal to the deposits were tied in to the survey to aid in mapping and the interpretation. A cartographic quality map of the surveyed deposits was generated and tied in to the 1984 MARSHALL et al. survey of the deposit locations (portion of map displayed in Figure 4 ). This map was georeferenced on Arc View and overlaid onto the topographic map of the island (provided by RoBINSON & DAvis, 1999). To support the breccia survey, a field investigation was con ducted of various locations of geologic or hydrologic signifi cance on San Salvador lsl.and. Several karst features were visited and eXplored including several of the well-known flank margin caves (CAREW & MYLROIE, 1994; MYLROIE & CAREW; 1994). Stops were made at locations cont;uning coastiu and soil breccia facies. In addition, stops were made at sites of active cave collapse in the island interior and talus slope de velopment.

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Karst genetic model for the French Bay Breccia deposits Breecla Deposit Facles ...... ,._ .Legend Sarp San Salva or bland.. Bahamas \. C.lcr. D DqlraaiOII or JanUIU')' 1000 Slln'i')' Solullepocbt Lee Floru,. John M)'ltole W1l1:w 0 8ft It Rvlll* N 8 s c C' Fig. 4. Partial map of January 2000 breccia survey. Carte partielle de La breche relewJe en Janvier 2000 Four samples were taken from one of the larger breccia de posits to use in petrographic analysis. These samples included: a sample from the country rock near the deposit, a sample from a clast contained within the deposit, a sample of the matrix, and a sample of the caliche boundary .separating the deposit from the country rock. Thin sections were made from these samples at the University of Kentucky Department of Geology, and the analysis was performed using a petrographic microscope at the Kentucky Geological Survey. Results The survey of the breccia deposits revealed a vertical restriction in development of+ 2 to + 7 meters above sea level (Fig. 4 ). Nearby solution features such as infilled solution pockets, "palmetto stumps" (CAREW & MYLROIE, 1994), and stalag mitic material (flowstone) in open phreatic pockets range from approximately +5 to +10 meters above sea level. The deposit morphologies are globular, with undulating bases (Fig. 4). These boundaries are distinct and in some locations present a thick caliche layer separating them from the coun try rock and cross cutting structure (Fig. 5). The inland bound aries of the deposits have detectable overhung lips in loca tions. The distribution of the deposits themselves is random, yet do follow a "bead on a string" description typically asso ciated with flank margin caves (VoGEL et al., 1990). Petrographic analysis of the deposits revealed that the brec cia clasts and the country rock are indistinguishable and are laminar-bedded oosparites, confirming results (MARSHALL et al., 1984). Both country rock and clasts display evidence of dissolution activity such as partially dissolved ooids and vug development. Both also contain sparry cements of two generations: a first generation equant isopachous cal cite and a calcite meniscus druse (Fig. 6). I Petrography of the matrix shows it to be unstructured and contain copious amounts of fine particulate detritus of Sa haran origin (MuHs et al., 1990) within a micritic calcite ce ment. The matrix also contains a large number of modified ooids weathered out of the original rock and occasional

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62 Fig. 5. Photograph of caliche boundary separating country rock (top) from breccia (bottom). Limite de caliche separant La roche calcaire en haut de La breche en bas. Fig. 6. Petrographic slide of clast material from breccia. Note dissolved ooids and two generations of calcite cement. Photographie du materiel clastique de La breche en lame mince. A noter les ooi'des dissous et les deux generations de ciment calcitique. L. Florea et al.

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Karst genetic model for the French Bay Breccia deposits biolithic fragments. Voids within the matrix contain arago nite fibers. The caliche boundary is structured, displaying prominent layering and consisting primarily of layered micritic calcite with some fine particulate Saharan detritus (Fig. 7). Voids within the caliche contain a calcite meniscus druse of vadose origin and whisker calcite cement commonly found in Bahamian cave walls (VoGEL et al., 1990). Discussion The vertical restriction of the deposits supports a karstic genesis. In the flank margin theory of cave development, the high est rates of dissolution are proximal to the shore at the inter section of the halocline and the water table. The elevations of the breccia deposits, +2 to+ 7 meters above sea level (Fig.4), are consistent with other flank margin caves on in the Bahamas that formed in response to the substage 5e sea level stillstand (MYLRotE & CAREW, 1990). The presence of paleosol features and stalagmitic material indicates dissolution activity at approximately the same time as the breccia formation. The elevations of these nearby solution features, +5 to +10 meters above sea level, indicate the presence of a paleo land surface at the breccia deposit elevation to a few meters above the breccia deposits (Fig. 4). Petrography of the country rock and clasts show dissolution has occurred (Fig. 6). The first generation equant isopachous calcite is consistent with a fresh phreatic cementation zone (HARRIS et al., 1985) that would have been deposited during void formation. The second-generation calcite meniscus druse would have been deposited in a vadose groundwater envi rqnment after sea level had fallen. The presence and structure of the caliche boundary layer supports a two-phase origin for the breccia deposits (Fig. 7): a void development phase in which the caliche is deposited as a secondary calcite deposit such as stalagmiti c material or through biologically enhanced micritization (BATHURST, 1975), and a second collapse phase in which the void is filled with a proto-breccia. What this evidence suggests is that the French Bay breccia deposits were formed through karstic processes. This does not eliminate talus from being a component of their formation. In fact, it is likely that talus generated from retreat processes is a portion of the material that filled these breached flank margin caves This process can be observed today oc curring on the other side of Sandy Point at Altar Cave (CAREW & M YLROIE, 1994 ). Conclusions The survey results as well as comparisons to morphologies of present day flank margin caves and sites of active talus formation show that the breccia deposits reflect qualities of a 63 Fig. 7 Petrographic slide of caliche material (country rock direction is toward bottom). Note layered micritic calcite. Photographie de la bordure de caliche en lame mince (La roche calcaire vers le bas). A noter La calcite micritique stratifiee. soil breccia filling in breached flank margin caves. These re sults combined with the petrography suggest the following sequence of events (Fig. 8): 1. A transgressive oolitic eolianite is deposited during the transgression of an oxygen isotope substage 5e highstand (CAREW & MYLROIE, 1985), approximately 130,000 years ago 2 A raise in sea lev e l during the substage 5e maximum ce mented thy eolianite and initiated dissolution along the ha loclinelwater tabl e interface, approximately 125,000 years ago. 3. Voids of significant size were produced in a short time span along the flank margin of this deposit (M YLROIE & CAREW, 1990).

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64 1 2,3 4,5,6 Fig. 8. Modified sequence of breccia development. Phases de developpement de La breche. 7 4. After sea level withdraw at the end of substage 5e 120,000 years ago, these voids were exposed to vadose conditions and secondary modification occurred. Precipitation of cal cite on the void wall developed a layer of stalagmitic ma terial, and biologic activity enhanced micritization of the wall rock. 5. Denudation of the land surface eventually intersected the voids. Soil and ceiling collapse collected on the floor of the voids creating a thick layer of proto-breccia. 6. Vadose recharge lithified the proto-breccia into the present day deposit. 7 Continued erosion has stripped the remaining overlying country rock and has left the deposits standing in positive relief along the French Bay sea cliffs. L. Florea et al. References BATHURST, R. G. C. (1975) Carbonate sediments and their diagen esis: Developments in sedimentology, 12, Elsevier, New York, 658 p. CAREw, J. L., & M YLROIE, J. E. ( 1985) The Pleistocene and Holocene Stratigraphy of San Salvador Island, Bahamas, with Reference toMarine and Terrestrial Lithofacies at French Bay. In: Pleis tocene and Holocene carbonate environments on San Salvador Island, Bahamas (CURRAN, H. A., Ed.), Guidebook for Geologi cal Society of America, Orlando annual meeting field trip, pp. 11-61. CAREW, J. L., & MYLROIE, J. E. (1994) Geology and Karst of San Salvador Island, Bahamas: A Field Trip Guidebook, Bahamian Field Station, 32 p. FLOREA, L. J., MYLROIE, J. E., & CAREW, J. L. (2000) French Bay Breccia Deposits. San Salvador, Bahamas: Evidence for Karst Genesis In: Karst Studies and Problems: 2000 and Beyond, Proc. Joint meeting of Friends of Karst, Theor. & Applied Karstology, and IGCP 448, Presa Universitara Clujeana, pp. 44-48. HARRis, P.M., KENDALL, C. G. St. C., & LERSHE, I. (1985) Carbon ate cementation -A brief review. In: Carbonate cements (ScHNEIDERMANN, N., & HARRis, P.M., Eds.), Soc. of Economic Paleontologists and Mineraloligists Sp .. Publ. 36, 379 p. JoNEs, B., & SMITH, D. S. (1988) Open and filled karst features on the Cayman Islands: Implications for the recognition of paleokarst. Canadian Journal of Earth Sciences, 25, p. 12771291. MARSHALL, P. E., RASOR, D., LAWSON, C., DECHENE, J. L., CAREW, G.; ScHORR, C., & MYLROIE, J. (1984) Investigation of Breccia Facies, San Salvador, Bahamas (abstract), Bull. of the South Carolina Academy of Science, 46, p. 109. MuHs, D. R., BusH, C. A., STEWART, K. C., RoWLAND, T. R., & CRITTENDEN, R. C. ( 1990) Geochemical evidence of Saharan dust parent material for soils developed on Quaternary limestones of Caribbean and western Atlantic islands. Quaternary Research, 33, pp. 157-177. MYLROIE, J. E., & CAREW, J. L. (1988) Solution Conduits as Indica tors of Late Quaternary Sea Level Position. Quaternary Science Reviews, 1, pp. 55-64. MYLROIE, J. E., & CAREW, J. L. (1990) The Flank Margin Model for Dissolution Cave Development in Carbonate Platforms. Earth Surface Processes and Landforms, 15, pp. 413-424. MYLROIE, J. E., & CAREW, J. L. (1991) Erosional notches in Bahamian carbonates: Bioerosion or groundwater dissolution? In: Proc. Fifth Symposium on the Geology of the Bahamas (BAIN, R. J., Ed.), Port Charlotte, Florida, Bahamian Field Station, pp. 185-191. MYLROIE, J. E., & CAREW, J. L. (1994) A Field Trip GuideBook of Lighthouse Cave, San Salvador Island, Bahamas. Bahamian Field Station, 10 p. MYLROIE, J. E., & CAREW, J. L. (1995) Karst Development on Carbonate Islands in Unconformities and Porosity in Carbonate Strata. AAPG Memoir, 653, pp. 55-76.

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Karst genetic model for the French Bay Breccia deposits M vuw1E, J. E & CAREW, J. L ( 1997) Geology of the Bahamas. In: Geology and hydrogeology of carbonate islands (VACHER, H. L., & QuiNN, T. M., Eds.), Elsevier, pp. 91-139. MYLROIE, J. E., CAREW, J. L., SEALEY. N. E., & MYLROIE,J. R. (1991) Cave Development on New Providence Island and Long Island, Cave Science 18, J, pp. 139-151. PALMEil, A. N. ( 1991) Origin and Morphology of Limestone Caves. GSA Bulletin, 103, pp. 1-25. PLUMMER, L. N. ( 1975) Mixing of sea water with calcium carbonate ground water. In: Quantitative studies in geological sciences (WHITIEN, E H T Ed .), GSA Memoir, 142, p. 219-236. REr.cli, M., MYLROIE, J. E., & J ENSON, J. W (2000) Cave and Karst De1'elopment of Guam: Implications for aquifer history. Program Guide, NSS Conv 2000, Elkins, WV, p. A-15. 65 RoBINSON, M. C., & DAVIS, R. L (1999) Preliminary Geographical Information System Analysis and Maps of Physical, Hydrologi cal, Archaeological, and Biological Resources, San Salvador Island, Bahamas. In: Proc. Ninth Symposium on the Geology of the Bahamas and Other Carbonate Regions (CURRAN: H., A. & MYLROIE, I., E., Eds.), Bahamian Field Station, San Salvador Bahamas, p. 101-109. SANFORD, W. E., & KoNJKOW, L. F. (1989) Porosity development in coastal carbonate aquifers Geology, 49, pp. 249-252 VOGEL, P. N., MYLROJE, J E., & CAREW, J L. (!990) Limestone pe trology and cave morphology on San Salvador Island, Bahamas. Cave Science, 17, pp. 19-30.

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Theoretical and Applied Karstology, 13-14 (2000-2001), pp. 67-73 Sur Ia presence de l'ardealite dans Ia Grotte de Topolnita (Plateau de Mehedinti, Roumanie) Gabriel Diaconu 1* & Delia Dumitra!J2 I Institut de Speologie "Emil RacoviJ(i", str. Frumoasa 11, 78114 Bucarest 12, Roumanie. Laboratoire des Resources Minerales, Institut Geologique, str. Caransebe 1, 78344 Bucarest, Roumanie. 11 y a 70 annees, dans Ia Grotte de Cioclovina (Monts Sebe, Roumanie) un nouveau mineral-!' ardealite-a ete decouvert en association avec le gypse et Ia broushite (HALLA, 1931; ScHADLER, 1932). Les auteurs ont identifie la meme association mineralogique dans Ia Gal erie Suspendue de Ia Grotte de Topolnita (Plateau de MehedinP,). L' echantillon preleve a ete analyse en RX, IR, TDA et chimiquement. Les donnees obtenues, comparees avec les donnees standard, ont mis en evidence I' ardealite, le gypse et Ia broushite. Le travail presente de meme un point de vue original sur les conditions du milieu speleique qui ant facilite Ia genese de cette association mineralogique. Mots-cles: mineralogie des grottes, ardealite, phosphates, sulfates, Grotte de Topolnita. On the presence of the ardealite in Topol nita Cave (Mehedinfi Plateau, Romania) Abstract Seventy years ago a new mineral-the ardealite-was discovered in Cioclovina Cave (Sebe Mountains, Romania), associated with with gypsum and brushite (HALLA, 1931; ScHADLER, 1932). The authors found the same mineral association in TopolniJa Cave (MehedinJi Plateau). The sample taken was investigated by means of RX, JR. TDA and chemical analyses; ardealite, gypsum and brushite were identified by comparison with standard data. The genetic condition of the speleal environment that contributed to the formation of this mineral association are also discussed. Key words: cave minerals, ardealite, phosphates, sulfates, TopolniJa Cave. Conformement a RADULESCU & DIMITRESCU (1966), l'annee 1931 est la date l::tquelle a F. Halla a realise un premier examen en RX d'un nouveau mineral preleve de la Grotte de Cioclovina (Monts Sebe), le hydrogeno-phosphato-sulfate de calcium tetra-hydrate, trouve en paragenese avec le gypse et Ia broushite. Une annee plus tard (1932) SCHADLER met au point la decou verte du Halla, en presentant le nouveau mineral, 1' ardealite, avec tous les details necessaires pour etre confmne comme tel, y compris une analyse chimique complete grace a laquelle il a etabli la formule chimique structurale fondamentale: *corresponding author. Fa;c: +40-1-2113874 .. 200 I, Editura Academiei Romine. All rights reserved. [Ca!(HP04)(S04 ) 4H!O], ayant comme rapports HP03 : S03 : cao : Hp = 1 : 0,863 : 1,834 : 3,980. Ulterieurement, ce nouveau mineral a ete decouvert dans dix autre pays, exclusivement dans le milieu speleique (HILL & FoRTI, 1997), sans qu'il eiit ete retrouve (pendant tout cet in tervalle de temps) dans une autre grotte de Roumanie. L'identi.fication de l'ardealite dans la Galerie Suspendue de la Grotte de Topolnita, toujours en association avec le gypse et la brushite, vient de completer les donnees existantes sur la mineralogie du domaine speleique national.

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68 La de(l'opolnita: donnees generales Ayant une longueur totale (connue jusqu'a present) de 20,5 km de galeries creusees dans le massif sur une denivellation de 109m (GORAN, 1981), La Grotte de TopolniJa est l'un des plus importants objectifs speleologiques de Roumanie. Les calcaires dans lesquels la cavite est creusee, affleurent au sud-ouest du Plateau de Mehedinp, a environ 30 km nord de la ville de Drobeta -Turnu Severin, etant encadree en grande ligne par le triangle des localites Cireu Jupfuleti -Marga . L' age des calcaires, appartenant a 1' Autochtone Danubien, est attribue au point de vue chrono-stratigraphique a !'inter valle Tithonique-Aptien. La barre des calcaires, orientee NNE-SSO, est delimitee a I' ouest par les schistes cristallins de la Nappe Getique (Lam beau de Bahna) et a 1' est par les roches sedimentaires en fa cies de flysch de la Nappe de Severin. ,... 1 .. -,\ I I \ ........._ \ \ \ \ \ ...)-.., G. Diaconu & D. Dumitra -La maniere de developpement des principales galeries de la grotte, ainsi que des observations sur la tectonique locale nous ont permis de supposer que, parallelement aux failles d' enca drement de la barre calcaire i1 y a une faille supplementaire (dans le voisinage de la Faille Ouest), toutes les trois etant affectees altemativement, du nord vers le sud, par des dis jonctions transversales (probablement plus nouvelles), arlen tees oso-ENE (Fig. 1). En general, le systeme de galeries de la Grotte de Topolnita est oriente d'une maniere preferentielle sur ces deux direc tions (Fig. 2). L' echantillon soumis aux analyses mineralogi ques a ete preleve du plancher de la Galerie Suspendue dont la longueur totale est de 226m (Fig. 2A). Dans la partie centrale de cette galerie i1 y a une grande salle avec des dimensions de 50 x 30 x 8 m. Dans une position excentrique, pres de la parois gauche (le secteur est de la salle), se trouve unimportant depot de guano provenant d'une colo nie de chauve-souris presente pendant la saison chaude a la vofite. Le depot, assez grand, est accumule sous la forme d'un 0 0 0 ... : Morga o 1km it:::==--:!===--Fig. I. Carte geologique de Ia zone d'emplacement de Ia Grotte de Topolnita. 1: schistes cristallins; 2: calcaires; 3: depots detritiques. Geological map of the region of Topolnija Cave. 1: crystalline schists; 2: limestones; 3: detrital deposits.

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Sur Ia presence de l'ardealite dans Ia Grotte de TopolniJa A 0 10 20 30m Gallerie de Staicu / _____ ____; J .\ ( I I l t ) 1 \ :%? /-------' t jl / --) j'f' : / Gallerie du Prosac .t. / ,. I Fig. 2. Carte de Ia Grotte de Topolnita. En vignette (A) Plan de Ia Galerie Suspendue ; pour I a 5 voir les explications dans le texte. Map ofTopolniJa Cave. Inset A: plan ofOverhanged Passage. For mineral zones 1-5 see explanations in the text. Tableau I. Les valeurs standard du gypse comparees avec les 69 dome depassant, dans sa partie centrale, 3m d'epaisseur, temoin d'unc presence continue de Ia colonic dcpuis bien longtemps. valeurs obtenues sur Ie diffractograme. Standard values of gypsum Dans le secteur circonscrit a Ia zone d'influence de Ia solution eliminee de I' accumulation de guano, le plancher est re convert d'une crofite minerale. Si a Ia limite exterieure Ia croG.te est bien cimentee et evidemment calcitique, dans le voisinage du depot de guano elle devient tres friable, etant pratiquement un agregat microcristallin gris-jaunatre, a as pect terreux. L'echantillon preleve de cette zone, analyse en RX, a mis en evidence une mixture composee (par ordre decroissante du poids) de gypse, d'ardealite et de broushite (totalement subor donne on a identifie de Ia calcite). Pour completer les analyses en RX, des analyses en IR, therrniques differentielles et chimiques ont ete egalement effectuees. Interpretation des _donnees analytiques Des quatre mineraux identifies a Ia suite de I' analyse en RX, nous detaillerons nos observations seulement sur les trois premiers (le gypse, I' ardealite et Ia broushite). La compared with those obtained for the sample. d : Glese 74-1905 I d : Gypse 42783 999"' 4.2780 3.1683 27 3.1590 3.0612 528 3.0660 2.8757 389 2.8770 2.7888 15 2.7920 2.4042 27 2.4080 2.2152 73 2.2150 2.0729 105 2.0740 2.0284 5 2.0370 1.8655 26 1.8670 1.8000 45 1.8030 1.7817 19 1.7830 1.64j3 20 1.6430 1.4398 27 1.4380 1.4185 21 1.4190 1.3256 15 1.3250 12032 19 1.2040 1.1400 23 1.1410

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70 G. Diaconu & D Tableau 2 Les valeurs standard de I'ardealite comparees avec les Tableau 3. Les valeurs standard de Ia broushite comparees avec valeurs obtenues sur le diffractograme. les valeurs obtenues sur le diffractograme. Standard values of the ardealite compared with those obtained for Standard values of the brushite compared with those obtained for the sample. the sample. d : Ardealite 83-1721 I d : Ardealite d : Brushite 72-0713 I d : Brushite 7.7480 999* 7 7630 7.5900 999* 7 6130 4.5627 323 4.5620 3.7950 46 3 8050 3.9323 419 3.9320 2.7950 46 2.7920 3 8740 89 3 8770 2.6022 199 2 6020 3.3392 301 3.3400 2.0990 39 2 0930 2 9777 116 2.9970 1.9969 62 1.9950 2 8516 261 2.8510 1.8975 17 1.8980 2 7343 107 2.7320 1.8752 98 1 8740 2.5428 107 2.5440 1.5331 24 1.5330 2 5024 37 2 5040 1.4819 2 1 4820 2.4465 134 2 4470 1.4622 4 1.4610 1.9661 57 1.9610 1.3664 15 1 .3670 1.8 I 22 100 1.8120 1.3397 19 1.3390 1.6698 29 1.6680 1.1523 15 1.1520 Tableau 4 Les parametres cristallographiques pour Ies trois mineraux de Ia Galerie Suspendue, Ia Grotte Topo1nita. Crystallographic parameters of the three minerals from the Overhanged Passage, TopolniJa Cave Mineral a (A) b (A) c (A) Po) V(A3 ) nUl Nl2l Gypse 5 682(7) 15.229(2) 6.494(1) 118 29(1) 495.014 6 36 Ardealite 5.722(1) 31.0 19(8) 6 238(2) 117 27(1) 984.155 9 47 Brushite 5.833(3) 15.170(6) 6.247(3) 116.65(3) 494.061 8 35 determination a ete fait en tenant compte des valeurs obtenues sur le diffractogramme comparees pour chaque espece minerale avec les valeurs standard d' International Center for D({fi-c1ction Data, fiches 7 4-1905 (gypse ), 83-1.721 (ardealite) et 72-0713 (broushite) (Tableaux 1, 2 et 3). Tableau 5. Les principales bandes d'absorption de 1'ardealite. Main absorption bands of the ardealite La concordance entre les valeurs obtenues et les valeurs standard, allant souv e nt jusqu'a l'identite, denote un haut degre de cristallisation et une forte purete des mineraux de l'ec hantillon. 11 n'existe done aucune incertitude sur le diag nostic, de sorte qu' on peut etablir les parametres cristallogra phiques pour l es mineraux determine s (Tableau 4). D'ailleurs, le diagnostic es t confirme par !'analyse en IR (Fig. 3). La comparaison entre les valeurs enregistrees et celles presentees dans le catalogue de MoENKE (1966) pour l'ardealite (Tableau 5), nous montre: La presence des bandes d'absorption de 528 cm1 et 860 cm 1 atte ste tant !'ex istenc e de I' anion phosphate que sa v ibration de liaison a v ec l'oxhydrile. L'anion sulfate est lui aussi tres bien mis en evidence par le s b an des d'absorption de 602 cm1 et resp ec tive men! de 672 cm1 Valeurs standard Valeurs de Topolnita (em-) (cm'1 ) 424 42 0 460 475 528 528 600 60 2 677 672 822 8 20 866 860 1013 1006 I 109 I 109 1145 1164 1675 1685 3370 3340 Les dernieres bandes d'absorption (1685 cm1 e t 3340 cm-1 ) confirment Ia presence de l'eau de cristallisation qui se trouve aussi dans Ia structure de l'ardealite.

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Sur La presence de l'ardealite dans la Grotte de Topolniia 90 so 70 50 40 3U 20 10 g .,. "' 4000 3500 3000 2500 2000 180C 1500 Fig. 3. Le spectre d'absorption en IR. IR absorption spectra. 0 -20 TG DTG -, "' \ ,.,.----------/ 140C 1200 1000 600 ----------,-: ---. \ \ I I -------------_ ............. . 755'---... ---40 -60 -80 -100 -120 -140 -160 -180 -200 -220 \ \ \ I DTA \ -. I . , I I : \ I ......... .. I , I I : I : I '-'162 100 200 300 478 400 500 600' 700 800 900 40J / I 950 1000 temperatw-e {"C) Fig. 4. L'analyse thermique diferentielle. Differential thermal analysis spectra. 71

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72 L'analyse thermique differentielle de l'echantillon (marquee par les courbes DTA, DTG et TG raportees a T"C) (Fig. 4) met en evidence un premier processus de deshydratation de clenche a 100 c qui finit autour de 300 c, souligne par les pies endothermiques sur les courbes DT A et DTG a 142 c et respectivement (plus faible), a 210 c. Le pic endothermique, tres large, marque au tour de 478 c est la consequence d'une impurete avec carbonate de calcium (fait confirme aussi par I' analyse en RX). Le pic exothermique tres bien surpris sur la courbe DT A autour de la valeur de 755 'C est, sans doute, determine par une mo. dification structurale des anions de phosphate et de sulfate. Le processus de desintegration finale est en outre bien mar que sur les trois courbes par des pies endothermiques a 950 c. L'analyse chimique de l'echantillon par rapport aux donnees obtenues par ScHADLER (1932) est presentee dans le Tableau 6 La presence de l'oxyde d'aluminium (Al203 ) dans l'echan tillon de la Grotte de Topolnita (2,44 %) associe avec un ex cedent de so., (1,40 %), peut nous suggerer !'existence d'un sulfate d' aluminium, probablement la basaluminite -AVS04)(0H)10 5H20 Mais, aucune des analyses presentees anterieurement (en RX, IR ou DT A) n' ont confirme cette sup position, aspect qui nous a fait presumer que l'echantillon a ete contamine avec argile provenue soit par voie eolienne, soit transportee par les eaux de percolation qui ont lave la couverture de sol. Tableau 6 Analyse chimique comparative entre l'echantillon preleve de Ia Grotte Topolnita et l'echantillon de Ia Grotte de Cioclovina (SCHADLER 1932) Comparat ive chemical composition of the sample taken from Topolnifa Cave and that analysed from Cioclovina Cave (SC HIIDWR, /932). Oxydes CaO S03 PlOs Al203 Fe203 H20 Rez. TOTAL Grotte Topolnita (%) 30.39 22 .91 19.46 2.44 0 .13 22 .90 0.90 99.13 Grotte Cioclovlna (%) 31.61 21.51 21.85 25.14 0.39 100.50 G. Diaconu & D. Dumitra Les conditions de g enese de I' association min e ralogique L'association mineralogique constituee d'ardealite, gypse et broushite est consideree comme une mixture specifique pour .-Ie milieu speleal classique (existant dans les cavites develop pees dans les roches calcaires). Sa genese, dans la plupart des cas, est liee a la presence des depots de guano (HILL & FoRTI, 1997). Dans la Galerie Suspendue de la Grotte de Topolnita cet aspect se confirme une fois de plus. ici, il y a une particula rite que nous tenons a mettre en evidence. Dans la Fig. 2A nous avons presente la position occupee par le depot de guano dans l'espace de la galerie. Done, il faut retenir que, dans le cas donne la solution generatrice de la paragenese mineralogique a circule d' une maniere centrifuge dans un plan quasi-horizontal, du cote du depot de guano vers l'exterieur et pas en profondeur. En consequence tout autour du depot de guano on peut departager, approximati vement, quelques zones d'influence a disposition centro radiaire dans la succession suivante: 1. guano granulaire, relativement frais; 2. guano humide non-granulaire; 3. un premier "anneau" constitue d'une tache humide que nous supposons broushitique; 4. un deuxieme "anneau", relativement seche, forme par un agregat terreux niicrocristallin (les echan tillons analyses ont ete preleves de cette zone) Sur d'autres diffractogrames en RX (non presentes dans ce travail), le contenu en calcite augmententforte ment vers l'exterieur de l'anneau. 5. la zone du plancher couverte d'une croute calcitique. Conclusions Conformement a HILL & FoRTI (1997), 1' ardealite represente le stade de debut de la degradation du calcaire au contact avec le depots de guano. Cette appreciation a ete confirmee aussi dans le cas de la Grotte de Topolnita mais, avec la spe cification que le processus d'enrichissement en phosphate et sulfate du carbonate de calcium s'est produit grace a une croute de calcite pre-existante sur le plancher Le fait que secteur de la galerie se trouve dans un mero climat de transition, influence par les variations climatiques de 1' exrerieur sous le controle de la morphologie locale, dont les temperatures positives durant la saison chaude ne depassent jamais 12-13 c, et dans la saison froide ne s' abaissent pas audessous de 6-7 c, a favorise la conservation de !'association

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Sur La presence de l'ardealite dans La Grotte de..TopolniJa mineralogique a l'ardealite. En outre, Ia position de Ia Gale rie Suspendue a l'extremite nord de Ia Galerie du Proslic, sa tisfait Ia condition d'une baisse de l'humidite, au moins dans ]es saisons chaudes, qui est aussi necessaire pour Ia formation de I' ardealite. Remerciements Nous remercions vivement !'Ecole des Mines de Saint Etienne, France, pour I' aide a Ia realisation des analyses en RX. 73 Bibliographie GoRAN, C. (1982) Catalogul sistematic al din Romlinia. Ed. C.N.E.F.S., Bucureti, 496 p. HALLA, F. (1931) Isomorphe Beizeihungen und Doppelsalzbildung zwischen Gips und Brushit. Zeit. f Kristallographie, 80, pp. 349-352. HILL, C. A., & FoRTI, P. Eds. (1997) Cave Minerals of the world. 2nd Ed., NSS, Huntsville, 464 p. ScHADLER, J. (1932) Ardealit, ein neues Mineral. Cbl.f Miner. A, pp. 40-45. RADULEScu, D. & DIMITRESCU, R. (1966) Mineralogia topografica a Romliniei Ed. Academiei RSR, Bucureti, 376 p.

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Abstract Theoretical and Applied Karstology, 13-14 (2000-2001), pp. 75-79 Ori the genetic conditions of black manganese deposits from two caves of Eastern Serbia Vladimir Ljubojevic1* Aleksandar Pacevski1 2 & Jelena Calic-Ljubojevic1 3 I . Student Speleologic and Alpinistic Club (ASAK), Studentski trg I6, I 1000 Belgrade, Yugoslavia. -Faculty of Mining and Geology, Dept. of Mineralogy and Crystallography, Studentski trg 16, I 1000 Belgrade, Yugoslavia. 3 "Jovan Cvijic" Geographic Institute, Serbian Academy of Sciences and Arts, Djure Jaksica 9, I 1000 Belgrade, Yugoslavia Portions of cave passages often have a black colour due to manganese deposits that occur as coatings on cave walls and ceilings, on clastic sediments, as well as on speleothems. On samples from the cave Buronov Ponor chemical analysis, infrared spectroscopy, X-ray diffraction and DT A analysis confirmed the presence of birnessite. In cave Cerjanska Pecina, the presence of manganese compounds in the black coating has been confirmed by chemical tests. In both caves it has been noted that cave passages with black coating have a distinct morphology. They are highly weathered showing an abundance of sharp protusions, potholes in the streambed and scallops. The paper studies these occurrences and the possible link between the manganese deposition, hydrology and morphology of the passages and petrologic composition. Although this link was not identified; some interesting questions regarding manganese deposition arose. It remains unclear why manganese deposition is limited only to a certain part of cave Cerjanska Pecina, and what caused the cyclicity in manganese deposition in the cave Buronov ponor. Keywords: manganese deposits, chemical analysis, speleomorphology. Sur Ia genese des depots noir de manganese dans deux grottes de Ia Serbie de /'Est Resume Certains secteurs des galeries souterraines presentent souvent une couleur noire due au.x pellicules de manganese qui peuvent couvrir en egale mesure les parois, La voute, les sediments ou les speleothemes. Les analyses chimiques, de spectroscopie en JR. de d(ffraction en RX et les analyses th ermiques differentielles effectuees sur des echantillons pre/eves de La grotte de Buronov Ponor ont releve La presence du birnessite. La presence du manganese dans La pellicule noire de La grotte de Cerjanska Pecina a ere aussi confirmee par /'analyse chimique. Dans les deux grottes on a observe une morphologie particuliere des secteurs des galeries couverts par cette pellicule noire. /ls sontfortement erodes, presentant en abondance des aretes vives, des vagues d'erosion et des trous dans le thalweg. Le travail traite de /'occurrence de ceu.x-ci et de La possible conne.xion entre La presence de Ia pellicule de manganese, l'hydrologie et La morphologie des galeries et La petrologie de La roche-mere. Meme si cette conne.xion 11 'est pas certaine, l' etude a mis en evidence quelques questions interessantes. C' est le cas de La presence du manganese seulement dans quelques zones de La Cerjanska Pecina et du depot cyclique du manganese dans le Buronov Ponor. Mots cles: depots de manganese, analyse chimique, morphologie speteale. Introduction Black sediments composed of manganese oxides are a common occurrence in caves. They occur as crusts or coatings covering cave walls, stream clasts, and, sometimes, even *corresponding author. E-mail address: fric@sezampro.yu 200 I, Editura Academiei Romane. All rights reserved. speleothems. They originate from stream water, which con tains manganese derived from surface organic material, prob ably precipitated due to bacterial activity (HILL & FoRTI, 1997, p.l25). Manganese deposits are not a rare occurrence in caves in Serbia, but they have not been studied previously.

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76 Manganese deposits in two caves -Buronov Pouor and Ce1:junska Pecina, were the focus of C!.:i interest. In both caves, we noted that distinct parts of the cave dif!'cr from the rest, both in color (i.e. sediments on cave walls) a.ud in Iuorphol ogy. The conspicuous parts of the caves are completely black. A thin layer of black coating covers not only the sediments on the floor, but also the walls, the ceiling and some of the speleothems. Besides that, the black pru ts of the cave differ from the rest of the cave also by their morphology: the pas sages are highly weathered, with abundant sharp rocky pro trusions, potholes in strcamded (SLABE, 1995, p.46), pendants, scallops etc. Buronov Ponor and Ccrjanska Pecina differ in geology and hydrological setting. Investig:!tions in both caves have been performed to find out the nature of the black coatings, and if there is a link bet ween ( Ieir Je{>Jsition and the mvrphology of the passages where they ocl:Uf. Buronov Ponor Buronov Ponor is located on Mt. Miroc, in Eastern Serbia, in the "Iron Danu!::e gorge. It is a.;1 interr.:iittent ponol' (swallet), with an entrance lo..:ated at 287 m a.s.l., and the deepest part at 85 m a.s.l., only 15m above Danube's current water level. Until late s, the "Iron Gate" Dam was built, Danube's some 20 mr'ower,' i.e. at 50 m a.s.l. The surveyed part of th
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Black manganese deposits in caves Fig. 2. Infrared spectrogram of the sample from Buronov Ponor. Spectrogramme en IR deL' echantillon de Buronov Ponor I I I I I .. I I I e .. tIE i 77 Fig. 3. X-ray diffractogram of the sample from Buronov Ponor. '9 Dijfractogramme en RX de L'echantillon de Buronov Ponor 89 79 69 :19 49 39 211 -19 -9 23811A. S H 23811A .Ill caused by the amorphous structure of the material. DT A of the samples gave only two endothermic peaks, one due to expulsion of water, and the other due to dehydratation of the amorphous material. Due to the amorphous structure of the coating, it was only possible to detect the presence of manganese in the form of birnessite. It is still impossible to tell whether any other min erals are present in the sample P e trographic analysis of samples from cave walls defined it as silty biornicritic limestone The limestone is often fractured, with occasional brecciated zones. Cerjanska Pecina Cerjanska Pecina is a through cave, located in the hills 12 km north from town of Nis, in South-eastern Serbia. It is 6 025 meters long, and it ends with siphons that are less than 200 m <;tway from the resurgence at spring Kravljansko Vrelo. Be sides the stream entering the cave, coming from Permian sand stone, there are no significant tributaries in the cave. At some 3 km from the entrance, a narrow siphon is located. The cave stream sumpSiin it, reappearing near the downstream end of the cave; still, the middle sector of the cave also shows traces of periodic waterflow (LJUBOJEVIC & GERZINA, 1997). After the sump at the third kilometer, an abrupt change in passage morphology occurs For the next 300 m e t e rs, th e

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78 0 passage resembles in all details to the one in the lower part of Buronov Ponor, except that the speleothems are lacking. The walls are black, covered with the same type of coating as in Buronov Ponor, that is occasionally almost washed away. Chemical tests (reaction with lead peroxide) proved the pres ence of Mn. Microscopic analyses of rock samples taken from Cerjanska Pecina show that most of the cave develops in lime stones; however, within the above mentioned 300m the host rock is a silty sparitic dolostone showing equal content of calcite and dolomite. Discussion Since Mn deposition occurs at water-air interface (ONAC_et ul., 1997), it is reasonable to suppose that the passages in both caves have been periodically inundated. This is easy to in case of Buronov Ponor, where passages with Mn 2km V. Ljubojevic et al. Fig. 4. Location and simplified map ofCerjanska Pecina. Carte de situation et plan simplijie de La grotte de Cerjanska Pecina. deposits lay just above the water table. In Cerjanska Pecina, there are traces of high waters and also of clastic infill of the cave, so periodic floodwaters could have been the source of Mn deposition there. The authors expected that similar morphology in both caves to be caused by similar rock composition. However, that was not the case. The outstanding morphology of lower parts of Buronov Ponor may be attributed simply to strong turbulent flow. High susceptibility to erosion, can also be attributed to the increased porosity of the rock, which is caused by frac tures and breccias in case of Buronov Ponor (SLABE, 1995). In case of Cerjanska Pecina, the difference in morphology might be attributed to greater susceptibility of porous dolostone to mechanical erosion. The Mn deposition in lower parts of Buronov Ponor can also be attributed to periodical inundation, due to vicinity of water table. However, in Cerjanska Pecina is still unclear why

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Black manganese deposits in caves the Mn deposition occurred only in the 300 m long portion of the cave in dolomites. If Mn is precipitated from a stream, the stream should have deposited Mn upstream and down stream from this part of the cave. Some of the possible causes of this anomaly in Mn deposition, that are yet to be studied in detail, include: higher susceptibility of the substrate (rock surface) for Mn deposition; presence of Mn-reducing bacte ria limited to dolostone Mn precipitation from dripwater coming from the rock above the passage BuroflOV Ponor also rise questions related to Mn deposition. Layers of black coating sandwiched between calcite layers on broken speleothems point to periodic inundation of the passages. By precise dating of the speleothems, an approxi mate timing of the events that led to the deposition of manganese could be established. During those events, a passage of relatively great dimensions was, at least temporarily, com pletely filled with water this suggests flow rates by few orders of magnitude greater than the ones currently flowing References HILL, C., & FoRTI, P. (1997) Cave Minerals of the World, Second Edition, NSS, Huntsville, AL., 464 p. LJuBoJEVIC, V., & GERZINA, N. (1997) New speleomorphologic re search of Cerjanska cave (Cerjanska pecina) Proceedings of3rd Symposium on karst protection, Beograd, pp. 233-252. MooRE, G. W. ( 1981 ) Manganese Deposition in Limestone Caves Proc. 8th Inti. Congr. Speleo/., Bowling Green, I & IT, pp. 642-644. ONAC, B. P., TvssELAND, M., BENGEANU. M., & HoFENPRADLI, A. ( 1997) Deposition of black manganese and iron-rich sediments in Yantului Cave (Romania). Proc. J2'h Inter. Congr. ofSpeleo/ogy, Switzerland, 1, pp. 235-238. 79 .)lrrough the cave. Once the environment and timing for cy clic manganese deposition is defined, one should try to find out if it was caused by climatic events and/or. variations of water table level (Danube River). This is one of the reasons we think it would be justified to study in detail the manga nese deposits in cave Buronov Ponor. Conclusion This is frrst research of manganese deposits performed on Serbian caves. Due to amorphous structure ofthe deposits, and lack of suitable laboratory facilities, incomplete results have been obtained. The link between passage morphology and manga nese deposition has not been established. However, some inter esting questions arose. In Cerjanska Pecina, it is still unclear why manganese deposition is bound only to a part of this single conduit cave. In Buronov Ponor, cyclicity of manganese depo sition implies a cyclicity of inundation of the lower parts of the cave, which could be correlated with climatic factors. PoTTER, R. M., & RossMAN, G. R. (1979) The tetravalent manga nese oxides: identification, hydration, and structural relation ships by infrared spectroscopy American Mineralogist, 64, pp. 1199-1218. SLABE, t. ( 1995) Cave Rocky Relief and its Speleogenetical Signifi cance. ZRC SAZU, Ljubljana, 128 p. ZLOKOLICA-MANmc, M., & MANDie, M. (1997) Buronov ponor. Proc. Jrd Symposium on karst protection, Beograd, pp. 245-253. ZLOKOLICA M., MANDIC, M., LJUBOJEVIC, V. (1996) Some significant caves at the western rim of Miroc karst. Theor Appl. Karstology, 9, pp. 77-88.

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Theoretical and Applied Karstology, 13-14 (2000-2001), pp. 81-85 Mineralogy and speleogenesis of the Ice-Cave from Poiana Vartop (Bihor Mountains, Romania) Nicoleta Feier1 Gabriel Munteanu1 & Bogdan P. Onac2* I Faculty of Biology and Geology, "Babe-Bolyai" University, Kogalniceanu 1, and "Politehnica" Caving Club, O.P 1, CP 449, 3400 Cluj-Napoca, Romania. 1 Quaternary Research Group, Dept. of Mineralogy, "Babe-Bolyai" University,Kogalniceanu 1, and Emil Racovita" Institute of Speleology, Cluj Department, Clinicilor 5, 3400 Cluj-Napoca Romania. Abstract The cave of Poiana Vartop in the NW Bihor Mountains hosts the fourth largest underground perennial glacier in Romania with a volume estimated to 12,000 ml. The ice accumulated within the cave as a result of trapping of subzero winter air through its single entrance near the top of the cave. The speleothem mineralogy is dominated by calcite, with minor amounts of included aragonite. Crusts of carbonate hydroxylapatite (associated with bat guano) and goethite (associated with pyrite i n the host limestone) are found at a few locations. Based on structural observations, dye traces, and cave galleries orientations, it is inferred that the cave is part of a much larger hydrologic karst system that also includes the nearby Humpleu-Poienita cave network Keywords: perennial ice block, speleothems, mineralogy, speleogenesis, Bihor Mts., Romani a. Mineralogie et speleogenese de Ia grotte de Poiana Vartop (Monts du Bihor, Roumanie) Resume . La Grotte de Poiana Vtlrtop abrite un des plus grands depots de glace perenne de Roumanie, dont le volume a ete estime a 12.000 m3 A pres Ia lo calisation geographique, une presentation des elernents geologique et un breve description de Ia cavite, le travail traite de La mineralogie des speleothemes et des conditions qui ontfavorise /'accumulation de Ia glace. En se basant sur les observations e.ffectuees, les auteurs concluent que Ia grotiefait partie du vaste systeme karstique qui inclut le reseau de Humpleu-Poienifa. Mots cles: bloc de glace perenne, speleothemes, mineralogie, speteogenese, Monts du Bihor, Roumanie. Geographic and geologic setting The Ice Cave from P oian a Vartop (Vartop Glade) (3415/3, in GoRAN, 1982) is located in the NW Bihar Mountains, within the plateau area that stretches between Ponorului Valley and Firei Valley (Lat. 46'96" N Long. 22'85" E), at an el evation of 1340 m a.s.l. (Fig. 1). The area has a temperate continental env ironment with pre cipitation evenly distributed throughout the year. The mean annual precipitation is approximately 1400 mm, whereas the mean annual temperature is 4 C. January is the coldest month *corresponding author. Email address: bonac@biog e.u bbcluj .ro 200 I Editurd Academiei Romilne All rights reserved. of the year (-7 C), and July the warmest one (10 C) From November to February most of the precipitation is snow; the snow cover preserves until late April. Normally between mid April and May, snow melts (BLEAHU & BoRDEA, 1981). According to BALINTONI (1997) the study area be longs to the Giurcufa Lithozone of Some litho-group that consists of schists, potassium feldspars-gneisses, amphibo lites, and feldspar quartzites Above these rocks, it lies the sedimentary unit of the Bihor Autochthonous (Alpine facies), that consists pf an 800 m-thick sequence of mixed beds of sandstones, conglomerates, marls, and limestones (MANTEA, 1985).

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82 '\ n ,,... .... The Ice-cave of -.. ""' Poiana Vartop n Vartopasu Cave Although the bedrock geology of this sector of Bihor Mountains is well known, little has been written about the karst geomorphology and caves of the area. The Ice-Cave from Poiana Vartop lies entirely within the Lower Cretaceous lime stone. At surface this rock is massive to medium-bedded, light blue-blackish limestone that weathers to a dark grey. A set of microfacies analyses carried on three limestone samples collected from different part of the cave (Fig. 2a) enabled the following calcareous algae and foraminifera to be identified in thin sections: Salpingoporella sp and Vercorsella scarselli (DE CAsTo). Their presence confirms the Barremian-Aptian age of the limestone (BucUR, pers. comm.). The limestone samples were X-rayed as being calcite or a mixture of calcite and dolomite. The local structure is extremely complex due to the presence of the Some Graben in the near vicinity. A number of high angle normal faults that show parallel strikes were mapped over the entire region. The cave itself lies near the intersec tion of two faults whose direction is NE-SW and N-S re spectively (MANTEA, 1985.). The strike of the faults and their spatial extension, along with the dye tracing performed by 0RASEANU (1996) provide the basis for a hydrogeological interpretation. The data suggest that the drainage pathways originated in organized or swallets around the Ice-Cave from Poiana Vartop (including this cave) and are all directed towards the underground stream of.Humpleu Cave (Fig. 3). N. Feier et.a/. Fig. 1. Geological map of the investigated area with the location of the Ice-Cave from Poiana Vfutop and Humpleu-Poienita karst system. 1: Lower Cretaceous limestone; 2: Albioara limestone (Tithonian); 3: Gosau Formation (limestone with Hippurites, grey conglomerates and sandstones; 4: Quartzitic sandstone and conglomerates (Lower Liasic). Carte geologique de Ia zone avec Ia situation de Ia grotte de Poiana Vartop et du systeme de Humpleu PoieniJa. 1: calcaires Cretace inferieur; 2: calcaires d'Albioara (Tithonique); 3: Formation de Gosau (calcaires a Hippurites, conglomerats et gres); 4: Gres quartzifores et conglomerats (Liassique inferieur). Description of the cave The cave was discovered and first mapped by the Speleological Club "Z" Oradea in 1978. In 1985, members of the "Politehnica" Speleological Club discovered the lower part of this large chamber after descending through a narrow "win" dow" opened due to the lowering of the ice block that forms 'the floor' of the Entrance Chamber. The access to the cave is through a semicircular collapse sink hole, on the northwestern side of the Vartop Glade. After a short descent over slide rocks covered by a thin soil layer, the 22 x S m cave porch leads to a chamber that hosts a 12,000 m3 peren nial ice block. The Entrance Chamber has 60 m in length, a maximum of 25 m in width and about 5 m in height (Fig. 2a). Along the southeastern wall, three narrow openings (1.5 x 0.5 m) give access to the lower part of the chamber through a 42 m long, steeply descending (40 ) ice slide (Fig. 2b). At the bot tom of this chamber large quantities of frost debris are to be found. The lowest point of the cave is-38m and it was reached in this sector, after descending another 5.5 m long and nar row passage (Fig. 2b). Mineralogy of speleothems Only conventional speleothems such as stalactites, flowstones and crusts were noticed in the Ice-Cave from Poiana Vartop. Most of these speleothems are inactive and deeply corroded.

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The Ice-Cave from Poiana Vdrtop 83 (a) t N (b) 10m L 0 10m Re-surveyed: Topography: Feier Nicoleta Munteanu Gabriel Munteanu Gabriel Feler Nicoleta o..-L-..... 10m Zaharia Luminita Fig. 2. (a) Map of the Ice-Cave from Poiana Vfutop. A-G =samples points; (b) Cross-section of the cave showing the ice block and the winter air circulation. (a) Carte de Ia Grotte-glaciere de Poiana Vartop. A-G =points d'echanntillonage; (b) Section transversale avec Ia situation du bloc de glace et Ia circulation d'air en hiver. m 1400 1200 Pod swallet 0 Vlirtop Glade swallet 2 Firei Valley SurileFirei 4km Fig. 3. Simplified hydrogeological transect showing the relationship between Firei Springs and the main swallets in the area of the IceCave from Poiana Vfutop (Humpleu Cave profile is tentatively located within the cross-section). Note that the vertical scale is exaggerated. Section hydrogeologique simplijiee montrant Ia relation entre Ia source de $urile Firei et les principaux ponors de Ia zone de Ia Grotte Glaciere de Poiana Vartop (Ia coupe de Ia Grotte de Humpleu est figuree approximative). A noter que l'echelle verticale est exageree. Macroscopic and optical microscope observations, as well as X-ray diffraction analysis on seven crust samples revealed the presence of the following four minerals: calcite, aragonite, goethite and carbonate-hydroxylapatite. Calcite makes up the bulk of the flowstone, stalactite and corraloid deposits. Aragonite has only been observed in thin sections as layers of minute crystals with radially oriented c-axes that are sandwiched within layers composed of more coarse-grained calcite crystals. Goethite and carbonate-hydroxylapatite speleothems are restricted to very few places within the cave. As expected, carbonate-hydroxyl-apatite was found as dark brown to black crusts in the near vicinity of an area that was earlier populated by bats. Therefore its origin was related to the reaction of phosphate solutions with limestone. The X-ray pattern shows a number of lines, most of them well marked and sharp. The strongest seven lines are listed in Table 1. The interplanar spacing and intensity values are very close to those recorded for carbonate-hydroxylapatite in the ICDD file 19-272.

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84 Table I Comparison of X-ray diffraction lines for carbonate hydroxylapatite collected in the Ice-Cave from PoilUla Vartop and those from !COD file Comparaison entre les /ignes de diffraction en rayons X de Ia carbonat-hydroxylapatite de Ia Grotte de Poiana Viirtop et celles desjichiers de 1'/CDD ICDD 19-272 Sample #1357 d(A) d(A) 3.46 25 3.45 13 2.78 100 2.79 100 2.68 40 2,70 25 2.49 6 2.49 15 2.28 6 2.29 17 1.92 16 1.90 17 1.85 10 1.87 15 Goethite crusts form centimeter-size patches on the wall near the bottom of the cave. Oxidation of some pyrite from within the limestone seems to be the source for iron in these speleo thems. Speleogenesis The cave is developed within an inclined lithologic contact, not far from the base of the aquifer. In vertical projection (Fig. 2b), the cave comprises an inclined passage that shows both phreatic features (pendants, scallops, corrosion pock" ets) and vadose (newly formed or corroded) speleothems. Recent observations made within the cave showed that the cave has received substantial amounts of allogenic gravel and sand. This is a situation similar to that encountered in many caves in the neighborhood, including the major cave system of Humpleu-Poienita. The morphology of the cave suggests that it could have been developed in two distinct phases: (i) A shallow phreatic stage, when waters collected (dif fuse or organized) from Groapa Larga and Viirtop Pla teau wer. e drained through the upper passages of Humpleu Cave, to feed small springs along Firei Val ley (Fig. 3). This is the stage when gradual removal of the rock by dissolution allowed huge passages to be formed (ii) In the second stage, following the connection of the drainage conduit to a major outlet (i.e., Firei Springs) the cave begun its evolution under vadose conditions (FoRo & WILUAMs,l989). Undercut by free surface streams, the cave ceiling and wall became N Feier eta/. weakened fact that led to massive breakdown in the cave. Speleothem deposition is superimposed on the phreatic features Frost wedging is also a late-stage process that was more effective near the cave entrance, but after accumulation of ice in the cave it became common throughout the cave. We believe the current entrance has been created by slope processes that enabled mass movement of the limestone bedrock along joints with slippage along bedding planes. The dye tracing experiments performed by 0RASEANU (1996) indicated that the surface streams located at E, NE and N of the Ice-Cave from Poiana Viirtop sink through the swallets in the Groapa Larga area and Viirtop Plateau. Therefore we believe the investigated cave is part of much larger hydrologic karst system that also includes the Humpleu-Poienita cave network. The entire system discharges at Firei Springs after cross ing Humpleu Cave; the average flow rate measured reaches c. 80 1/s (0RASEANU, 1996). Origin of the ice block The Ice-Cave from Poiana Viirtop is a descending cavity that opens to the surface only on its upper part. For this reason it belongs to the category of cavities with bi-directional ventila tion, in which the active phase is limited to the winter season (RAcovrrP., 1975). During the winter, cold and dense external air enters the cave and replaces an equivalent volume of rela tively warmer underground air (Fig 2b). In summer this exchange ceases somewhere at the surface of the ice block be cause the thermal ratio reverses and the cold cave air accumu lated throughout the winter cannot rise to the surface. The long term effect of such a thermo-circulation system is that the cave constantly accumulates cold air, and finally a glacial-type topoclimate is established within the cave. Therefore, one may conclude that cooling by accumulation of cold air represents the mechanism that is responsible for the perennial ice block formation in the Ice-Cave from Poiana Viirtop. Like in the case of Sclirioara Ice-Cave, melting of snow and ice at the bottom of the cave entrance slope and the percola tion water seems to be the source of water that subsequently accumulate in the form of ice layers in the Ice-Cave from Poiana Viirtop. Unfortunately, the ice block structure is hidden behind a thin ice layer formed during summer when melting waters reach the undergro und environment with sub-zero temperatures The ice block lies in one large chamber occupying 2/3 of its volume. A rough estimation of the overall ice block volume is 12,000 m3 which means that the Ice-Cave from Poiana Viirtop hosts Romania's fourth largest underground glacier after Sclirioara, Focul Viu and Bortig.

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The Ice-Cave from Poiana Viirtop Acknowledgements We are indebted to Dr. loan Bucur (University of Cluj) for carrying out the microfacies analyses and to Ovidiu Pop, Jos and Geert Notenboom for their assistance in the field. Vlad Breazu is thanked for providing the GPS data. The fieldwork for this study was partly financed through the ANSTI grant B37/2000 to Tudor Tlima. References B ALINTONI, I. ( 1997) Geotectonica terenurilor metamorfice din Ro mania. Ed. Carpatica, Cluj, 176 p. 85 BLEAHU, M.,l & BoRDEA, S. (1981) Muntii Bihor-Vladeasa. Ed. Sport-Turism, Bucuresti, 496 p. FoRo, D. C., & WILLIAMS, P. W. (1989) Karst geomorphology and hydrology. Unwin Hyman, London, 602 p. GoRAN, C. (1982) Catalogul sistematic al peterilor din Romania. ISER & FRTA-CCSS, Bucureti, 496 p. MANTEA, G. (1985) Geological Studies in the Upper of the SomeUl Cald Valley and in the Valea Seac1i Region (Bihor Vladeasa Mountains). An. IGG, 68 pp. 1-91. ORASEANU, I. (1996) Contributions to the hydrogeology of the karst areas of the BihorVladeasa Mountains, Romania. Theor. Appl. Karstology, 9, pp. 185-214. RAcovrrA, G. (1975) La classification topoclimatique des cavites souterraines. Trav. Inst. Speol. "E. Racovitw", XIV, pp. 197-216.

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Theoretical and Applied Karstology, 13-14 (2000-2001), pp. 87-92 La genese et l'evolution des grandes dolines ( obans) de Ia zone karstique de Mangalia (Dobroudja du Sud, Roumanie) Traian Constantinescu & Silviu Constantin lnstitut de Speologie Emil RacoviJa str. Frumoasa 11, 78114 Bucarest 12, Roumanie. Resume Pour expliquer Ia genese et I' evolution des grandes do lines ou obanes de Ia zone karstique de Mangalia, Obanul Mare est le plus representatif, du fait qu'ici ont etc effectues de nombreux forages et qu'll son bord s'ouvre Ia celebre Grotte de Movile. Les sediments accumules dans I' oban sont des reperes pertinents qui argumentent Ia genese du celui-ci par effondrement karstique Au cours de leur evolution, ces grandes dolines ont connu trois phases principales : de doline-lac, de doline-marecage et de doline-seche. Mots cles: oban, obans, doline-Iac, doline-marecage, doline-seche, Mangalia, Grotte de Movile. The genesis and evolution of the great sinkholes (obans) 'f rom the karst area of Manga/ia (Southern Dobrogea, Romania) Abstract In order to explain the genesis and the evolution of the great sinkholes or 'obanes' from the Mangalia karstic area the structure of "Obanul Mare" is discussed based on a series of boreholes and exploration pits and due to its proximity to the Movile Cave The geolog i cal structure of the sediments accumulated in these sinkholes suggests their genesis through a karstic collapse mechanism. Subsequently, the great sinkholes underwent three main evolutionary phases: the "lake-sinkhole" phase, the swamp sinkhole" phase and the "dry-sinkhole" phase Key words: oban obanes, lake-sinkhole, swamp-sinkhole, dry-sinkhole, Mangalia, Movile Cave. La zone karstique de Mangalia se trouve a 1' extremite sud-est de Ia Roumanie, au bord de la Mer Noire (Fig. 1A). La region presente une horizontalite evidente. Les altitudes absolues soot comprises entre 0 et 40 m. La morphologie generale montre deux larges vallees, Valea Mangaliei et Valea Obanelor, separees par un interfluve (CoNSTANTINEscu, 1989). Dans ces vallees affleurent des calcaires sarmatiens qui ont favorise Ia formation d' un exokarst I oban ( s ing .)= gr.ande doline ; on de maintenir le mot roumain ains i : oban (sing ) obanes (pl.). En Rounilrin, le pluriel se prononce : (( obane *correspond i ng author. E-mail address : Silviu.Constantin@geol.uib.no 200 I, Editura Academiei Romane. All reserved specifique. Tres representatives soot les depressions karstiques grandes dolines denommees en Dobroudja du Sud oban 1 On peut reconnaitre trois secteurs avec de telles dolines, representant trois complexes exokarstiques dont celui de Movile est le plus important. ll comprend un groupe de trois dolines : Obanul Mare, Obanul Mic et Obanul Blebea (CoNSTANTINESCU, 1995, Fig. 1). Obanul Mare oil se trouve la Petera de La Movile (La Grotte de Movile) est le plus representatif pour la genese et !'evolu tion de tC>utd ces grandes dolines. L'Institut d'Etudes et Projets d'Amenagements Fanciers (l'ISPIF) et l'lnstitut Geologique ont effectue en deux reprises en 1986 et 1994 des forages et des puits qui ont apporte des donnees nouvelles sur sa structure de profondeur.

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88 La morphologie generale de Obanul Mare Dans le cadre du complexe de Movile, Obanul Mare s'impose d'emblee parla morphologie des deux composantes: Labor dure et La depression proprement dite. 0 Obanul Mare \ L 100 200m IOI1.IGI2. s. ..... G 1. 0 a. 8 9. T. Constantinescu & S. Constantin 1. La bordure, avec une largeur de 40-70 m, est composee essentiellement de calcaires sarmatiens et s' elargit progres sivement vers le sud. Notons que Ia morphologie de Ia bordure sud a subi des changements importants apres 1989, car plusieurs petites dolines ont ete totalement colmatees par les dechets apportes de Ia ville .a. de Ia 1 Obanul Mare 2. Obanul Mic A BULGARIE Fig. I Carte geomorphologique de Ia zone karstique d'Obane. Position de Ia zone de Movile en Roumanie (A) et dans Ia region de Mangalia (B). 1. Movile (monticule calcaire conique) ; 2. Doline ; 3. Doline-ponor ; 4. Source permanente ; 5. Marecage ; 6. Abrupt ; 7 Courbe de niveau ; 8. Cote ; 9. Limite de l'ouvala de. La Movile ; 10. Drainage souterrain demontre. Geomorphic map of the karstic area ofObane. General location of the Movile area within Romania (A) and within the region of Mangalia (B). I. "Movile" (conical limestone hillock); 2. Sinkhole; 3. Swallet-sinkhole; 4. Perennial spring; 5. Swamp; 6. Cliff; 7 Contour ; 8. Elevation; 9 : Limit of the "La Movile" ouvala; 10. Proved underground drainage.

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La genese et l'evolution des grandes dolines La specificite de la morphologie est donnee par 1' ensemble moviles (= monticules)--dolines. L'altitude absolue la plus elevee, de 29,0 m, a ete mesuree sur un monticule situe entre l'Obanul Mare et l'Obanul Mic. Les plus grandes dolines, par exemple celles qui se trouvent dans la partie sud, sont le resultat d'effondrements de la voOte des vi des sou terrains. Les autres sont 1' effet de la presence de vides sou terrains de dimensions plus petites (semblables a celles de la Grotte de Movile), qui n'ont pas subi en core des effondrements karstiques. 2. La depression proprement dite a une denivellation generale de 10-14 m. La plus petite altitude absolue, de 9,5 m ( c'est-a-dire la plus grande profondeur de l'oban) se trouve dans la partie nord-est. La denivellation maxi mum dans le cadre de l'oban est done de 19,5 m. Le fond de la depression prese111e un petit soulevement dans la partie centrale (13-14 m au centre et 10,0-10,5 m ala peripherie). Resultats des forages de Obanul Mare Initialement, 1' oban a eu une profondeur plus grande qu'aujourd'hui, mais il a ete colmate avec des materiels lressoldes, transportes par le vent et des argiles lacustres. La presence des ces depots a ete demon tree lors des forages effectues par l'ISPIF en 1986 ( coordonateur Emanoil Constantinescu ; GEoRGEscu et at., 1987), qui ont permis de preciser que leur epaisseur depasse 70 m (Fig. 2). L'analyse sommaire des depots a mis en evidence deux niveaux de sediments, differencies au point de vue mineralogique et de la texture, fait tres important pour expliquer la genese et I' evolution de l'oban. Le niveau superieur dont 1' epaisseur est de 15-20 m, est constitue principalement de sols fossils developpes sur des depots lressoYdes. La presence des depots lressoYdes solifies indique !'existence d'une depression qui a ete colmatee avec les depots mentionnes. Les depots ont des couleurs di verses ( variant du brune au jaunatre ). Les horizons de sols fossiles, correspondent aux.diverses phases clima tiques dans I' evolution de l'oban. II faut mentionner que dans la partie inferieure de ce niveau on a trouve des blocs calcaires non alteres, qui peuvent representee les depots d'effondrement karstique les plus recents. Le niveau inferieur est constitue de depots argileux ayant une epaisseur de 25-30 m, compose de divers horizons d' argiles avec des intercalations des blocs calcaires. Tbeo riquement, ces depots peuvent se former, au mains parti ellement, par la dissolution des calcaires sarmatiens mais leur structure, les couleurs et leur disposition spatiale (Fig. 2) suggerent qu'ils peuvent etre, en partie, allochtones. 89 Ace niveau tousles forages ont intercepte des blocs calcaires faiblement alteres ou meme non-alteres ayant c.Ies-epaisseurs qui varient entre 0,5 et 2 m. La genese et I' evolution d'Obanul Mare On a anticipe que l'
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Obanul Mic 9h I 0 "" 20 10 0 -10 -20 -!0 -40 -50 -60 -70m F202 27JJ'llt 30 20 10 0 -10 -20 -30 -40 -50 -60 -70m Obanul Mic JO a N -- marecage : : :J Mmr .z:: z 0 -10 -7.0 -30 -40 -50 -60 ...:1om s Obanul Mare 25 0 SOm f77)] 1.1:LLLJ 2. g Jll1 4.ca a.liiJ 7 9. 10. LR._j 11.L.:.:..:J rEliil 0 100 200 m E \0 0 :-'! g ::s "' iS ::s s Ro g iS ;:, S

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La genese et l'evolution des grandes dolines 91 Fig. 2. Sections geologiques les obans d'apres les donnees de forages de l'ISPIF (interpretees par les auteurs). En vignette (a), plan de situation des forages et des puits. F=forage ; P=puits. Les chiffres places en bas des forages indiquent Ia profqndeur de ceux-ci. 1 Sols actuels; 2. Sols fossiles; 3. Depots argileux; 4. Calcaires du Sarmatien; 5. Intercalations argileuses; 6. Fragments calcaires non alteres; 7. Blocs calcaires faiblement alteres ou non-alteres; 8. Altitude absolue des forages (puits); 9. Vides karstiques ; 10. Source mesothermale ; II. Horizons des sols. Geologic profiles through the "obans" interpreted by the authors after the data of exploratory boreholes and wells of ISPIF. Inset (a) shows the situation of the boreholes and wells. F=borehole; P=well. The numbers at the bottom of the boreholes indicate their final depth. I. Holocene soil; 2. Fossil soil; 3. Residual clayey deposits; 4. Sarmatian limestones; 5. Clayey intercalations; 6. Unaltered fragments of limestone; 7. Slightly altered or unaltered limestones; 8. Absolute altitude of the boreholes (wells); 9. Karstic voids; 10. Mesothermal source intercepted by the borehole; 11. Soil horizons. La phase de lac a ete, done, la premiere dans 1' evolution de I' oban. A ce temps Ht, la Grotte de Movile se trouvait au dessus du niveau de lac (le fond de l'oban) et communiquait probablement avec l'exterieur. b) La Phase de Man!cage. L'assechement du lac a ete declenche par : 1' accumulation des dep6ts argileux et/ou lressoYdes dans 1' es pace de l'oban qui a barre progressivement les sources ascensionnelles de !'aquifere mesothermale, sulfureux; une possible infiltration de l'eau du lac vers !'aquifere karstique, favorisee par la texture poreuse des calcaires lumachelliques du Sarmatien ; En meme temps, des depots lressoYdes colmataient graduelle ment 1' oban, de sorte que sa profondeur a ete diminuee et le lac a ete graduellement transforme en marecage. Dans cette phase, il est tres probable que le fond de 1' oban a ete souleve jusqu'au niveau de la grotte et meme au-dessus de celui-ci, en interromprant ainsi sa communication avec l'exterieur mais, theoriquement, en phase de marecage !'interruption de Ia liaison avec l'exterieur pouvaient n'etre que temporaire. Fig. 3. Obanul Mic (phase de man!cage) et Ia bordure sud d'Obanul Mare. Obunul Mic (swamp phase) and the southern margin of the Obanul Mare. c) La Phase d'Oban Sec. En suivant la diminution du debit d'alimentation l'oban est reste a sec. Le colmatage avec des depots lressoYdes a continue et le fond de 1' oban a ere souleve au-dessus du niveau de la grotte, qui a ete fermee: situation qui se maintientjusqu'a aujourd'hui. Conclusions On peut affmner que dans son evolution, l'Obanul Mare a parcouru trois phases principales : oban-lac, oban-marecage, oban-sec. En !'absence des preuves certaines en faveur de !'existence de ces phases, la presence dans la region d'autres obans se trouvant en differentes phases de colmatage, peut etre consideree comme un argument pertinent. Par exemple, la phase d'oban-lac est representee actuellement par le lac de Kara-Oban, la phase de marecage par la Mlatina (=Mare cage) de Mangllia et par Obanul Mic (Fig. 3) et la phase d'oban sec, par O_!Janul Mare (Fig. 4). Le cavernement initial a ete creuse par 1' eau de 1' aquifere meso thermal, ascensionnel de la Dobroudja du Sud. Ce cavemement

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92 a ete detroit par effondrement karstique. La formation du niveau inferieur, des sediments argileux, peut etre partielle ment attribuee a la dissolution des calcaires. A cet egard, on peut rappeler que to us les fora ges ont intercepte des interca lations argileuses lenticulaires dans les calcai res sarmatiens (Fig. 2). Mais la phipart des sediments argileux, qui forment aujourd'hui un melange avec des blocs calcaires ont ete deposes dans des lacs formes dans I' espace des obanes. En dessous de ces depots, la karstification des calcaires sarmatiens a continue jusqu' a present. Compte tenu de 1' des depots identifies dans les for ages on peut affirmer que la profondeur maximale de 1' Obanul Mare a ete de plus de 70 m, dans sa partie sud (F107). Par colmatage graduel, le lac s'est transforme en marecage et, ulterieurement, il a seche completement; la partie superieure des dolines a ete remplie de depots lressoYdes qui ont coupe aussi la communication avec l'cxterieur de l'6tage superieur du cavemement, dont la grotte de Movile en fait partie. Bibliographie T. Constantinescu & S. Constantin Fig. 4. Obanul Mare: Ia depression proprement dite '(phase d'oban-sec) et Ia bordure est. La fleche blanche indique le plus haut monticule (29,0 m) de Ia zone. Obanul Mare : the depression (dry oban phase) and the eastern margin. The white arrow indicates the highest hillock of the area (29.0 m asl.) CoNSTANTINESCU, T. (1989) Considerations sur Ia zone karstique La Movile" (Mangalia, Dobrogea de Sud, Roumanie), Misc. Speol. Romanica, 1, CoNsTANTINEscu, T. (1995) Le karst de type Movile (Mangalia,Dobrogea de Sud, Roumanie). Theor: Appl. Karstology, 8, pp.91-96. GASPAR, E., & ORASEANU,I. (1987) Natural and artificial tracers in the study of hydrodynamics of karst. Theor. Appl. Karstology, 3, pp. 31-107. GEORGESCU, 1., TRIFAN, L., CONSTANTINESCU. E., & SELETCHI, E. ( 1987) Cercetarea complexli a unui arrip!asament in conditii speciale, in zona CET-Mangalia. Lucriirile JSPIF, pp. I 01-109 LAscu, C. (1989) Paleogeographical and hydrogeolo6ical hypoth.. esis regarding the originof a peculiar cave fauna. Misc. Speol. Romanica, 1, pp 13-18. LAscu, C., PoPA, R., & SARBU, S. (1995) Le karst de Movile (Dobrogea de Sud) (1). Revue Roum. Geogr., 38, pp.86-93.

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Theoretical and Applied Karstology, 1 3-14 (2000-2001), pp. 93-99 24 h Tracer Tests on Diurnal Parameter Variability in a Subglacial Karst Conduit: Small River Valley, Canada Jan-Henning Ross 1 *, Feride Serefiddin2 Michael Hauns3 & Chris C. Smart4 I Gottelmann +Ross, Beratende Geowissenschaftler, Schulstrasse 4, D-78462 Konstanz, Germany. 2 School of Geography and Geology, McMaster University, 1280 Main Street West Hamilton ON L8S4Ml, Canada. 3 lnstitut for Hydrologie, Universitiit Freiburg,Fahnenbergplatz, D-7'9098 Freiburg, Germany 4 Depw1ment of Geography, University of Western Ontario, London Ontario NGA 5C2 Canada Abstract Repe a ted dye tracer tests were undertaken for two complete diurnal discharge cycles at Small River Glacier British Columbia. The injection s ite is a well developed glacier moulin. Monitoring was done at a karst spring in a cave entrance 1530 m down valley The spring is the major outlet of glacial meltwater and also drains karstified glacier forefields High flow velocities and low dispersivities indicate a very well developed conduit flow system. Discharge and velocity show strong diurnal cycles and are controlled by the amount of meltwater. The rela tionship of increasing velocity with discharge is approximately linear. Dispersivity values do not show any significant variation under diurnal discharge cycles. These show the importance of diurnal variation in a transient groundwater system. Keywords: subglacial karst hydrogeology, diurnal discharge-velocity relationships, tracer tests Tests de trat;age de 24 heures sur Ia variabilite des parametres journaliers dans un conduit karstique sous-glaciaire: Small River Valley, Canada R e su me D e s experiences de trarage au cours de deux cycles journaliers complets ont ete entreprises sur La Small River Valley de British Columbia. Le point d'injection est un moulin glaciaire bien developpe. Le traceur a ete monitorise 1530 men a val. dans La sour c e kar s tique d'une grotle La source est une exutoire majeur de L'eau de fusion de La glace qui draine aussi des terrains karstifi es non-gl aci aires. Les vitesses d 'ecouleme.nt elevees et Les dispersivites basses indiquent un systeme d 'ecoulement par conduits tr es bi e n de v eloppe. Les debits et Les vitesses sontfortement variables au cours d'un cycle journalier et sont controles par La quantiz e d eau de fusion La relation entre La vitesse d' ecoulement et Le debit est presque Linea ire La variation des valeurs de La d i spersivit e n 'esc pas signijlcative au cours des cycles journaliers. Les resultats montrent ['importance de La variation diurne dans un sys t e me phreatique en regime transitoire Mots cles : hydrogeologie karstique sous-glaciaire, relation debit diurne-vitesse d'ecoulement, tests de trarage. Introduction Glaciers are well known as highly dynamic hydrologic sys tems with strong seasonal and diurnal discharge variation. Cyclic changes in key climatic factors such as radiation and temperature cause a transient flow system. Seasonal develop ment of a glacial flow system is e.g. described by HocK & corresponding author. -mail address: ross@geowissenschaftler.de 200 I Editurd Academiei Romane. All rights reserved. HooKE (1993). NIENOW et al. (1996) focused on diurnal cy cles in a glacial system. SMART (1983, 1997) examined the influence of glacier hydrology on subglacial karst systems at Castleguard Cave and at Small River Glacier. Glacial melt water is the main input source to these karst systems. Dis charge variations of glacial meltwaters stimulate the flow re gime in subglacial karst systems. Thus discharge of subglacial karst springs linked to variations in the system feeding gla cier discharge.

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94 "7"-r-r cliff D Carbonates t ... j Siltstone f:.'"j Till over Siltstone J.-H. Ross et al. --... ____ ----Fig I Small River Glacier with underlying geology and cross-section from the tracer injection moulin to South Spring (based on SMART, 1996 and 0RWI N pers comm ) Situation geol o gique de Ia Small River Valley et section entre le moulin d'injection du traceur et le South Spring (d'apres SMART, 1996 et 0RWJN, comm pers ) Small River Glacier is a temperate glacier in the Western Canadian Rocky Mountains of British Columbia (Fig. 1). The glacier surface is 2 5 km2 from 1900 m up to 2900 m a.s .l. The glacier is underlain by two northeastwar
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24 hours tracer tests on dirnal parameter variability 1000 ........... o; 0.400 .... Q) 0 ttl 200 0 223.0 ''-.._ ,, "_..i.'" .. 4'\ ... ....... . ,, v v I ./ I I! \ \ \ \. 223.5 ..... f-'-. ......... \..., ''"". '-F \ . I ".. i J \., 224.0 JuianDays .... l "' . ............ :. ... '\_ -.:,,.:.. .. ,,.,..., --Uranine -RWT' ....... Di sct-arge 224.5 225.0 Fig 2. Tracer breakthrough curves on 11/12 August and discharge. Rising discharge in the afternoon of Julian day 223 is a regular meltwater pattern The bigger flood during the night to day 224 is due to a thunderstorm. Courbes d'apparition du traceur durant Ia nuit de 11112 Aout et variation du debit. L'augmentation du debit l'apres-midi du 223-e jour julien appartient au modele normal de fusion. La crue enregistree Ia nuit du 224 e jour a ere provoquee par un orage 1000 "Ci
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96 Tracer monitoring was done with a CGUN-FL02 flow-through field fluorometer (ScHNEGG & DoERR..INGER, 1997) Tracer con centrations were recorded with a time step of 4 minutes (test I) and 10 seconds (test II) with this device. Alternating ap plied tracers were the fluorescent dyes Rhodamine WT (RWT) and Uranine. 13 injections were made within 24 hours (in cluding a 6 hour gap due to a thunderstorm) with 2 hour in tervals from ll'h to 12th of August 1999 (Fig 2) A second diurnal cycle was traced on 14th and 15th August 1999 with 7 injections and 4 hour intervals (Fig. 3). A single test was added after storm flow on the evening of the 15th. During the repli cate tracer injections discharge of the supraglacial stream was in the range of 50 lis to 80 lis with peak flow in the afternoon. Tracer injection mass varied from 0.08 kg to 0.18 kg. In Fig. 2 and 3 tracer concentrations are divided by injection mass in order to compare breakthrough curves of different tracer tests. The following flow parameters were estimated by tracer break through curves: 1 Time between dye injection and arrival time of the tracer peak at detection site 2 Aow velocities (assuming a triangulated straight-line of 1530 m from moulin to spring, hence the true dis tance remains unknown). 3. Dispersion coefficient, which describes the dispersion of the tracer during the discharge process according to analytical solutions ofMALOSZEWSKI & ZUBER (1990), implemented in the model code TRACI (WERNER, 1997) and by SAUTY & KINZELBACH (1988) (imple mented by HAuNs & JEANNIN, 2000) Dispersivity is represented by the spreading of tracer within one flowpath. The dispersivity is equal to dispersion divided by mean velocity Results Spring discharge Discharge at South Spring shows regular diurnal changes from low t1ow in the morning to peak flow in the evening as a consequence of daily glacial ablation. During the 1999 moni toring period discharge varies from 450 lis to 1050 lis. In previous years recorded floods were up to 1500 lis. Water temperature was very stable at ca. 1.6 C. Electrical conduc tivity was about 40 j.JS/cm with slight anti cyclic alterations. Water turbidity was about 3 NTU This regular diurnal pat tern is displaced by stormflow events leading to quick flood reactions at the karst spring During those events there is a minor increase in electrical conductivity. A much more sig_ nificant reaction to stormflow events is shown by turbidity, which increases by more then 10 NTU (Fig 4). J.-H. Ross et al. Dye tracer tests Injected tracer arrives very quickly at the spring after a flow time of 2-.:.3 hours. Maximum flow velocities are in the range of 540 mlh and 746 mlh while corresponding peak flow ve locities were between 472 mlh and 643 mlh. The peak of the breakthrough curve is very sharp and quick with a short, steep tailing. The breakthrough curve finishes after a short period, this means there is only a small retardation of dye within the COJ!duit system. Calculated dispersion is in the range of 0.2 m2/s to 0.5 m2/s and dispersivity is about 2-3 m. These high flow velocities and low dispersivitiy values indicate a very well developed conduit system. Aow conditions are close to piston-flow (Fig 2, 3, 4. and 6). Flow velocities vary as a consequence of diurnal discharge variations, but without any extreme changes. There is a strong linear correlation between discharge and flow velocities at both events (Fig. 5). Peak flow velocities (V peak) can be de scribed with the following relation to discharge Q (correla tion coefficient 1.2 = 0.98): v""ak = 0.36Q + 311 This correlation is valid, of course, only within the obserVed discharge range Significant hysteresis effects, as described for diurnal variations of flow velocities in englacial conduits by NIENOW et al (1996) were not observed at South Spring Diurnal hysteresis effects in englacial systems are caused by changes of the englacial flow patterns Most of the South Spring conduit system is within the karstified limestone and only some 100 m of the passages are estimated to be within the ice. No meaningful correlation for the variation of dispersivity values and diurnal discharge cycles was found. Differences between single values are riot much larger than the results of replicate fitting approaches. All observed dispersivity values represent very well developed flow conditions (Fig. 6). Lin ear changes in flow velocities and stable dispersivity values indicate a stable conduit flow system without significant changes in flow paths. Hydraulic border conditions appear to be stable within the observed discharge ranges stable and a high percentage of the conduit system might be phreatic This interpretation fits direct observations in Marmot Cave: South Spring emerges from a .. siphon in the cave entrance area, c. 50 m further on the cave river is accessible again, but soon disappears under another siphon. Hence the experiments were performed during medium discharge rates, extreme events might show different parameter behaviour. Compared to other karst conduit systems South Spring flow velocities are very high and have extremely low dispersivities. The karst conduit system of the Rinquelle (Swiss Alps) has flow velocities in the magnitude of 111 mlh to 263 mlh and higher dipersivities (RIEG, 1994). This applies to most karst conduits of the Swabian Alb, Germany (JAKOWSKI, 1995), too.

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24 hours tracer tests on dirnal parameter variability 1.100 ......... 1.000 rE --Discharge Pis] Turbidity [NTU] E ........ 900 0 Peak Flow Velocities '(J 0 Q) BOO > 3: 0 700 LL ro Q) 600 0... 500 ........ Q) 0) L.. 400 ro (/) 0 300 200 ---------%------------o<> ...................................... 223 224 225 226 Julian Days Fig. 4. Diurnal patterns of discharge, turbidity and flow velocities at South Spring. 227 228 Modele des variations journalieres du debit, de La turbidite et des vitesses d'ecoulement de South Spring. 700 6fD :c -...600 >. ....... "(3 0 Qi 5fD > 3: 0 u:::: 500 Rl Q) c... 4fD 400 400 500 700 Dischcl'ge [L's] Vaocities 11.112. Vaocities 14./15. -Unea" 15 10 5' 1-z ........ 5 1(lX) Fig. 5. Scatter-plot of peak flow velocities and discharge Flow velocities vary significant as a consequence of discharge variations. Diagramme de correlation entre les vitesses d'ecoulement maximales etle debit. Les vitesses d'ecoulement sontfortement injluencees par les ''ariations du debit.. 97

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98 E > c;; .... Q) c.. "' 0 1.-H Ross et at. 3 <> <> <> <> <> <> <> <> 2 <> <> Dlsperslvltles 11 112 August + Dispersivltles 14115 August 400 500 600 700 800 900 1000 Discharge [1/s] Fig 6. Scatter-plot of dispersivities and discharge. Low and almost constant dispersivity values are indicating a well developed conduit system Diagramme de correlation entre les dispersivites et le debit Les dispersivites basses et presque constantes indiquent un systeme de conduits bien developpe Conclusions Within the investigated discharge range the flow sys tem remains stable in one conduit system without changing flow paths. This conclusion is based on a linear discharge-velocity correlation and stable dispersivity values. Case study Small River Valley The spatial scale of South Spring at Small River Gla cier makes this site a suitable place for investigations on diurnal cycles of hydrological processes in a sub glacial karst system Short travel times of injected tracer and low dispersivity allow several injections a day without interference of single tracer tests (Fig. 2, 3) Whereas flow velocities are strongly correlated to di urnal alternating discharge, dispersivity does not show significant changes. South Spring/Mannot Cave is a very well developed "high speed" conduit karst system with significant diurnal flow velocity changes. Analytical modeling results show geohydraulic con ditions extremly close to piston-flow. The hydraulic system is partially under pressure flow conditions as interpretated by tracer tests and as directly observed in the cave. The variation of storm flow induced events exceeds the variation of diurnal run-off cycles. Subglacial Hydrology Online-fluorometers combined with dataloggers (SCHNEGG & DOERFLINGER, 1997; SMART & ZABO, 1997) are crucial tools to investigate on diurnal processes in alpine hydrology Otherwise logistic problems in sampling and data processing would be tremendous. A single tracer tests gives only a random result within the diurn .al parameter range of flow velocity without accurate information about parameter variabilitiy Replicate tracer tests are necessary for estimating the geohydraulic parameter range of a flow system with diurnal cycling patterns.

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24 hours tracer tests on dirnal parameter variability Acknowledgements Small River Research is supported by the Natural Sciences and Engineering Research Council of Canada and the Uni versity of Western Ontario. Thanks to John Orwin for data logger support and Andy Calarco for surveying. Thanks to Shauna Flanagan and Kumari Karunaratne for assistance in the field. Reviewing by Jose M. Calaforra and Paul G. Marinos gave helpful suggestions and is gratefully acknowledged. References HAUNS, M., & JEANNIN, (2000) Tracer transport in karst con duits: a computational fluid dynamics-based modeling approach. In: Karst Studies and Problems: 2000 and Beyond. Proc. of the joint meeting of Friends of Karst, Theoretical and Applied Karstology/IGCP 448, July 2000 Cluj-Napoca, Romania pp. 56-62. HocK, R., & HooKE, R. Le B. (1993) Evolution of the internal drain age system in the lower part of the ablation area of Storglaciiiren, Sweden. Geol. Soc. Am. Bull., 105, 4, pp. 537-546. JAKOWSKI, A. ( 1995) Ermittlung der Dispersion und anderer geohydraulischer Parameter aus Markierungsversuchen in Karstund Kluftgrundwasserleitem BadenWiirttembergs. Ph.D. Thesis. TH Darmstadt. 546 p. LowE, D. J. (1983) The Anglo-Canadian Rocky Mountain speleo logical expedition, 1983. Trans. British Cave Research Ass., 10 pp. 213-244. 99 MALOSZEWSKI, P., & ZuBER, A. (1990) Mathematical Modelling of Tracer Experiments in Fissured Rocks. Water Res. Res., 26, 7 pp. 1517-1528. NIENOW, P., SHARP, M., & WILLIS, I. (1996) Velocity-discharge rela tionships derived from dye-tracer experiments in glacial melt waters: implications for subglacial flow conditions. Hydrologi cal Processes, 10, pp. 1411-1426. ORWIN, J. F. (pers. comm.) Geomorphological Map of Small River Glacier, British Columbia (unpublisMd). RIEG, A. (1994) Zur Hydrologie im Karstgebiet Churfirsten -Alvier. Ph. D. Thesis. University of Freiburg. SAUTY, J.P., & KINZELBACH, W. (1988) CATTI (Computer Aided Tracer Test Interpretation). Delft, Indianapolis, 79 p. ScHNEGG, P.-A., & DoERFLIGER, N. (1997) An inexpensive flow through field fluorometer. I2'h International Congress of Spele ology, I997 Switzerland, 2, pp. 47-50. SMART, C. C. (1983) The Hydrology of the Castleguard Karst, Co lumbia Icefields, Alberta, Canada. Arctic and Alpine Research, 15,4,pp.471-487. SMART, C. C. (1997) Hydrogeology of glacial and subglagiacal karst aquifers: Small River, British Columbia, Canada. J2'h Interna tional Congress of Speleology, I997 Switzerland, 2, pp. 315-318. SMART, C. C., & ZABO, L. (1997) Experimental design, technique and protocol in fluorometric tracing of ground water. I2'h Inter national Congress ofSpeleology, I997 Switzerland, 2, pp. 5154. WERNER, A. (1997) Model Code TRACY. ZABo, L. (1995) Fluorometric tracing of Subglacial Hydrology, Small River Glacier, British Columbia, Canada. MSc Thesis, Univer sity of Western Ontario.

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A bstract Theoretical and Applied Karstology, 13 (2000), pp. 101-111 Contaminant transport in karst aquifers Dorothy J. Vesper, Caro.line M. Loop & William B. White* Department of Geosciences, and Materials Research Laboratory, The Pennsylvania State University, University Park, PA 16802, USA. Contaminants are easily injected into karst aquifers through sinking streams, sinkholes, or through open fractures and shafts in the carbonate rock Transport of the contaminants through the aquifer is by a variety of mechanisms depending on the physical and chemical properties of the contaminant. Contaminants consist of (1) water soluble compounds, both organic and inorganic, (2) slightly soluble organic com pounds, less dense than water (LNAPLs), (3) slightly soluble organic compounds, more dense than water (DNAPLs), (4) pathogens, (5) metals, and (6) trash Water soluble compounds (e g nitrates, cyanides, carboxylic acids, phenols) move with the water. But rather than forming a plume spreading from the input point, the contaminated water forms linear stringers migrating down the conduit system toward the discharge point. LNAPLs (e.g petroleum hydrocarbons) float on the water table and can migrate down the water table gradient to cave streams where they tend to pond behind obstructions. DNAPLs (e.g. chlorinated hydrocarbons), in contrast, sink to the bottom of the a quifer In the conduit system, DNAPLs pond in low spots at the bottom of the conduit and infiltrate sediment piles. Transport of both LNAPL and DNAPL is dependent on storm flow which can force LNAPL through the system as plug flow and can move DNAPLs by mobi lizing the sediment piles. Pathogens (viruses, bacteria, parasites) are transported through the karstic drainage system because of the absence of filtration and retain their activity for long distances. Metals (e.g. chromium, nickel, cadmium, mercury, and lead) tend to precipitate as hydroxides and carbonates in the neutral pH, carbonate rich water of the karst aquifer. Metal transport is mainly as particulates and as metal adsorbed onto small particulates such as clays and colloids. Metal transport is also episodic. Metals migrate down the flow path under flow conditions that take small particulates into suspension. Trash is carried into karst aquifers through sinkholes and sinking streams It is, in effect, a form of sediment, and can be carried deep into the conduit system where it can act as a source term for other contaminants leached from the trash. Keywords : LNAPL, DNAPL, metal contaminants, transport, aquifers. Le transport des contaminants dans les aquiferes karstiques Resume L e s contaminants sontfacilement introduits dans les aquifires karstiques par l'intermediaire des pertes, des dolines, des fractu r e s ou v ertes et des puits creuses dans Ia roche carbonatee. Le transport des contaminants dans l'aquifire depend des proprietes physiques et chimiques du contaminant. Les contaminants peuvent etre: ( 1) des composes solubles (organiques et mine raux). (2) des composes organiques peu solubles et moins denses que l'eau (les LNAPL), (3) des composes peu solubles et plus denses que l'eau (les DNAPL), (4) des pathogenes, (5) des metaux et (6) des ordures. Les composes solubles dans l'eau (par exemple les nitrates, les cyanates, les acides carboxyliques, les phenols) sont transportes avec I' eau en formant des filets lineaires orientes vers le bas du systeme de conduites, vers I' exutoire. Les LNAP L (par ex. les hydrocarbures du petrole) flottent a Ia surfa c e de l'eau et peuvent migrer dans les rivieres souterraines et s'accumuler derriere des obstructions. Au contraire, les DNAPL (par e x l e s hydrocarbures chlores) ont Ia tendance a couler au fond de l'aquifire eta s'accumuler dans les points bas et cl s 'i nfiltrer dans les sediments Le transport des LNAP L comme des DNAP L peut etre bien different en conditions de crues qui peuvent pous s er l e s LNAP L dans le systeme et aussi deplacer les DNAPL en mobilisant les remplissages sedimentaires. Les pathogenes (virus, b ac ter ies, parasites) sont transportes toutle long du systeme karstique en {'absence de filtration et peuvent etre ai:t ifs sur de !ungues distances. Les metaux (par ex le chrome, le nickel, le cadmium, le mercure et le plomb) ont tendance a precipiter comme des hydroxydes et des carbonates dans les eaux karstiques carbonatees eta pH neutre. Le transport des metaux se fait so u s forme particulaire et estfacilite par /'absorption de ceux-ci a La surface des argiles et des colloi'des. Les metaux ala surface des par ticules en suspension migrent vers Ia base de l'aquifire en conditions d'ecoulement normales. Enfin, les ordures sont deversees dans les aquiferes karstiques dans des do lines et des pertes. Elles sont en fait une forme de sediments clastiques et peuvent etre transportees sur de tongues distances dans le systeme de conduits ou elles agissent comme une nouvelle source pour d autres contaminants. Mots ctes: LNAPL, DNAPL, contaminants mitaOUjues, transport, f11JUiferes karstiques. corresponding author. E-mail address: wbw2@psu.edu. CD 200 I, Editura Academiei RomD.ne. All rights reserved.

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102 Introduction It is a truism that karst aquifers are more vulnerable to con tamination than other types of aquifers. Sinking streams, sink hole drains, and open fract)Jres in the bedrock provide little or no filtration of incoming water. Large aperture solution openings provide easy pathways for the movement of con taminants. Localization of ground water flow in open con duits means that contaminants can be transported long dis tances with little dilution All of these statements have been repeated many times. What has been given less attention is the great variability in both volume and velocity of water moving through conduit systems and the impact of this vari ability on contaminant transport. In those aquifers with developed conduits, peak flows may be 100 times the base flows. Velocities within the conduit system are much higher during storm flow than during base flow. A further variable is the characteristics of the contaminants themselves All con taminants do not respond equally to the driving forces for transport through the karst aquifer The ability of the conduit system to store and release con taminants is dependent both on the nature of the contami nants and on the storm flow characteristics of the system Although there is an extensive and rapidly growing literature on contaminants in porous media and fracture aquifers, the analysis of contaminant transport in karstic aquifers is just beginning (e.g HoKE & WicKs, 1997). Our objective in the present paper is to describe the various types of contaminants and summarize some of the ways in which they are stored and transported in karst aquifers. The examples are drawn from our own research and from some previous thesis work at the Pennsylvania State University. Sources and types of contaminants Investigations of contaminant transport often classify the source terms into "point sources" and "diffuse sources" de pending on whether the contaminant source is highly local ized such as a pipeline break or spread out such as the runoff of agricultural chemicals from croplands. This distinction less use f ul in karst where most contaminants tend to be input through sinkholes and sinking streams and thus are intrinsi cally point sources. A more useful distinction is between "spills" and "leaks". A spill is an abrupt input of (usually) a large volume of con taminant. For example, a gasoline tanker truck wrecks on the highway. The gasoline flows into a nearby sinkhole. A leak is a conti nuous input of (usually) a relatively small volume of contami nant. The b est examp les are leaky underground age tanks which continuously drip their contents into the un derlying aquifer. The volume of contaminant is small at any givep tim e although the quantity of contaminant may become quite large over lon g periods of time. D. J. Vesper et at. Contaminants can be classified depending on their physical and chemical properties. For liquids, the pertinent properties are their solubility in water, their density, and their vapor pres sure (Fig. 1). Some liquids such as low molecular weight alcohols, are miscible with water in all proportions. Others sufficient solubility that they are taken completely into solution at the concentrations that occur in ground water sys tems. Still others have low solubilities so that they separate from water to form immiscible phases separated from the water. The density of immiscible liquids is a key parameter If the immiscible phase is less dense than water, it will float on the water surface. If it is more dense, it will sink. The third variable is the vapor pressure which separates organic liquids into a "volatile organic compound (VOC)" class and a "semi volatile organic compound (SVOC)" class The bound ary vapor pressure is set at an arbitrary 5 Torr (0.667 kPa) Although the boundaries in solubility and vapor pressure are set by arbitrary choices, it is important to remember that no compound is completely insoluble and no compound is com pletely non-volatile. This caveat is especially important in karst aquifers. u 0 > p u 0 > rJJ (f One-phase t t Two-phase DNAPL p = l LNAPL ffi I t Saturation t solubility in water Defined p. I vapor pressure (0.667 k Pa) Fig. I. Variables describing liquid and water-soluble contaminants. Variables controlant les contaminants liquides et solubles

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Contaminant transport in karst aquifers With these and other aspects of contaminants in mind, it is possible to construct the following classification: (1) Water soluble compounds. These are materials which would be taken completely into solution at all concen trations likely to be found. Water soluble inorganic compounds include ammonia and the nitrate ion, mostly derived from human and animal wastes and perhaps the most widespread of inorganic contami nants. Also water soluble are other inorganic ions such as chloride and sulfate as well as some highly toxic species such as cyanide ions derived from some in dustrial wastes. Some organic compounds are also water soluble such as alcohols, carboxyllic acids, phenols and some agricultural chemicals. (2) Light, slightly soluble organic compounds. Light, non-aqueous phase liquids (LNAPLs) are those that will float on water. Gasoline, diesel fuel, home heat ing oil and related petroleum hydrocarbons are the most common examples. Gasoline is a complex mixture of low molecular weight, relatively volatile, saturated hy drocarbons. It is the presence of percentage quantities of aromatic hydrocarbons, benzene, toluene, ethyl benzene, and xylene (BTEX) that give gasolin e its toxicity. (3) Heavy, slightly soluble organic compounds. Dense, non-aqueous phase liquids (DNAPLs) will sink in water Mostly these are chlorinated (or brominated) compounds They i nclude such low molecular weight. relatively volatile compounds as methylene chloride, CH,Cl,, trichloroethylene, C,HC11 (TC E), and perchlo roethyiene, C2Cl4 (PCE) which are widely used as sol vents, de-greasers, and dry cleaning agents. These materials are transported in tank car quantities and are often stored in underground tanks. Other DNAPLs include a family of compounds called polychlorinated b i phenyls (PCBs) These materials are non-volatile, oily liquids which w ere once extensively used in elec trical transformers and have been widely injected into karst and other aquifers by salvage operations intended to re c over copper from scrap transformers For some re a son, old limestone quarries have frequently been the site of such oper a tions. (4) Metals The t e rm "metal", of cours e i s am biguous About two-thirds of the elements on the periodic table are metals Most of these do not impose environmen tal problems because they are rare in nature and are r ar ely used in commercial products We deal h ere only with a limited set of m e tallic elements, whi c h, how. e ver, cover much o f th e range of behav i o r o f the re maini n g e lem e nts T w o m e tal s iron and m angan es e, make up most of the natural background. These met als occur widely in sedimentary rocks and their ox ides and hydrated oxides are common in cave d e pos its. Nickel and chromium appear in waste from chrome-103 plating and other non-ferrous metals industry and are typical representatives of the iron-group or transition group elements. Both are toxic and both have been implicated as carcinogens. Zinc ores occur in carbon ate rocks Zinc and the chemically similar but more toxic cadmium occur widely as "galvanized" coating s on utensils, building materials, and other objects likely to end up in trash dumps. (5) Pathogens. Viruses, bacteria, protozoa, and larger or ganisms are easily transported into karst aquifers be cause of the absence of filtering from the soil. Most wide spread of these are the fecal coliform group of organisms and the fecal streptococci bacteria The pres ence of these organisms is the most common indicator of pollution from sewage or animal waste Of most concern among protozoa is "Giarida Lamblia which is released in a cyst form in animal feces and i s present in many surface waters Sinking streams carry the stable cysts to the subsurface (6) Trash. Rural residents and even entire communities have from long tradition used sinkholes as waste dis posal sit e s. Farmers routine l y use sinkholes t o d i spose of dead animals and also e mpty containers of their agricultural chemicals Unique among aquifers, sink ing streams and sinkhole drains provide routes along which bulk trash can be carried for long distances in side the aquifer. The deposition of trash as clastic sediment" provides a source term for leaching and re lease of contaminants for long p e riods of time Transport and Storage of Contaminants The defining characteristics of karst aquif e rs are the r apid throughput times, locali z ation of flow within e ssen ti ally on e dimensional flow paths within the conduit system, and the presence of deposits of clastic sediments in most of the con duits. Each of these characteristics plays a role but a different role depending on the specill c contaminant and on the de tailed hydrogeology of the karst aquifer. Water Soluble Contaminants Soluble contaminants move with the water. In karst aquifers the water from diffuse infiltration through the soil from sink hole drains and from sinking streams ultimately makes i t s way into the conduit system. The concentration of s ol uble contaminant should b e d e t e rmined by th e c onc e ntr atio n a t th e source a djusted for diluti o n by oth e r w a ter s o urc e s m e r g ing in th e main conduit. By thi s m odel, th e concentration o f nitrates or other water soluble contaminants should d e creas e during storm flow because of dilution by the storm wat er. Although storm water dilution has been observed, wh a t is observed in many cases, is a puls e o f contaminant during s t orm

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104 D. J. Vesper et al. 14.00 12.00 10.00 'iii Ql 8 .00 Dl ... Ill .c 6.00 u Ill 0 4.00 2 .00 0.00 t--. "' 0 t--. C"') 0 t--. co 10 co "": It) 10 CD ,... ,... co 0) ..., 'ot ' ..., 'ot -.-Nitrate-Nitrogen Loading at Rock Spring During May 30-31 and jWte 4-6 Storm Events \ J I'\. r------11 "' 0 ,... "' 0 ,... C"') 0 ,... "' 0 ,... "' co "! co '": co co 0) 0 -N "' "' ..., Ill ll) CD ,... ,... ll) Ill Ill Ill Ill ll) Ill Ill Ill Ill ll) Ill ...-...-.-Julian Time t"--. '-0 ,... C"') 0 t--. "' 0 "! "! co Ol 0) 0 --N Ill Ill Ill CD CD CD CD .,.... .,.... .,.... Fig. 2 Nitrate bursts during storm flow in Rock Spring Basin, Centre County, Pennsylvania. Data from UNDERWOOD (1994). Pies de nitrates pendant les erues de Rock Spring Basin, Centre County, Pennsylvania. Donnees extraites de U Nor:Rwoon ( 1994). 1200 1000 ::;-800 -Dl .s Ql 600 c: N Ill .... -< 400 200 0 Atrazine Variation over Time in Rock Spring 3 / 20/92 through 1V30/92 ... ...... .. ..., 1 2 :0 0 1 0 a: Ql Q. ... :::J 8 0 .c ..; ... Ql 6 Q. Dl z 4 M 0 z Ill 2 Ill Ill ::c 0 50.00 100.00 150.00 200.00 Julian nme 250.00 300.00 350.00 Fig 3 Atrizine bursts during storm flow in Rock Spring Basin, Centre County, Pennsylvania. Data from Underwood ( 1994) Pies d'atrazine les crues de Rock Spring Basin, Centre County, Pennsylvania. Donnees extraites de VNtJEH.woon ( 1994)

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Contaminant transport in karst aquifers flow. The contaminant tends to ride the hydrograph, reaching a maximum concentration during peak flow (Fig. 2). The data in Figure 2 are from central Pennsylvania (UNDERWOOD, 1994). Similar results have been observed in Kentucky (CURRENS, 2000). Nitrate levels in conduit fed springs tend to be highly vari able because of the effects of dilution by storms whereas nitrate levels in fracture-fed springs tend to be relatively con stant although the actual nitrate levels vary greatly from one spring to another (KASTRINOS & WHITE, 1986). The agricul tural chemical atrazine also exhibits a storm pulse (Fig. 3). Since both flow and contaminant increase during storm flow, the actual flux of contaminant discharged from the aquifer is the convolution of the hydrograph and contaminant chemograph integrated over the storm pulse. Flux = fQ(t)C(t)dt (ll Although the source of the spike in the contaminant is not known for certain, it seems possible that the role of storm now is to leach contaminants stored in the overlying soil or in the epikarst. Light Non-Aqueous Phase Liquids LNAPLs will float on ground water. This has led to some remarkable contamination problems such as a lake of gaso line nearly two meters deep floating on the water table near Mechanicsburg, Pennsylvania (RHINDRESS, 1971). LNAPLs will float on underground streams and be carried along with the flowing water. The LNAPL will pond when the water ponds behind obstructions and becomes temporarily en trapped. Conduits generally create a trough in the water table so the LNAPL contamination in the conduit tributaries and in the fracture system tends to migrate toward the master con duit. During flood flow, the trough fills and conduits with free surface steams shift into a regime of pipe flow. Ponded LNAPL is lifted with the rising water and pressed against the ceiling. Any pockets in the ceiling will form traps for the LNAPL (EwERs etal., 1991). If the ceiling is tight, the LNAPL is forced through the obstructions as piston flow. A burst of LNAPL then continues down the conduit. For this reason, spills of LNAPL do not necessarily appear at the karst springs immediately after the spill. Alternatively, if the ceiling is frac tured, the piston flow drives the LNAPL upward where the vapors may rise into structures on the land surface. Fume problems in homes and other structures overlying conduit systems contaminated by LNAPLs may arise long after the initial spills (STROUD et al., 1986). Many common light hydrocarbon compounds have substantial solubilities and vapor pressures (Table 1 ). For accumula tions of LNAPL ponded behind obstructions in conduits, the continuous sweep of fresh water beneath the pool will even tually dissolve and remove the pool. Likewise, the ponded lOS LNAPL will gradually evaporate because of the vapor pres sure of the compounds. In the process, of course, tbe air-filled cave passages become contaminated with hydrocarbon fumes. The turnover in cave air due to barometric changes will even tually flush out the contaminants but while they are present they are a substantial hazard to cave explorers, especially those who explore by carbide lamp. One of the most serious inci dents occurred in Howard's Cave, Georgia in 1966 where a gasoline explosion set off by carbide lamps claimed three lives (BLACK, 1966). Table 1. Solubilities of some light aromatic hydrocarbons (selected from FETIER, 1993). Solubilites de quelques hydrocarbures aromatiques (d'apres FETTER, /993) Compound Benzene Toluene o-Xylene Ethyl Benzene Solubility in water (mgll) 1780 500 170 150 Dense Non-Aqueous Phase Liquids The pathways for heavy organic liquids migrating below the level of the epikarst will be fractures, shafts, and chimneys of various kinds. Possible storage sites in the aquifer include cavities and dry cave passages in the vadose zone, fractures in the phreatic zone, and the main conduit system where DNAPL can collect in pools beneath the water surface, and become incorporated into the clastic sediments that occupy the conduit. Because of the density difference, DNAPL com pounds can occupy the pore spaces within the sediment pile where they can be sequestered for long periods of time. The water table generally stands higher near the boundaries of karst ground water basins with hydraulic gradients that point toward the conduit system. DNAPLs reaching the wa ter table do not necessarily follow the ground water down gradient toward the conduit but can continue to move verti cally into any available storage spaces below local base level or can follow the dip of bedding planes in directions quite different from the hydraulic gradient. The transport of DNAPL has both similarities and differences to the transport of LNAPLS. Processes in common include volitilization although this process is not as effective because in the case of DNAPL, the overlying water provides a pro tective blanket. Either type of contaminant can degrade in the carbonate environment. The effectiveness of this process is strongly dependent on the specific DNAPL being considered. DNAPLs have a finite solubility (Table 2) and are also gradually stripped away by the continuing flow of fresh water in the conduit. DNAPL that forms distinct pools beneath flowing stream s or in low places in water-filled con-

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106 D. J. Vesperetal. Table 2. Vapor pressures and solubilities of some chlorinated hydrocarbons (FETIER, 1993). Tension de vapeuret solubilite de quelques hydrocarbures chlores (FETTER, 1993). Compound Vapor Pressure (Torr, 20 C) Solubility in Water (mg/1) Methylene Chloride Carbon Tetrachloride Vinyl Chloride Trichloroethylene (TCE) Tetrachloroethylene (PCE) 349 90 2660 60 14 duits dissolves at rates given by the exposed area of the DNAPL pool and the specific dissolution kinetics of the par ticular compound. DNAPL pools can also be regarded as a sort of bedload and can be dragged downstream when flow velocities exceed a necessary threshold. Higher velocities may actually entrain the DNAPL pool so that it is flushed downstream in suspension. Unlike LNAPLs floating on the water surface and thus continuously in contact with the wa ter, DNAPL that has sunk into the sediment pile on the floor of the conduit is protected. There will be a slow percolation of water through the sediment much like any other porous media f1ow but like other porous media flow, the flow ve locities are very small, with only a slow turnover with the fast-moving water above. Thus, the ofDNAPL from the sediment pile will be much slower that the stripping of DNAPL constrained in distinct pools. DNAPLs and other compounds are slowly degraded by chemi cal reaction with the water. The actual kineti.fs of this pro cess have been measured by Knauss et al. (1999) for the spe cific example of trichloroethylene. The degradation reaction is: 2C2HCI3 +302 +2H20<::>4C02 +6H+ +6Cl-The end products of the breakdown process are and HCI. Because the reaction is with oxygenated water which is al ways in supply, the rate equation has the simple form: dC n -= -kC0 dt (2) By laboratory experiments, KNAUSS et al. (1999) found n = 0.85 and k = 5.8 x lQ-7 sec-1 at 100 C. A process that applies to DNAPL but not as much to LNAPL is the movement of the sediment pile itself. Sediments in ac tive conduits themselves form a continuous flux. New sedi ment is continuously injected-into the conduit system and must be continuously flushed through and discharged at the spring. Otherwise, the conduit system would eventually clog com pletely. Unlike the flow of water, the flow of sediments is episodic. Flood flows must reach a certain threshold before the sediments can move as bedload and an even higher thresh-20,000 800 1.1 1100 150 old before the sediment pile becomes completely entrained so that both sediment and any incorporated DNAPL are trans ported downstream. A conceptual model for DNAPL transport in karst aquifers has been published by WoLFE et at. (1997). The rather com plicated process of storage and DNAPL transport in karst aquifers has been reviewed by Loop & WHITE (2001). Their conceptual model for DNAPL transport is given in Figure 4. Metals Metals in karst aquifers can be divided into three categories (a) alkaline earth metals derived from the carbonate rock mainly calcium and magnesium with minor amounts of stron tium and barium, (b) heavy metals occurring as part of the natural background-mainly aluminum, iron, and manganese with trace amounts of many other metals, and (c) contami nant metals introduced into the aquifer through human influ ences. The chemistry of the alkaline earth metals in karst gtound waters is the subject of a huge literature on karst wa ter geochemistry and is not of concern here. However, the concentrations and transport of other metals in karst systems has received much less attention. In a recent study, HoDGE et al. (1998) assessed trace metal con centrations in a carbonate spring as an indicator of the trace metal concentrations in the ancient marine environment. As expected, calcium and magnesium were present at much higher concentra tions (10-3-10-4 mol/kg) than the potentially toxic meals arsenic, copper, chromium, and cobalt (10-7 -10-'J mol/kg). QuiNLAN and RoWE (1977) found nickel and chromium in a Kentucky karst spring presumably derived from a metal plating plant in the up per reaches of the ground water basin. To get a sense of the range of metals that might be expected, a composite sample was prepared from springs draining the Fort Campbell Army Base in western Tennessee/Kentucky. Water from the iarge regional Millstone Spring was mixed with sediment from the smaller Blue Spring. The clastic ma terial was allowed to settle and the slightly turbid water was analyzed by inductively coupled plama-mass spectrometer. (Table 3). These data are indicative of the range of metallic elements that might be carried by karst ground waters.

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Contaminant transport in karst aquifers Sinking stream Soil and epikarst Sediment pile Sinkholes and sinkhole drains Deep fractures and channels Deep storage Overflow springs Underflow springs 107 Fig. 4. Conceptual model for DNAPL storage and transport in karst aquifers. From LooP & WHITE (2001). Modele conceptuel pour le stockage et le transport des DNAPLs. D'apres Loop & WHITE (2001). Table 3. ICP-MS analyses of carbonate spring waters. Analyses ICP-MSdes sources carbonatees. Element Concentration (pg!L) AI 16,300 As 17 Ba 157 Ca 51,000 Cd 0.93 Cr 26 Cu 13 Fe 11,000 K 4280 Mg 5800 Mn 1350 Na 5370 Ni 20 Pb 24 Zn 81 The aqueous chemistry of individual metal-water systems is, in general, well understood (BAES & MESMER, 1976; STUMM & MoRGAN, 1996) and thermodynamic calculations can be made to determine the limiting solubilities. Figure 5 illus trates the case of the Ni-0-H system where nickel hydroxy complexes control the solubility. In karstic systems, the high carbon dioxide activities cause carbonates to be the limiting insoluble phase. Calculations for such systems as the Zn-0-H, Cd-0-H and Pb-0-H systems show that in all cases, pre cipitation of hydroxide or carbonate phases will limit the con centration of metal ions in karstic waters to low values. How ever, in all cases, at the pH and Pco2 values of karst water, the equilibrium metal solubility would be well above drink ing water standards. The controlling factor in metal transport appears to be ad sorption onto various substrates rather than equilibrium solu bility. Metals can adsorb onto clays and other clastic particu lates, onto organic material in the water, and onto iron or manganese oxides which often form coatings on cave streams.

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108 CNi (moi/L) 1 0 D. J. Vesper et al. Fig. 5. Calculated speciation diagram for the system Ni-0-H. Ni(OH)z is crystalline nickel hydroxide. Ni( OHh Diagramme de speciation du systeme Ni-0-H. u Ni(OH)2 est l'hydroxyde cristallise de nickel. Ni(O H)z0 1 o-I o 0 2 4 6 8 10 12. 14 pH Table 4. Chemical analyses of iron and manganese oxides from Rohrer's Cave, Pennsylvania. Data extracted from WHITE et al. ( 1985). Composition chimique des oxydes de fer et de manganese de Rohrer's Cave, Pennsylvania. Donnees extraits de W H!TE et al. ( 1985) Specimen Fe (wt %) Mn(wt%) Iron Oxide stalactite 43 0.01 Iron Oxide stalagmite 50 <0. 0 1 Manganese Oxide Coating 3.5 12.4 Manganese oxides, precipitated onto stream sediments by t h e oxidation of the natural manganese background (WHrrn, 1997) act as extremely effective scavengers for heavy metals. Chemi cal analyses of manganese oxides from a selection of karst conduits revealed percentage quantities of such metals as copper, zinc, nickel and-in one case-cobalt (Table 4) The se data also illustrate a "mutual exclusion ." The hydrated iron oxide deposits contain negligible concentrations of other metals including manganese while the manganese oxide coat ing s are highly enriched in other transition metals but contain only relatively small amounts of iron. McCARTHY & SHEVENELL (1998) confirmed the link between metals and solids for ground water in the karst aquifer that und erlies the Oak Ridge Reservation, Tennessee. They de t ermined colloidal compositions via: (a) the che mical differ ence i n total and filtered water samples, (b) direct soil mea surements using X-ray diffraction, scanning electron micros copy, and energy dispersive X ray spectroscopy, and (c) spe ciation modeling. In most well s they found that aluminum, Co(wt%) Ni(wt %) Cu(wt%) Zn(wt%) <0.01 <0.01 0.01 0.01 <0.0 1 <0.01 O.Ql 0.01 1.60 1.57 0.45 1.52 iron, manganese, and nickel were present primarily in the solid phase Storm-associate d changes in aquifer hydrology are known to impact ground water and karst spring chemistry. Recent re search by ATIEIA & KoZEL (1997) found that the abundance, size, and type of colloids discharged at a spring changed dur ing storm events. The greatest abundance of large colloids was discharged coincident with the rising limb of the spring hydrograph. This has been interpreted as the re-suspension of colloids in the conduits due to increased ground water ve locities. Colloid s identified during the study included clays, granular minerals, and bacteria. Although the study of metal transport in karst aquifers is far from complete, it is apparent that metals are stored in th e aqui fer primarily by adsorption onto various substrates. They mov e through the aquifer t o the discharging spring when the par ticulates on whi c h they are adsorbed are swept out of the aqui fer by storm pulses

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Contaminant transport in karst aquifers DAVE'S GALLERY SAND CANYON HUNTLEY'S CAVE'-....,_ fHTIIAHU STREAiool 00 DRY SUNPS SIHKII< CREEK SIPHON 109 CHffiC SNEAKY CREEK CAVE STREAM SINKING CREEK RESURGENCE NATURAL ORIDOE IE > IE [!) 0 ...J 2 IE gj 5 lE i: lE 8 ...J lE lE Sf'n'LE LOCI\Tl!Jl DI\Y(21 l CO..IFORI1 ml BACTERIA I 1E 1E 8 ...J 0 LE iii a! 1E !:! lE z: lE IE 0 000 SYMI:LINAL AXIS APPROIC. 6 UWI\.f LOCATION SAM'lE LOCIITI ON IJA\'(53 l COLIFORJ1 m! BIICTERI II Fig 6 Bacterial levels at various locations (shown on map) in the Butler Cave-Sinking Creek System, Bath County, Virginia, for day 21 (left plot) and day 56 (right plot) measured from August l, the beginning of the water year. Data from CHESs ( 1987). Niveaux bacreriologiques dans divers endroits (indiques sur La carte) dans Butler Cave-Sinking Creek System, Bath County, Virginia, pourlejour 21 (diagramme de gauche) et lejour 56 (diagramme de droite) mesures ii partirdu 1., Aout, debut de l'annee hydrologique. Donnees d'apres CHESS (1987). Pathogens Although it has long been recognized that cave streams should not be used for drinking water, in reality, many cave streams and the springs to which they discharge are used as domestic and sometimes public water supplies. Because there is little filtering of recharge water from sinking stream s or from storm runoff into sinkholes, it is quite obvious that microorganisms, including pathogenic ones, can be easily carried into the un derground system. Typical sizes for microorganisms range from the submicrometer to hundreds of micrometers, in the range of fine-grained sediment. Organisms can be transported in suspension in the water and as attachments to particles of sediment or organic material. Questions of the survival rate of microorganisms in karst aqui fers is another matter. Recent investigations of cave microbi ology (see e.g. SASOWSKY & PALMER, 1994) have revealed a rich diversity of organisms that seem to thrive very well deep within karst systrms. On the other hand, those organisms that pose the greatest threats to humans might be expected to ex hibit a high die-off rate Hard data are sparse. An investiga tion of total bacteria and coliform bacteria in the Butler Cave -Sinking Creek System of Virginia (CHESS, 1987) showed

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110 no evidence of die-off anywhere in the system. Roughly the same populations of organisms were found in streams deep within the system and at the discharging spring as occurred in the sinking surface streams (Fig. 6). Trash In many karst areas, sinking streams have cut small blind valleys into the land surface These depressions, along with the ubiquitous sinkholes, have been used as trash receptors as long as there have been human populations. Sinkhole dumps are as much characteristic karst land features as the sinkholes themselves Two aspects of sinkhole dumps relate to the gen eral problem of ground water contamination in karst aqui fers. Sinkholes act as funnels, collecting storm water runoff and channeling it into the sinkhole drain The trash pile in a sinkhole behaves as an unlined landfill. Storm water leaches through the trash and what enters the karst drainage system below is essentially landfill leachate. Secondly, inwash dur ing intense storms and soil piping failures of the sinkhole sedi ment combine to transport solid trash into the underlying con duit system. The trash becomes a form of clastic sediment and is moved down the flow field during intense storm flow in the same manner as any other clastic sediment. Trash car ried deep within the conduit system becomes a source term References A TrElA, 0 & Koi'..EI., R ( 1997) Particle size distributions in water from a karstic aquifer: from particles to colloids. J.of Hydrol ogy, 201 pp. 102-119. BAES, Jr. C. F., & MESMER, R. E. (1976) The Hydrolysis of Cations. John Wiley, New York, 490 p. BLACK, D. F. (1966) Howard's Cave disaster. NSS News, 24, pp 242-244. D L. ( 1987) Comparisons of microbiology and selected ions for surface and subsurface stream waters for the Aqua Spring watershed of Burnsville Cove, Virginia. M.S. Thesis, The Pennsylvania State University. CuRRENs, J. C. (2(.100) Ground water quality in a karst aquifer fol lowing BMP implementation (abstract). Proc Natl. Speleol. Soc Convention, Elkins WV, pp Al8-19. EWERS, R 0., A. J ESTES, E K., IDSTEIN, P J., & JOHNSON, K. M ( 1991) The transmission of light hydrocarbon contami nants in limestone (karst) aquifers In: Proceeding of the Third C onference on Hydrogeology, Ecology, Monitoring, and Man agement of Ground Water in Karst Terranes, Association of Ground Water Scientists and Engineers, pp. 287-306. Fr.TTER, C. W (1993 ) Contamina,nt Hydrogeology Prenti ce Hall, Upper Saddle River, NJ, 500 p. D. J. Vesper et al. for continuing contamination of the ground water and is lo cated where clean-up is essentially impossible. Trash injections into karst systems have not been systemati cally examined. Categories include domestic waste -a mix of materials not different from those usually deposited in en gil!eered landfills, dead, often diseased farm animals, and -in more recent time chemical waste. The latter takes the form of improperly cleaned containers for paint and agricul tural chemicals which may be dumped in sinkholes as an al ternative to proper recycling. Conclusions Contaminants to karst aquifers have been broadly classified into water-soluble organic and inorganic contaminants, slightly soluble organic contaminants, metals pathogens, and trash. For each of these categories, there are multiple, com plex, and interacting mechanisms for the transport, storage, and eventual release of the materials. Some of these are be coming understood Others await detailed investigation. The subject of contaminant transport in karst is per haps the most important of the current generation of karst research subjects. HoooE, V F., STETZENBACH, K. J., & JoHANESSON, K. H. ( 1998) Simi larities in the chemical composition of carbonate ground waters and seawater. Environmental Science and Technology, 32 pp. 1481-1486. HoKE, J A., & WICKS, C. M. ( 1997) Contaminant transport in karst aquifers In: The Engineering Geology and Hydrogeology of Karst Terranes, (BECK, B F & STF.PHF.NSON, J B., Eds.), A .A. Balkema, Rotterdam pp. 189-192. KAsTRJNos, J R., & WHrre, W B. (1986) Seasonal hydrogeologic and land-use controls on nitrate contamination of carbonate ground waters. In: Proceedings of the Environmental Pro[?lems in Karst Terranes and Their Solutions Conference, National Water Well Association, pp. 88-113. KNAUSS, K. G., DIBLEY, M J., LEIF, R.N., MEW, D. A., & AINF.S, R. D (1999) Aqueou s oxidation of trichloroethene (TCE) : A kinetic analysis. Applied Geochemistry, 14, pp. 531541. LooP, C. M.,& WHITE, W B. (2001)Aconceptual model forDNAPL transport in karst. Ground Water 39, pp 119-127 McCARTHY, J. F., & SHEVENELL, L (1998) Processes controlling col loid composition in a fractured and karstic aquifer in eastern USA. J of 206, pp 191-218. QUINLAN, J. F & RoWE, D. R. (19 77 ) Hydrology and water quality in the Central Kentucky Karst: Phase I. University of Kentucky Water Resources Research Institute Research Report, No.101, 91 p.

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Contaminant transport in karst aquifers RHINDRESS, R. C. ( 1971) Gasoline pollution of a karst aquifer. In: Hydrogeology and Geochemistry of Folded and Faulted Rocks of the Central Appalachian Type and Related Land Use Prob lems (PAIUI.EK, R. R., WHITE, W. B., & LANGMUIR, D., Eds.), Earth and Mineral Sciences Experiment Station, The Pennsylvania State University, Circular 82, pp. 171-175. SASOWSKY, I. D., & PALMER, M. V. (1994) Breakthroughs in Karst Geomicrobiology and Redox Geochemistry. Karst Waters Insti tute Special Publication, 1, Ill p. STROUD, F. B., GILBERT, J., PowELL, G. W., CRAWFORD, N. C., RIGATTI, M. J., & JoHNSON, P. C. (1986) U.S. Environmental Protection Agency emergency response to toxic fumes and contaminated ground water in karst topography: Bowling Green, Kentucky. In Proceedings of the Environmental Problems in Karst Ter ranes and Their Solutions Conference, National Water Well Association, pp. 197-226. 111 STIJMM, W., & MoRGAN, J. J. (1996) Aquatic Chemistry (3 .. Edition) John Wiley, New York, 1022 p. UNDERWOOD, K. L. (1994) Evaluation of pesticide and nitrate mo bility in a conduit-flow dominated karst basin. M.S. Thesis, The Pennsylvania State University, 204 p. WHITE, w. B., SCHEETZ, B. E., ATKINSON, s. D., IBBERSON, D . & CHEss, C. A. (1985) Mineralogy of Rohrer's Cave, Lancaster County, Pennsylvania. NSS Bulletin, 41, pp.17-27. WHITE, W. B. (1997) Thermodynamic equilibrium, kinetics, activa tion barriers, and reaction mechanisms for chemical reactions in karst terrains. Environmental Geology, 30, pp. 46-58. WoLFE, W. J., HAUGH, C. J., WEBBERS, A., & DIEHL, T. H. (1997) Preliminary conceptual models of the occurrence, fate, and trans port of chlorinated solvents in karst regions of Tennessee. U.S. Geological Survey Water-Resources Investigations Report 97-4097, 80p.

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Theoretical and Applied Karstology, 13 (2000), pp. 113-117 Microtus (Terricola) grafi miciaensis (Rodentia, Mammalia), une nouvelle sous-espece du site mousterien de Gaura Lupului {Craciuneti, Hunedoara, Roumanie) Patrick Brunet-Lecomte1 & Alexandra-Cristina Paunesco2* I UMR CNRS 5561 Biogeosciences, Laboratoire de Paleobiodivesite et Prehistoire de L'EPHE, Centre des Sciences de La Terre, 6, Bd. Gabriel, F-2100 Dijon, France. 2 Laboratoire Departemental de Prehisioire du Lazaret, 33 bis, Bd. Franck Pilatte, 06300 Nice, France et L'lnstitut de Speologie Emil RacoviJ(i str. Frumoasa 1 I, 78114 Bucarest !2, Roumanie. Resume Les particularites morphometriques de Ia population de M. (Terricola) graft du site mousterien de Gaura Lupului (village de Craciuneti, departement de Hunedoara, Roumanie), nous a incites a lui donner un rang sub-specifique. Elle est decrite sous le nom de Microtus (Terricola) graft miciaensis. Mots cles: rongeurs, Arvicolidae, Pleistocene superieur. Microtus {Terricola) grafi miciaensis (Rodentia, Mammalia): a new subspecies from the Mousterian site of Gaura Lupu/ui (Craciune!}ti, Hunedoara, Romania) Abstract The morphometric features of the population of M. (Terricola) grafi from the Mousterian site of Gaura Lupului (Criiciunejti village, Hunedoara county, Romania) entitled us to attribute it a specific rank. It is further on described under the name of Microtus (Terricola) grafi miciaensis. Key words: rodents, Arvicolidae, Upper Pleistocene. Introduction Le gisement mousterien de Gaura I..:'upului, dans l' ouest des Carpates a livre de nombreux restes de micromammiteres parmi lesquels les six premieres molaires inferieures (M1 ) se rapportant a une espece du sous-genre de campagnol Microtus (Terricola). Notre objectif est de preciser le statut specifique de cette espece, compte tenu d'une part de !'interet de ce groupe dans l'etude de la speciation, et d'autre part de la si tuation biogeographique particuliere de cette region. *corresponding author. E-mail address: acpaunescu@hotmail.com 200 I, Editurd Academiei Romane. All rights reserved. Materiel Le materiel etudie se compose des six premieres molaires inferieures (M1 ) de Terricola provenant du gisement mous terien de Gaura Lupului et de 14 M1 actuelles de la localite de Nandru. La grotte Gaura Lupului est situee dans le secteur kars tique Bitita-Crliciuneti, a une vingtaine de km au nord de la ville de Deva (departement de Hunedoara), et a environ 1,5 km en direation NNO du village de Criiciuneti. Elle est creusee dans le massif calcaire de Mligura Peterii a une altitude relative de 527 m. Les fouilles ont ete entrepri ses par Alexandru Pllunescu, en 1999, et elles nous ont per mis le recueil de nombreux restes de microfaune.

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114 Le materiel actuel provient des pelotes de rejection d'un ra pace nocturne, ramassees ala base de son nid, sur le territoire du village de Nandru (departement de Hunedoara) Ce materiel a ete compare a : 15 populations actuelles (310 dents) de M (T.) subterraneus de France, Suisse et Pologne, 3 populations actuelles (59 dents) de M. (T.) tatricus de Polo gne (Tatras et Beskidy) et Slovaquie (Tatras) et 10 popula tions stratigraphiques de l'espece fossile (164 dents) M. (T.) graft du Pleistocene superieur de Bacho Kiro, Bulgarie (BRUNET-LECOMTE et al., 1992). Methode Vingt-trois variables, notees V1 a V23 sont prises sur la sur face occlusale de laM, (BRUNET-LECOMTE, Onze i ndices odontometriques sont calcules: longueur rela tive de la partie de laM, LRP A=(V6-V3 )N6x 100, inclinaison du rhombe pitymyen RP=V4-V3, fermeture de la boucle anterieure BA =(V20-V 18)N21 x 100, le rapport lon gueurllargeur de laM, V6V21=V6N21 et 7 autres variables de Ia partie anterieure de Ia M, V10V9=(V10-V9)N6x 100, VII V9=(VI1 -V9)N6x 100, V12V10=(V12 -V10)N6x 100, Vl2Vll=(Vl2-V11)1V6x 100, V18V17=(V18-V17)/ V2lx 100, Vl9Vl7=(V19-V17)/V21x 100 et V20V19=(V20-Vl9)N21 X 100. La morphologie generale de laM, est etudiee : {i)-par une analyse en composantes principales (ACP) faite entre les va riables prises sur la surface occlusale de la dent entre les 20 dents des deux populations roumaines et (ii) -par une ana lyse canonique discriminante (ACD) faite entre les deux po pulations roumaines comparees aux 28 populations actuelles et fossiles de M (T.) subterraneus, M. (T.) tatricus et M (T. ) gra.fi. Les indic es odontometriques ainsi que Ia lon g ueur totale de Ia M, (variable V6) sont compares entre les deux populations roumaines par un test t, complete par un test de Wilcoxon en raison des faibles effectifs des populations P. BrunetLecomte & A.-C. Pllunesco Le logiciel statistique est celui de SAS. R esult ats Morphologie generale de la M 1. Les trois premiers facteurs de 1' analyse en composantes prin cipales expriment respectivement 59, 12 et 11% de Ia variance total e. La description et Ia comparaison de la moyenne de ces fac teurs entre les deux populations roumaines sont donnees dans le Tableau 1. Les moyennes ne sont pas differentes (p>O,IO) pour le facteur 1 qui exprime un effet de taille, alors que les deux populations sont proches d'etre differentes (p compris entre 0,05 et 0,10) ou differentes {p<0,05) pour les facteurs 2 et 3 respectivement qui expriment une variation de forme La distribution des 20 dents dans le plan 2-3 des axes factoriels est donnee dans Ia figure 1: on observe une separation par tielle des deux populations, notamment dans le quart -/-du plan pour lequel5 des 6 dents de Gaura Lupului sont presen tes contre seulement 1 dent sur 14 pour Ia population de Nandru. Les deux premiers facteurs de I' analyse canonique discrimi nante faite entre les 30 populations expliquent respectivement 39 et 18% de la variance inter-populationnelle. La distribution des centres de gravite des 30 popUlations dans le plan 1-2 (Fig 2) monlre que: 1' axe 1 separe les populations de M. (T. ) tatricus de celles de M. (T.) subterraneus et de M (T.) graft., l'axe 2 separe les populations de M. (T.) subterraneus de celles de M. (T.) graft.. Les deux populations roum aines occupent dans le plan 1-2 des positions sensiblement differentes : Ia popula tion de Nandru occupe une position intermediaire entre les populations de M (T.) subterraneus et celles de M (T. ) graft. alors que Ia population de Gaura Lupului occupe une posi tion intermediaire entre les populations de M. (T.) tatricus et celles de M. (T.) graft. sur l'axe 1 et une position en limit e superieure de celles de M. (T.) graft surl'axe 2 montrant ainsi une position relativement isolee dans le plan 1-2. Tableau I Description et comparaison des facteurs 1 2 et 3 de I' analyse en compqsantes principales obtenue partir des mesures prises sur Ia surf a c e occlusal e de Ia dent e ntr e l es populations de Nandru et Gaura Lupului. Description and comparison of the factors 1, 2 and 3 after the main components analysis based on measurements of the occlusal surface of the populations from Nandru and Gaura Lupului, respectively. Population fossile Popul ation actuelle Test de Variable (Grotte Gaura Lupului) (l'!_andru) N=14 Test t (p) Wilcoxon (p) Moyenne Ecart Min Max Moyenne Ecart Min Max type type Axe 1 0,50 1,21 -1,44 1,68 -0,21 0,86 -2,65 0 ,7 p=O,l52 NS p=O,l74 NS -0,65 0,96 -2,15 0 ,76 0 ,2 8 0,91 -1,53 1,69 p=0,054 NS p=0 ,091 NS Axe3 0 ,9 0 0 ,4 0 1 ,33 -0,38 0,39 0 93 -1, II 2,03 p= 0 004S

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Microtus (Terricola) graft miciaensis M i -3 -3 -2 .-1 3 2 " 1 ... -2 -... 'It " "-'1 -2 ... 2 ... ... 1 ... ... :A ... 1 ... -1 .. -2 Axe2 - 1 Axe 1 ... 2 3 " 115 Fig. 1. Distribution des premieres molaires inferieures des deux popu lations de Nandru etGaura Lupului dans le plan 2-3 de !'analyse en composantes principales obtenue a partir des mesur es prises sur Ia sur face occlusale de Ia dent. Distribution of the first lower mo lars of the two populations from Nandru and Gaura Lupului within the plan 2-3 of the main compo nents analysis obtained by mea surements on the occlusal surface of the teeth. Gaura Lupului Nandru M. (Terricola) subterraneus M. (T.) grafi M. (T.) tatricus Fig. 2. Distribution des centres de gra vit e dans Je plan 1-2 de ) analyse canonique discriminante faite entre Jes popul a t i ons de Nandru, Gaura Lupului de M (T. ) subterran e us (15 populations), M. (T.) tatricus (3 populations) et M (T. ) graft (10 populations) Distribution o f gravity c e nters within the plan 1 2 of the canonic dis c riminant analysis perfo rmed b e tween the popul a t io n s of Nandru Gaur a Lu p ului M. (T. ) subterraneus (15 populations) M. (T.) tatri c us (3 populations) and M. ( T.) g raft (10 populati ons ) Analyse des indices odontometriques La description et Ia comparaison de Ia longueur totale de Ia dent (V6) e t des 11 indices odontometriques entre les deux popul a tions roumaines sont donnees dans le Tableau 2. D eux indic e s, Ia longueur relativ e d e Ia parti e anterieure d e Ia d ent (LRPA) et l'inclinaison du pitymyen (RP), sont dif ferents (p < 0,05) quel que soit le test utilise et deux indices, V6V21 et V19V17 sont differents (p < 0,05) le test t et proches d'etre differents (0,05 < p < 0,10) a ve c le test de Wilcoxon entre les deux populations. La popul a tion de Gaura Lupului se diff6renci e ou e st proche de se differe nci e r de Ia population de N an dru par une longu eur rel a tive d e I a dent moins developpee, un rhombe pitymyen moins incline, une dent d'aspect plus etroit (V6V21) et l'indice V19V17 plus ouvert

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116 P. Brunet-Lecmnle & A.-C. Pllune.tco Tableau 2. Description el comparaison de Ia longueur totale de Ia premiere molaire infcrieure (V6) el des II indices odontomctriqucs calcules entre le.'l populations de Nandru el Gaura Lupului. Description and comparison of the total Length of the jir.ft Lower molar (V6) and the eleven odontometric indexes calculated helllleen the populations of Nandru and Gaura l..ufJULui. Population fossile Popuhttion actuelle Test de Variable (Grotte Gaura Lupului) N=6 (Nandru) N=l4 Test I (fJ) Wilcoxon (p) Mo-Ecart Min Max Mo-Ecart Min Max yenne type yenne t ype V6 (mm) 2,672 0,224 2,290 2,900 2,581 0,173 2.070 2,740 p=0,340 NS p=0,283 NS LRI'A (%) 50,7 1,6 48,2 52,9 52,7 1,7. 49,8 55,5 p=0,023 s p=0,035 s RP (nun) 0,080 0,075 0,010 0,220 0,012 0,027 -0,040 0,050 p=0,007 s p=O,O.I8 S BA(%) 20,7 10,6 6,7 30,7 15,4 V6V21 (sans unite) 2,83 0,19 2,62 3,10 2,67 VIOV9 (%) 15,1 1,0 14,0 16,3 15,5 VIIV9 (%) 1,5 1,9 -0,4 4,7 0,6 VI2V10 (%) 3,2 1,1 2,2 4,7 2,1 VI2VII (%) 16,7 1,9 14,1 19,6 16,9 VI8VI7 (%) -4,1 6,9 -13,9 5,6 0,3 VI9VI7 (%) 2,9 1,6 0,0 5,6 1,4 V20VI9 (%) 13,7 7,5 0,0 20,8 14,3 Discussion ct conclusion faiblc c!Tcctif des deux populations ctudiccs doit inciter a Ia prudence dans !'interpretation des resultats obtcnus. Tou tcfois, !'analyse de Ia morphologic generale etl'ana1yse des indices odontometriques monlrent que lcs deux populations roumaines sont assez diffcrentes, ct ne doivent pas ctre ran gees dans le meme taxon. La population actuelte de Nandru ctant morphologiquement proche de M. (T.) subterraneus, peut ctre Hllribuee ala forme M. (T.) subterraneus dacius decrite
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Microtus (Terricola) graft miciaensis M (Terricola) subterraneus de Nandru (de 1 a 5) et M (T. ) graft miciaensis de Gaura Lupului (de-6 a 9) M. (Terricola) subterraneus from Nandru ( 1 to 5) and M. (T ) grafi miciaensisfrom Gaura Lupului ( 6 to 9 ) Bibliographie BRUNF.T-LF.COMTF., P ( 1988) Les campagnols souterrain.f (Terricola, An1icolidae, Rodentia) actuels etfossiles d'Europe occidentale. These Doctoral de I'Universite de Bourgogne, Dijon, 146 p. 6 117 2 3 4 5 7 8 9 BRUNET-LECOMTE, P., NADACHOWSKI, A. & CHAI.INE, J. ( 1992) Microtus (Terricola) graft nov. sp. du Pleistocene superieur de Ia grotte de Bacha Kiro (Bulgarie) Geobios, 25, 4 pp. 505-509.

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Theoretical and Applied Karstology, 13-14 (2000-2001) Speleological Atlas of Serbia Predrag Djurovic, Editor Ed "Jovan Cvijic" Geographicallnst., Serbian Academy of Sciences & Arts, Special Issue 52, Belgrade, 199 8 290 p (+32 unnumbered pages), 14 color photographs, A3 format, hardcover, ISBN: 86-80029 -15-7. Bilingual (Serbian a nd English). price: US D 50; on s al e to the "Jovan Cvijic" Geographical Institute, Djure Jaksica 9 11000 Belgrade, Yugoslavia. email: gijcsanu @ eunet.yu Book Reviews The official reference-year of this book i s 1998, but it was only in March 1999 that it was actually printed. As much as I would try to keep this re v ie w far from politics, I still cannot disregard that this atlas appeared in the middle of a war! And, as a speleologist, a frequent visitor of the Serbian karst and a friend of Serbian cavers, I cannot stop wondering how the publishing of this book was still possible, given circumstances ... The Speleological Atlas of Serbia is structured in two parts : the first, gen eral section, is dedicated to several presentations of the Serbian karst as viewed from geological, hydrogeological and geomorphic perspec ti ves It also includes outlines of the present know ledge in some specialized speleo logical fields, such as: cave paleontology, biospeleology prehistoric s ites and cave use and management in Serbia. This synthesis is especially useful to the foreign reader since little has been published so far on the karst from Serbia, which was always eclipsed by its Dinaric counterpart. In the second section 81 caves and potholes are presented according to a model that includes: a short description of the cavity and its important fe a tures, a general location map, a small topographic and another geolog i cal map that would give the reader an idea about the basic settings and on th e opposite page, the plan and/or the profile of the respective cave. If there is a criticism I have for this book it is at this point since, in my opinion, both the topographic and the geologic maps are sometimes hard to read because of too many contours and/or details This is especially the case of the ca v i ties located in deeply dissected relief or in complicated geological settings However, due to the large-size format of the book, the cave maps are gen erally clear and easy to read. The quality of the print is overall very good, except, perhaps for the 14, full-page, color photographs that introduce each chapter Apart form th i s slight weakness, the book offers what we would expect any atlas to offer : many maps accompanied by concise and professional scientific informa tion. Therefore, I can only congratulate the Editor and the authors for their har d work. The Speleological Atlas of Serbia is a very fine book, desp ite (or, maybe, especially due to!) the numerous economical and political prob lems that our Serbian colleagues had to face during the last ten years And I daresay that it is the kind of national spele9logical atlas that many coun tries (including mine!) woufd like to be abTe to offer to the i nternational speleological community Silviu Constantin

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120 If one ever starts working on karst and in caves, then inevitably one of the first questions asked is how are caves formed under various geomorpho logic and geologic settings? The simpler the question, the more complex the answer. This is why 44 authors from 15 nations have put their knowl edge into one integrated volume that aims to present the advances made in recent decades in our understanding of the formation of dissolutional Speleogenesis. Evolution of Karst Aquifers is an extensive collection of pa pers covering the fields of karst groundwater flow, fundamentals of speleo genetic processes, development of cavities and cave systems in various set tings, and the mesoand micromorphology of caves. Speleogenesis in non carbonate lithologies and some practical aspects of speleogenetic stud ies such as porosity and permeability, the role of speleogenesis in the devel opment of hydrocarbon and mineral deposits, etc. are also presented. After the introduction, in which the Editors make a concise radiography of the book, a chapter is devoted to overviewing speleogenetic studies from a historical perspective. Chapter 3 (Geologic and Hydrogeologic Controls of Speleogenetic Devel opment), Chapter 4 (Theoretical Fundamentals of Speleogenetic Processes), and Chapter 5 (Development of Cavities and Cave Systems in Various Set tings) are the heart of the book. These chapters present the results of new research and provide new perspectives on existing information by discuss ing case studies. Unfortunately, many well-known karst and cave sites are missing (Chinese subtropical karst, caves such as Frasassi, Lechuguilla, and large and deep shafts from the Alps, Mexico, Mulu, etc.). In addition, some of the case studies are of limited interest to the general reader. Furthermore, not all of the subchapters are equally readable. For example, the chemistry and dynamics of cave genesis might be difficult to comprehend for non specialists. In many ways, it is these three chapters that make this book worth buying, because they provide a challenging and refreshing examination of Ule most important issues of speleogenesis. With few exceptions all chapters are well written; some of them, although succinct, provide fascinating accounts with a distinctly global flavor. Fur thermore, the editors have skillfully interspersed them with major contribu tions in most of the chapters. The book represents a testimony of a continuous interest in the evolution of karst aquifers and an example of a true multidisciplinary study maintained over a long time span. It will appeal to a wide readership in karst and cave science, as well as to general hydrogeologists dealing with karst terrains. The Editors of this book should be commended for their dedication to such a tremendous wqrk, without which we would have had to search through endless lists of publications on these topics. The book has been well edited, illustrated (occasional imperfections on dia grams or photos will be forgiven by readers), and produced by the National Speleological Society. It will definitely serve as a reference book, until, we can hope, it will be superseded by a future edition covering this topic in another 20 years or more. Bogdan P. Onac Book Reviews Speleogenesis. Evolution of Karst Aquifers. Klimchouk, A. 8., Ford, D. C., Palmer, A. N. & Dreybrodt, W., Editors National Speleological Society, Hunts ville, Alabama, 2000. 528 p, letter format (8 1/2x 11 "), hard cover, ISBN 1-879961-09-1. standard price: USD 60; online orders at: http://www .caves.org

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Theoretical and Applied Karstology, 13-14 (2000-2001) 121 Precis de Karstologie par Jean Noel Salomon Presses Universitaires de Bordeaux, Bordeaux, 2000. 250 p, format 15.5 x 24 em, 75 fig, 9 tab, 22 photos, ISBN: 2-86781-262-3. prix: 32 (210 FF). La litterature karstologique vient de s'enrichir avec une nouvelle publica tion, due a Jean-Noel Salomon, professeur de geographie physique a l'Uni versite Michel de Montaigne de Bordeaux, directeur du Laboratoire de Geographie Physique Appliquee de Ia meme universite et president de I' As sociation de Karstologie. Tel que le titre le montre d'emblee, il s'agit plutot d'un manuel que d'un veritable traite scientifique. Mais ceci n'empeche point que, specialement pour Ia France, sa parution constitue une necessaire et longtemps attendue mise au point sur les multiples proble mes lies au relief karstique et sur l'etat actuel des connaissances acquises dans ce domaine. C' est ce qui se detache clairement de Ia preface signee par le President d'honneur de I' Association de Karstologie, le pro fesseur Jean Nicod. L'ouvrage debute avec une breve recapitulation des proprietes que presen tent les roches susceptibles de constituer le support lithologique des formes propres au karst, notamment Ia roches carbonatees, et des particularites de Ia corrosion en tant que mecanisme fondamental qui preside a leur constitu tion. Sont passees ensuite en revue les principales formes qui composent le relief exokarstique, a savoir les lapies,les depressions ferrnees et les vallees developpees dans les regions calcaires. Mentionnons que, quoiqu'il admette que Ia limite entre les poljes classiques et les autres types de depressions karstiques est parfois difficile a tracer, I' auteur n' utilise le terme de polje que pour designer les vastes depressions a fond plat et dont Ia longueur est de I' ordre de plusieurs kilometres. Les deux chapitres suivants sont consacres au facteurs qui interviennent dans le processus de karstification, en precisant le role que jouent, d'une part, .Ja structure et Ia tectonique des roches calcaires, et d'autre part, le contexte hydrodynamique dans lequel se deroule ce processus et qui est dependant en grande mesure du relief de surface. D'un interet particulier sont les pages qui traitent de }'organisation erdu fonctionnement des aqui feres karstiques, car l'auteur insiste sur le fait que ceux-ci sont intimement lies a Ia porosite secondaire des roches carbonatees, dans lesquelles Ia cir culation des eaux se fait uniquement le long des fractures et des joints de stratification. II s' ensuit que I' aquifere karstique se distingue nettement d'une nappe phreatique, ce qui fait que le qualificatif de phreatique attribue souvent aux galeries des grottes ou au regime d'ecoulement souterrain n'esc guere justifie. Une importante partie de l'ouvrage est reservee a !'influence que le climat exerce sur le relief karstique, en imprimant Ia specificite si evidente des formes developpees dans chacune des grandes regions climatiques du globe terrestre, depuis les karsts tropicaux et jusqu'a ceux des zones de hautes altitudes et latitudes. Elle est suivie d'une analyse de la karstification en relation avec le facteur tempore}, qui aboutit a Ia conclusion que le paysage karstique est Un cumul d'heritages, car il conserve generalement les an ciennes formes de surface par suite de Ia disparition du reseau hydrographi que sous-aerien. Apres un rapide ex amen des elements dont I' etude fournit des informations utiles pour Ia reconstitution de Ia genese et I' evolution du karst (drainages s6uterrains, morphologie des galeries, depi)ts autochtones et allochtones), I' ouvrage prend fin avec une -recapitulation des principales modalites par lesquelles sont mises en valeur les ressources du karst et des problemes que souleve !'exploitation economique de celles-ci.

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122 Ecrit dans un langage qui allie Ia rigueur scientifique a un expose plutot didactique des faits et des theories, le Precis que nous propose Jean-Noel Salomon s' adresse non seulement a ceux qui, par leur specialite ou par leurs occupations, s'interessent au phenomene karstique, mais aussi au large pu blic En effet, le lecteur y trouve nombre d'informations qui doivent occu per leur place legitime dans Ia culture generale et qui sont presentees de maniere a pouvoir etre aisement comprises et assimilees. II n'y a done aucun doute que le premier beneficiaire de cette nouvelle publication sera la karstologie elle-meme. Gheorghe Racovifii The author of this book belongs to the young generation of Romanian kar stologists but his pxpertise in this field of science is already vast. Mter a long stage as an an\ateur caver, he became a researcher at the "Emil Racovita" Institute of Speleology in Cluj-Napoca and graduated postdoctoral stages in Norway, Sweden and the USA. He also visited and explored many caves in Europe, Latin America and South Mrica. This book appears as a neces sity, a "summum" of his activity researcher and as a senior lecturer at the "Babe-Bolyai" University. Although the title of the book is "Geology of Karst Terrains", by content it is in fact a course of Karstology, in all meanings of this term: interdisci plinarity, complexity and systemic relations. The first chapters deal with geological issues: mineralogical and petrographical characteristics of. karst rocks, physical and chemical principles of dissolution, elements of karst hydrogeology. The following section of the work addresses karst geomor phology: karst landforms, speleogenesis mechanisms and morphology of the underground. Other geological issues with specific relevance for karst landscapes are also addressed: the role of caves as a sedimentation environ. ment (detrital, organic and chemical deposits), and a special topic on the crystallography and mineralogy of speleothems. The interpretation of Qua ternary history based on cave deposits is another interesting part of the book; here, the new dating methods are thoroughly presented. Mter a short ap proach to cave climatology, including the specific problems of ice-caves, Bogdan Onac presents in a modern way the morphoclimatic systems and their associated karst landscape, the cyclic evolution of karst regions and the problem of paleokarst interpretation. The last section is dedicated to the management and protection of karst regions, including their economic is sues. The quality of the book is enhanced by a great number and variety of fig ures : maps, graphs, diagrams and photographs. AJ.l the chapters end with extended abstracts written in English and significant bibliographical lists. "Geology of Karst Terrains" is a valuable synthesis of the newest informa tion and trends in karstology and a book that will be welco_med by any specialist working in soluble rocks regions. Sorin Roatii Book Reviews Geologia regiunilor carstice by Bogdan P. Onac Ed. Didactica Pedagogica A.A., 2000 400 p, format 16.5 x 24 em, ISBN: 973-30-2266-7 "Geology of Karst Regions", in Romanian; extended abstracts of each chapter in English. price: USD 38 (postage included); on sale to the author: bonae@ bioge.ubbcluj.ro.

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Theoretical and Applied Karstology, 13-14 (2000-2001) 123 Scari!loara Glacier Cave. Monographic study by Ghe orghe Racovita & Bogdan P Onac Ed. Carpatica, Cluj-Napoca, 2000. 140 p, format 17 x 24 em, 52 fig, ISBN: 973-98752-1-1. price: USD 15 (postage included); on sale to the authors: bonac@bioge.ubbcluj.ro. Before the discovery of the Movile Cave in 1986, Sciirioara Ice-Cave, was undoubtedly the most studied cave in Romania. And though to day Movile seems to be, internationally, the most famous Romanian cave, for the Romanian public this first position is still occupied by Sclirioara. The first researches in this cave were carried out by the great scientist Emil as early as 1921. Systematic studies were launched by Racovita's successors approximately four decades ago and pursued within two stages, 1963-1968 and 1982-1992 More than 40 papers have been published, most of them being dedicated to the huge subterrannean ice-block and to its significances for the cave genesis and evolution. The lines above are intended to emphasize the importance of this work, in fact the first Romanian cave monograph of a high scientific level. So far, the most important and/or beautiful caves of the country have been only presented in picture books. The authors, reputed speleologists, have structured their work in logical and didactical sequence of nine chapters. From the very beginning (the In troduction) one can learn, among others, that Sclirioara is the biggest un derground ice accumulation in Romania, with a volume of over 75,000 m1 A short chapter dedicated to the cave exploration and research history, fol lows. The third chapter deals with the regional geographical, geological and hydrogeological settings. Sclir:ioara is here described as part of the extensive Ocoale-Ghefar-Dobre-Iti karst system of the Bihar Mountains. Further on, a presentation of the cave (Chapter 4) is accompanied by a con cise section dedicated to the speleogenesis ofOcoale-Ghe{ar-Dobreti karst system (Chapter 5). More than half of the book is dedicated to the under ground topoclimate and to the ice speleothems (Chapters 6 and 7) This is perfectly understandable if one takes into account that most of the system atic studies above-mentioned were specifically addressing those issues. The conclusions reached by our colleagues from Cluj after more than 15 years of extensive researches are of outstanding value. They systematically deal with the interpretation of specific parameters, such as: the ventilation sys tem, the air movement and temperature, the meroclimatic structure of the cave, the ice temperature, the relative humidity, the evapocondensation, the morphology and structure of ice speleothems, dynamics of ice speleothems at the paleoclimate information stored in the ice block. Apart from the study of those parameters, which intimately control the func tioning of the underground system, an attempt to reconstruct the last 3,000 years paleoclimate based on the ice block structure is also presented. Cal cite speleothem mineralogy and the results of U-series datings performed on samples from Sclirioara are only briefly discussed. The last chapter is dedicated to the cave fauna, which was also intensively studied since, due to the peculiar topoclimate of this cave, it may be consid ered as living close to the borders of the ecological tolerance. Consequently the underground biocenosis is dominated by a single troglobiont species, the Pheleuon proserpinae glaciale. In the end, we shall stress once again the great value of this first mono graphic paper dedicated to 'a Romanian cave and our hope that it will be followed by further publications on other equally well-studied and impor tant caves of the country. Traian Constantinescu

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124 Most of us dealing with activities-'-'related to karst" tmve-heard about Dr. Petar Milano vic and his vast experience in engineering diffe;rent projects in karst environment. It is worth mentioning the project implemented in classical karst area of the Trebisnica River that, in the early 70's, was the biggest in Europe. In fact this was only the beginning of a fruitful career including many other projects in Turkey, Iran or Greece. However, perhaps not many are aware of the existence of his latest book, entitled Geological Engineering In Karst. Why is this book so important? First, because geological engineering in karst areas is a delicate matter both from the perspective of genuine envi ronment preservation and from that of the reliability of the project itself. Secondly, because it is not a classical textbook considering only the theo retical aspects of the domain; it is rather the examples and the author's personal expertise that support the most important methods and technolo gies described. The introductory chapters represent a comprehensive review of karst phe nomena and grou-ndwater in karst areas, viewed according to their possible impact on the engineering projects to be implemented in such areas. The initial advantage of karst knowledge is highly exploited in the follow ing chapters. Geological investigations, performed all over the world, for dam sites, reservoirs, tunnels, grouting operations as well as water tapping and protection have built up, through the years, authors' greatest expertise. That is why these major issues, supported by specific examples streamlin ing to major problems and their solutions are largely described and com mented as Chapters 3 to 11. Methods and techniques for geological investi gations aiming to increase the knowledge of the possible impact of karst features on projects are listed or presented in detail There is no discrimination in showing either the success of the attempts or some failed projects in karst areas and the causes that led to failure. This is important since, in many cases learning from someone's mistakes may be possible ... The most important chapter is Grouting in karst, a collection of more than 30 examples described over 112 pages, considering that grouting is an essential preliminary operation for any further construction of dams and reservoirs on karstified bedrock. The final chapters, apparently less consistent than the previous ones are still clearly based on the author's (and his close collaborators) field experience and attempt to address several very specific issues that are still under de bate, such as the criteria for groundwater protection zoning in karst re gions, groundwater tracing techniques or application of geophysical meth ods in karst. The latest one is focused on high-tech procedures that can provide reliable information about underground extension and abundance (magnitude) of karst features. The book will be of substantial benefit to any geologists, civil engineers and all types of professionals and experts, that can find an answer to their problems when dealing with karstified rocks. Adrian Jurkiewicz Book Reviews Geological engineering in karst by Petar T Milanovic Ed. Zebra, Belgrade, 2000. 347 p, format 16.5 x 24 em, 190 fig, 11 color pages, hardcover, ISBN: 86-7489-125-X. price: USD 50 (postage included); on sale to the publisher: zebra@EUnet.yu.

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Theoretical and Applied Karstology, 13-14 (2000-2001) 125 Caves Beyond Time by Cristian Lascu Edited by Group of Underwater and Speleological Exploration (GESS), Bucharest, 2001. 176 p, 155 color photographs, A4 format, hardcover, ISBN: 973-85372-1-5. English and Romanian versions available. price: USD 35 (postage included); on sale to the editor : gess@dial.kappa.ro A picture book is particularly hard to review. Since we are specifically dealing with artistic emotions, reviewers' comments can only be subjective. This latest album of the reputed speleologist and cave photographer Crist ian l.o.scu makes no exception. For this reason, I will try to limit my comments only to the ingenious way the author has chosen in order to communicate his artistic and scientific message. The 'catch' with this book comes when one is trying to fit it into a precise category. "Caves beyond time" is not what we would normally expect from an album dedicated to the Romanian caves. It lacks the customary geo graphic approach and some sort of rigidity that this approach would bring along. Of course, the book is abundantly illustrated and the photographs are taking us from the Black Sea coast to the high Carpathian ridges, from deep gorges to the tranquility of karst plateau meadows, from huge chambers through canyon-like passages, along rapids and waterfalls to the deepest Romanian sumps. But the order that links all these images into a coherent masterpiece is not the 'geographical' one. The pictorial succes sion seems to obey a combination of geological and philosophical prin ciples and reflections regarding the Cave, which is seen both as an outcome and a witness of the immemorial Time. It is at this point when one may feel the necessity of additional clarifications in order to fully understand the succession of the images within the book And it is what the author has done by five short, but extremely suggestive, essays. The first one, "The unknown geography" attempts to explain why, despite the little extension of our karst, caves are so important for Roma nians, and what can our karst offers to the world. A second essay, called "The Stone House" invites the reader to decipher the harmony and the sim plicity of the underground architecture. The third part, "Water and time droplets" is dedicated to the traditional 'stars' of almost any Romanian famous cave: the speleothems and the crys tals. Here, again, the intimate combination of scientific information and philosophical reflections make up a highly unusual and innovative compo sition. "Caves, the first altars" is, to my knowledge, one of the very few works addressing the historical links between the people living around the caves of the country and their rituals, myths, and religion. The journey starts from the prehistoric times, goes through pre-Christian periods and ends in our days, when orthodox monks are still using natural or artificial caves for meditation. The finally chapter, "The Cave Beyond Time" is the only one that breaks the 'countrywide approach' since it is entirely dedicated to the world-famous Movile Cave. In a foreword entitled "A Foreign Visitor's View of Romanian Caves", Robert Cronk wrote: "There is an old rethorical question: If a tree falls in the forest and there in no one to hear it, does it make a sound? There can be a similar question for the caves: If a cave remains undiscovered and in dark ness, can it be beautiful?" As a Romanian speleologist, I think that Cristi Lascu's latest book may be indeed that trunk falling ... and I am glad that I have been in the forest! Silviu Constantin

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126 Protection of karstic areas is a very hot subject nowadays and often a topic of headed discussions. Therefore, Raymond Tercafs' book appears to be a waited event. Senior Research Associate of the Belgian National Fund for Scientific Research in the Department of Animal Physiology of the Univer sity of Liege (Belgium), Raymond Tercafs has more than 30 years of expe rience in exploring and studying caves in Europe, North Africa, South America and Southeast Asia. With extensive knowledge on ecology, geol ogy and computer application in cave management, his interest in cave pro tection is well known among the biospeleologists. The protection of the subterranean environments. Conservation principles and management tools includes twelve chapters structured on several is sues. The first chapters represent an introduction in karstology, biospeleol ogy and karst kinetics by explaining the basic principles governing the functioning of the very complex karstic systems. Such systems can be mod eled and processes can be simulated, as is exemplified in one of these intro ductory chapters. One of the most original parts for a book treating this subject is the psycho logical approach on the protection problems, explaining attitudes for and against environmental values. The causes of deterioration of the subterranean habitats and their fauna are thoroughly and extensively treated, representing another important part of the book. Many examples of the author's personal experiences and taken from the bibliography are the foundation for the next chapters, which present the principles of management. Ordinary caves or show caves can be pro tected in a better manner with the help of the computer-elaborated models of management. Given the importance of the legislation concerning the cave protection an interesting chapter compares the laws form different North American and European countries. Some ideas of Raymond Tercafs are gathered in the conclusion, chapter leaving the readers to meditate over the differences between conservation and protection and over our abilities to elaborate really etiicient manage ment plans in the subterranean environment. Always in the context of the general problematic of environment protection and using a rich and diverse bibliography, Raymond Tercafs has published the .first book on the protection and management of underground habitats. Oana Moldovan Book Reviews The Protection of the Subterranean Environment. Conservation Principles and Management Tools by Raymond Tercafs PSP Production Services Publishers, Luxembourg, 2001. 402 p, format 27.5 x 25 em, 75 fig. ISBN: 2-9599798-0-X.

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Theoretical and Applied Karstology, 13-14 (2000-2001) Petre-Mihai Samson 1930-2001 Le 22 avril, l'Institut de Speleologie a perdu l'un de ses chercheurs d'excellence par Ia disparition du Dr. Petre Mihai Samson. Sa carriere fut decisive dans Ia seconde moi tie du siecle passe pour le developpement de Ia paleobiologie des mammiteres en Roumanie et, en genenil, pour les disci plines se rapportant a I' etude du Quaternaire. II etait ne le 7.fevrier 1930 en France, a Toulouse ou son pere suivait des cours de specialisation a l'Universire Paul Sabatier . Avant qu'il commence ses etudes primaires, sa famille arrive en Roumanie et s' installe a Ploieti, ville oil il va accomplir son education au lycee Saints Pierre et Paul. Pendant son enfance et son adolescence son pere lui avait appris l'amour et le respect de Ia nature dans de longues promenades aux alentours de sa ville d' adoption Ainsi s' eveilla en lui sa vocation de naturaliste. II suit les cours de Ia Faculte de Biologie de l'Universite de Bucarest oil il est l'eleve de Margareta Dumitrescu qui condui sait Ia chaire de Zoologie des vertebres et qui orienta sa carriere vers I' etude des mammiteres fossiles. licencie en Biologie (1955), il commence ses etudes de paleontologie dans le cadre de l'Institut de Speleologie "Emil Racovitza" a peine reorga nise sous Ia direction des professeurs Constantin Mota, Traian Orghidan et Margareta Dumitrescu. En 1956, il conduit les fouilles dans Ia grotte La Adam en Dobrogea centrale qui seront executees pendant plus de seize ans, la premiere decouverte mettant au jour un ensem ble mithriaque renfermant, entre autres objets de culte, deux bas-reliefs representants le dieu Mithras. D'autres fouilles, dans Ia meme region, sont emplacees dans Ia grotte de Casian et dans Ia Grotte des Chauves-souris a Gura Dobrogei qui fournissent de riches faunes de rnicromammiteres du Pleisto cene moyen, completant ainsi les donnees sur le Pleistocene superieur acquises dans Ia grotte La Adam A partir de 1962, il entreprend des investigations paleontologiques minutieuses dans Ia Depression de BraOV en collaboration avec le Laboratoire de Geologie du Quaternaire conduit par Henriette Alimen et le Musee de Sfantu-Gheorghe represente par Kovacs Sandor. 127 In Memoriam En 1969, il presente au Congres IN QUA, tenu a Paris, Ia stra tigraphie du Pleistocene superieur en Roumanie, basee sur les resultats des fouilles entreprises dans le karst du centre de Ia Dobrogea et dans les depots fossiliteres stratifies de I a Depression de BraOV. Chercheur passionne, tenace et lucide il s'engage a prospecter et explorer les gisements plio pleis tocenes du secteur median de Ia vallee de I' Oltet ( 1960-1963) ou des riches faunes de mammiferes sont decouvertes a Tetoiu (Bugiuleti) et lrimeti. II continue en parallele ses etudes sur les mammiferes du Plio-Pleistocene et soutient (1975) sa these de doctorat en Biologie: Les Equides fossiles de Roumanie (Pliocene moyen-Pleistocene superieur) qui para1t un an plus tard dans Ia revue italienne Geologica Romana. Ses recherches continuent avec Ia decouverte d'associations de rnicromarnmiteres datant du Pliocene superieur et du Pleisto cene inferieur dans Ia vallee de I' Olt a Slatina, Drligl1neti-Olt et autres localitesdu secteurouestdu Bassin Dacique (1977-1983 ). Mentionnons aussi les fouilles entreprises dans le Pliocene in ferieur et moyen de Drl1nic et Podari dans Ia vallee du Jiu, avec Ia collaboration d'une equipe franyaise sous Ia direction du dr Sevket Sen du Museum national d'Histoire naturelle de Paris Esprit vif, anime d'une grande soif de conna1tre, il s'engage dans des contrats de recherches qui le determine de tourner son attention ve.rs les micromanunmileres du Miocene moyen et superieur du bassin de CriUl Alb (1978-1980). Quelques annees plus tard, une collaboration etablie avec les docteurs Jean-Louis Hartenberger et Jean Sudre du Laboratoire de Pa Ieontologie des vertebres du CNRS a Montpellier lui ouvre un nouveau domaine d'activite relatif aux mammiferes multitubercules d'age mesozoique final du bassin de Hateg J' ai eu le privilege d' etre son ami et collaborateur pendant pres que 50 ans, partageant avec lui aussi bien Ia fatigue des longues journees sur le terrain que Ia joie de chaque nouvelle decouverte Esprit d'une grande fmesse,le dr. Petre-Mihai Samson se dis tinguait par sa prodigieuse culture, son extreme exigence pous see jusqu' au scrupule et son sens aigu de Ia critique. Epris de peinture et dessinateur accompli, il executait lui-meme I' illus trations de ses travaux. II aimait aussi Ia litterature, Ia musique et ladanse. Sa personnalite d'exception, son intelligence penetrante et son talent de brillant causeur resteront graves dans Ia me moire de taus ceux qui se sont honores d' etre ses amis et ses Personnellement, je lui garderai un tres fidele souvenir tout le reste de rna vie. Dr. Constantin Riidules c u Membre correspondant de l'Academie Rouma i ne

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fragmentation, cave patterns, and the localization of karst ground water basins: the Appalachians as a test case. p 9 Tudor Tama, & Christiane Causse UTh TIMS chronology of two stalagmites from V11 Cave (Bihar Mountains, Romania). p. 25 Bogdan P. Onac Mineralogical studies and Uranium-series dating of speleothems from Glacier Cave (Bihar Mountains, Romania). p. 33 Silviu Constantin, Stein-Erik Lauritzen, Emanoil & Alexandru Petculescu Karst evolution in the Danube Gorge from U-series dating of a cave bear skull and calcite speleothems from de Ia Gura Ponicovei (Romania). p. 39 John Mylroie & John Jenson The Carbonate Island Karst Model applied to Guam. p. 51 Lee Florea, JOhn Mylroie & Jim Carew-Karst genetic model for the French Bay Breccia deposits, San Salvador Bahamas. p. 57 Gabriel Diaconu & Delia Dumitra, Sur Ia presence de l 'a rdealite dans Ia Grotte de Topolnita (Plateau de Mehedinti, Roumanie). p. 67 Vladimir Ljubojevic, Aleksandr Pacevski & Jelena CaliC:-Ljubojevic On the genetic conditions of black manganese deposits from two caves of Eastern Serbia. p 75 Nicoleta Feier, Gabriel Munteanu & Bogdan P. Onac Mineralogy and speleogenesis of the Ice Cave from Poiana Vartop (Bihor Mountains Romania) p. 81 Traian Constantinescu & Sllvlu Constantin La genese et !'evolution des grandes dolines (obans) de Ia zone karstique de Mangalia (Dobroudja du Sud, Roumanie) p. 87 Jan-Henning Ross, Feride Serefiddin, Michael Hauns & Chris C. Smart-24 h Tracer Tests on Diurnal Parameter Variability in a Subglacial Karst Conduit: Small River Valley Canada. p. 93 Dorothy J. Vesper, Caroline M. Loop & William B. White Contaminant transport in karst aquifers. p. 101 Patrik Brunet-Lecomte & Alexandra-Cristina Paunesco-Microtus (Terricola) grafi miciaensis (Rodentia, Mammalia) une nouvelle sous-espece du site mousterien de Gaura Lupului Hunedoara, Roumanie) p. 113


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