Geochemische Untersuchungen an Travertinen der Slowakei

Travertines are characterized by high rates of deposition. Waters from which travertines are precipitated have more than ten times the calcium concentration of mean continental surface waters. Calcium has been dissolved at some depth as sulfate and as carbonate the latter in bicarbonate rich waters.38 samples from the important travertine deposits of Slovakia have been analyzed for the major elements including sulfate and 4 minor elements (Sr, Mn, Zn, Cu). Strontium and magnesium are correlated with the sulfur content. Due to its isotopic composition sulfate can be of Triassic origin. 9 out of 16 spring waters from the areas of travertine deposition contain more than 1000 ppm HCO ₃ ^– +H₂CO₃ and 10 out of 16 more than 500 ppm SO ₄ ^2– . A high carbonate content of waters is correlated with isotopically heavy carbon of travertines. Heavy carbonate carbon occurs also in travertines from CO₂ discharging areas in Italy, Persia and Jugoslavia. A magmatic or metamorphic source of carbon dioxide can be considered for the carbonate of the majority of the Slovakian travertine deposits.

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Die Arbeiten, die von Dr. R. Demovi durchgeführt worden sind, wurden aus Mitteln der Humboldstiftung unterstützt. Für die großzügige Hilfe sei hiermit der Stiftung gedankt. Die Autoren sind ferner den Herren Dipl. Ing. O. Franko und Dipl. Ing. S. Gazda vom Geologischen Institut Diony tùr, Bratislava, SSR, zu besonderem Dank verpflichtet, da sie die Wasseranalysen beigetragen haben. Herr Dr. Carlo Savelli stellte freundlicherweise die Proben aus Tivoli bei Rom, Herr Dr. Bernhard Damm (Heidelberg) die Proben aus Persien und Herr Dr. Friedrich Lippmann die Proben aus Wolfegg und Cannstatt zur Verfügung.     

A sedimentological and stable isotopic study of travertines and associated sediments within Upper Triassic lacustrine limestones, South Wales, UK

The Upper Triassic in South Wales is composed of up to 100 m of red, dolomitic mudstones of the Mercia Mudstone Group which overlie and are laterally equivalent to basin margin coarse clastic deposits. In the Sully Island and Dinas Powys areas, a series of carbonate deposits was laid down within small basins adjacent to the main Bristol Channel Basin. The rocks consist of dolomites containing replaced evaporites, overlain by perilittoral freshwater limestones. The limestones are fenestral intrasparites and contain abundant pedogenic and stromatolitic horizons, as well as locally developed travertines. Evidence for vadose diagenesis within the limestones is common. The travertines consist of sheets of fibrous calcite (flowstone) associated with pisoids and flöe calcite. Most of the travertines consist of single sheets several millimetres in thickness although ‘mounds’up to 1 m in height and 5 m in diameter are also present. The topmost metre of the limestones, which has been dolomitized, is deformed into tepee and megapolygonal structures. The carbon and oxygen stable isotopic composition of the limestones suggests that they were precipitated in low salinity waters. Successive samples from individual bands of flowstone show a covariance of δ¹⁸C and δ¹³C which is consistent with the mixing of resurgent groundwaters with pools of more evolved waters at the surface. The sedimentological and geochemical evidence suggests that the limestones were deposited in a small, enclosed basin fed by upwelling meteoric groundwaters in an environment distinct from that in which the laterally equivalent gypsiferous red mudstones were formed.     

A new technique for precise uranium-series dating of travertine micro-samples

Secondary carbonate formations, such as travertine and calcareous tufa deposits, are important archives for quaternary continental climate studies and archaeology. The extremely complex growth mechanisms result in some serious problems for precise mass spectrometric uranium-series dating. Often, detrital and organic particles contaminate the carbonate and large pore volumes yield a great potential for open system behavior. We utilized microscopic, mineralogical and geochemical methods prior to sample selection to determine the abundance of primary calcite, i.e. micrite and spar. Furthermore, the state of alteration was characterized by cathodoluminescence and trace-element analysis. We conclude that travertine and calcareous tufa are appropriate for precise U-series age determination if a) micrite and/or spar are the dominant phases; b) cathodoluminescence of both phases is weak or absent; c) Fe and Al levels are low; and d) Sr concentrations are close to the average of the studied site. We mapped and sampled solely areas of major micrite/spar abundance having minor alteration for accurate U-series dating. When this new method was applied, travertines located in eastern Germany (sites Bad Langensalza, Burgtonna and Weimar-Ehringsdorf) gave single ²³⁰Th/²³⁸U-ages consistent with the lithological growth sequence and greatly improved compared to previously published chronologies. In addition, we determined ²³⁰Th/U isochron ages on bulk samples that confirm our single ages. In contrast to primary calcite, pore cements are homogeneously distributed throughout the travertine fabric and reflect early diagenetic processes and/or weathering.     

High strontium contents and Sr/Ca-ratios in Lake Constance waters and carbonates and their sources in the drainage area of the Rhine River (Alpenrhein)

Algal and mollusk carbonates in Lake Constance sediments proved Sr/Ca-ratios unusually high for fresh water environments. In most cases the observed Sr/Ca-ratios for mollusk shells fall into the range of marine mollusks. These high ratios can be attributed to a high Sr/Ca-ratio (6 ± 0.5) in Lake Constance water. In the Alpenrhein River, the main influent of Lake Constance, Sr/Ca-ratios were found to vary between 4.7 (at high water discharge) and 10.7 (at low water level). High Sr/Ca-ratios correspond to high sulfate contents. From all tributaries of the Alpenrhein, the Ill River revealed to have the highest Sr-contents and Sr/Ca-ratios. A detailed study of its drainage area led to the detection of exceptionally high Sr-contents (up to 11.6 mg/l) and Sr/Ca-ratios (up to 116.5) in springs of the Triassic Ladinian stage of the Austroalpine nappe zone (Ostalpine Deckenzone). The fact that high Sr-concentrations occur together with high sulfate contents leads to the assumption that celestite is leached within Ladinian rocks. This assumption is confirmed by the evidence that celestite deposits have been reported from the same stratigraphic section (Wettersteinkalk) from other localities in the Northern Calcareous Alps.

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Zusammenfassung In Bodensee-Sedimenten auftretende biogene Carbonate zeigen ein für Süßwasserbildungen ungewöhnlich hohes Sr/Ca-Verhältnis; die meisten bei Mollusken gefundenen Werte fallen in den marinen Bildungsbereich. Diese hohen Sr/Ca-Verhältnisse können durch das hohe Sr/Ca-Verhältnis des Bodenseewassers (6 ± 0,5) gedeutet werden, das seinerseits vom noch höheren Sr/Ca-Verhältnis des wichtigsten Zuflusses, des Alpenrheins (4,7 bei Hochwasser, 10,7 bei Niedrigwasser) geprägt wird. Hohe Sr/Ca-Verhältnisse fallen mit hohen Sulfatgehalten zusammen. Von allen Nebenflüssen des Alpenrheins zeigt die Ill die höchsten Sr-Gehalte und Sr/Ca-Verhältnisse. Eine Untersuchung des Einzugsgebietes der Ill führte zur Auffindung von Bächen und Quellen mit ungewöhnlich hohen Sr-Gehalten (bis 11,6 mg/l) und Sr/Ca-Verhältnissen (bis 116,5), die im Ladin der Alpinen Trias der Ostalpinen Deckenzone entspringen. Da hohe Konzentrationen mit hohen Sulfatgehalten zusammenfallen, kann angenommen werden, daß Coelestin aus Gesteinen des Ladins ausgelaugt wird und die hohen Sr/Ca-Verhältnisse der Wässer bedingt. Diese Annahme wird durch die Tatsache erhärtet, daß Coelestin im gleichen stratigraphischen Horizont (Wettersteinkalk) an mehreren anderen Stellen der Nördlichen Kalkalpen beobachtet wurde.

     

Travertines of the northern Caucasus

Mineralogical and isotope-chemical characteristics of carbonate travertines of the Greater Caucasus are investigated. It is shown that concentrations of many chemical elements, which predominantly precipitate together with iron hydroxides, decrease along the strike of the travertine dome. At the same time, δ¹³C and ¹⁸O values in carbonates systematically increase due to kinetic effects of isotope fractionation. This leads to the formation of isotopically heavy calcite (δ¹³C up to 16.3‰) near the travertine dome base. Concentrations of other elements (Mg, Sr, Ba, Na, S, and Li), which form a isomorphic part of calcite crystal lattice, almost do not change along the strike of the dome. Comparison of concentrations of these elements in travertines and initial water solutions makes it possible to get ideas on trends of their redistribution in the carbonate-water system. Correlations found in this work define not only TDS content and concentration of some ions, but also REE spectra and formation temperatures of ancient fluid systems.     

Impact of lake‐level changes on the formation of thermogene travertine in continental rifts: Evidence from Lake Bogoria,Kenya Rift Valley

Travertine is present at 20% of the ca 60 hot springs that discharge on Loburu delta plain on the western margin of saline, alkaline Lake Bogoria in the Kenya Rift. Much of the travertine, which forms mounds, low terraces and pool‐rim dams, is sub‐fossil (relict) and undergoing erosion, but calcite‐encrusted artefacts show that carbonate is actively precipitating at several springs. Most of the springs discharge alkaline (pH: 8·3 to 8·9), Na‐HCO₃ waters containing little Ca (<2 mg l^?1) at temperatures of 94 to 97·5°C. These travertines are unusual because most probably precipitated at temperatures of >80°C. The travertines are composed mainly of dendritic and platy calcite, with minor Mg‐silicates, aragonite, fluorite and opaline silica. Calcite precipitation is attributed mainly to rapid CO₂ degassing, which led to high‐disequilibrium crystal morphologies. Stratigraphic evidence shows that the travertine formed during several stages separated by intervals of non‐deposition. Radiometric ages imply that the main phase of travertine formation occurred during the late Pleistocene (ca 32 to 35 ka). Periods of precipitation were influenced strongly by fluctuations in lake level, mostly under climate control, and by related changes in the depth of boiling. During relatively arid phases, meteoric recharge of ground water declines, the lake is low and becomes hypersaline, and the reduced hydrostatic pressure lowers the level of boiling in the plumbing system of the hot springs. Any carbonate precipitation then occurs below the land surface. During humid phases, the dilute meteoric recharge increases, enhancing geothermal circulation, but the rising lake waters, which become relatively dilute, flood most spring vents. Much of the aqueous Ca²⁺ then precipitates as lacustrine stromatolites on shallow firm substrates, including submerged older travertines. Optimal conditions for subaerial travertine precipitation at Loburu occur when the lake is at intermediate levels, and may be favoured during transitions from humid to drier conditions.     

Geochemical,and stable and radiogenic isotope records in Devonian and Early Carboniferous carbonates from Valle de Tena,central Pyrenees (Spain): evidence for their diagenetic environments

Mineralogical, textural and geochemical investigations were made to determine the post-depositional evolution of Devonian and Early Carboniferous carbonates from Valle de Tena. The carbonate association is made up of low-Mg calcite, which occurs as micrite, spar cements, neomorphic patches and spar filling veinlets. Non-stoichiometric dolomite and ankerite occur as cements (dolomite also as replacements) in the Middle Devonian, post-dating calcite types. All these phases pre-date tectonic stylolites, indicating compaction after stabilization of the carbonate minerals. Strontium concentrations indicate that Early Devonian and Early Carboniferous micrites initially precipitated as aragonite; Middle and Late Devonian micrites precipitated as high-Mg calcites. Both precursors were diagenetically stabilized to low-Mg calcites through interaction with meteoric waters in phreatic environments. Trace elements in dolomite and ankerite indicate precipitation from Sr-enriched meteoric water. All studied carbonates, except Middle Devonian limestones, precipitated in reducing environments, which favoured incorporation of Fe and Mn. Late calcite generations precipitated from more saline waters than micrites. Light ¹⁸O values in micrites suggest alteration mainly in meteoric-phreatic environments. The dolomites and ankerites precipitated from more ¹⁸O-depleted fluids than the calcites, suggesting a greater contribution from meteoric waters. Variations in ¹³C of micrites represent primary secular trends, according to published ¹³C variations. The ¹³C oscillations within each succession probably relate to sea-level oscillations. Strontium isotopes also point to a meteoric origin of diagenetic fluids. Model calculations suggest that O and Sr isotopes equilibrated between calcites and fluid at relatively low water/rock ratios, whereas C isotopic signatures are inherited from limestones.     

Die Verteilung des Strontiums in oberjurassischen Karbonatgesteinen der Nördlichen Kalkalpen

Several publications on the environmental control of strontium in carbonate rocks have stimulated this investigation. Samples from three lithologically different units of the marine Upper Jurassic in the Northeastern Alps are analysed for strontium (x-ray fluorescence, atomic absorption, microprobe). Reported data on Sr in Recent carbonate secreting organisms, Recent and fossil carbonate sediments, on partition between calcite, aragonite and seawater have been used for comparison with those of the Upper Jurassic carbonate rocks. Reef sediments predominantly consisting of aragonite and high magnesium calcite lost extreme portions of their original Sr during diagenesis. Some layers (Oberalmer Schichten, St. Koloman) of probable bathypelagic origin are still comparable in strontium with primary marine calcite (about 0,1 % Sr).The pattern of the Sr distribution in the investigated Upper Jurassic limestones is mainly due to different courses of diagenetic change from different primary carbonates into low magnesium calcite. The change in Sr concentrations of diagenetic solutions is a function of the type of the supporting carbonate in an closed or open system of carbonates with porous solutions and is a function of seawater- or freshwater influence on the latter. A small strontium portion of these rocks occurs in apatite crystals with abnormal sulfur contents which could be identified as fragments of fish teeth.

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Wir danken Herrn Dr. A. Schkbidbb, (Göttingen) für zahlreiche Mikrosondenuntersuchungen und Herrn A. FENMNGER (Graz) für die quantitative Bestimmung der Tonrückstände in den Kalken. Für einen Teil der analytischen Arbeiten wurde ein Röntgenspektrometer der Deutschen Forschungsgemeinschaft benutzt.     

U/Th dating of the travertine deposited at transfer zone between two normal faults and their neotectonic significance: Cambazli fissure ridge travertines (the Gediz Graben-Turkey)

Abstract

The neotectonic characteristics of the travertines that outcrop near Cambazli Village to the west of the Gediz Graben in the Western Anatolia and the age determination of the travertine were carried out using the ²³⁰Th/^234,238U disequilibrium method. The Cambazli fissure ridge travertines represent the travertine depositions that develop at a transfer zone. The extent of these travertines is at NW-SE and NE-SW orientations and the ridge crest-trend of these travertines range between approximately 55° and 82° and they are located at an intersecting position. The evaluation of the fissure ridge travertine directions indicated that the compression stress that was responsible for the deposition of the Cambazli travertine was determined to be in the N-S orientation and the extensional stress was determined to be in the E-W orientation. The orientation of the dominant extension in Western Anatolia during the neotectonic period was N-S and this orientation is not in accordance with the directions of stress for the travertines. This situation indicates that the travertines were deposited along a transfer zone in N10W orientation between two normal faults. The travertines were determined to be active since the Upper Pleistocene as indicated by the age determination conducted using the ²³⁰Th/^234,238U disequilibrium method. The dilation rate of the travertines during dilation and the post-dilation period and the average dilation rate of the Cambazli travertines to the north of the Gediz Graben were calculated as 0.01–0.02 mm yr^?1 during deposition and as 0.05 mm yr^?1 during the post-dilation period. These dilation rates indicate lower tectonic activity along the northern ridge of the Gediz Graben than along the southern ridge.

© 2011 Lavoisier SAS. All rights reserved     

Travertine formation in Plitvice National Park, Yugoslavia: chemical versus biological control

Hydrochemical studies of the Plitvice Lakes and their tributaries (Croatia/Yugoslavia) were coupled with micromorphological investigations on carbonate lake sediments and recent travertines. Karst springs discharge water from aquifers in Triassic and Jurassic dolomites and limestones and collect in lakes, which are ponded behind accreting travertine dams. Waters at springs have a high CO₂ partial-pressure (greater than 7000 ppm) and are slightly undersaturated with respect to calcite (saturation index less than —0·03). CO₂ partial pressure is quickly reduced in swift running streams, leading to very high supersaturation with carbonate minerals (saturation indices between 0·74 and 0·53). Calcite deposition, however, is restricted to the lake bottoms (formation of lake marl) and to the tufa dams. The annual carbonate precipitating capacity of the system based on water balance and downstream loss of dissolved ions is estimated to be on the order of 10 000 t CaCO₃ as cascade deposits (tufa dams) or as micrite in lakes behind the travertine dams. The initial stages of travertine formation as a result of morphological, biological, and chemical factors are (i) moss settling on small ridges in the creek courses, (ii) epiphytes (diatoms and cyanobacteria) settling on the moss surface, (iii) micrite particles resuspending from lake bottoms and being trapped on mucous excretions from bacteria and diatoms, and (iv) inorganic calcite precipitating as sparite at nucleation sites provided by these crystal seeds. Geochemical studies of the lake marl and tufa dams show that amino acids are dominated by aspartic acid. Carbohydrates come from structural polysaccharides of diatoms. The sticky excretions, rich in aspartic acid, are necessary for the initiation of calcite precipitation. They may be a response of algal and bacterial metabolism to environmental stress by either nutrient depletion or high calcium concentrations in ambient waters. The formation of tufa and micrite (lake marl) appears to be initiated by localized biological factors and is not governed by mere calcite supersaturation of the water. Oligotrophy may be an essential precondition for the formation of fresh water carbonate deposits.     

Hydrochemical and isotope characteristics of spring water and travertine in the Baishuitai area (SW China) and their meaning for paleoenvironmental reconstruction

A method of combining hydrochemical data logging and in situ titrating with measurement of stable carbon and oxygen isotopes was used to reveal the hydrochemical and isotopic characteristics in the Baishuitai travertine scenic area of SW China. It was found that the travertine-forming springs have a very high concentration of calcium and bicarbonate, and accordingly very high CO₂ partial pressures, which are not likely to be produced by biological activity in soil alone. Further analysis of the stable carbon isotopes of the springs shows that the high pressure of CO₂ is mainly related to an endogenic CO₂ source. That means the Baishuitai travertine is endogenic in origin. This is contrast to the commonly accepted saying that the travertine deposition in this study simply is a product of warm and humid conditions in a karst ecological environment. Rapid CO₂ degassing from the water is triggered by the much higher partial pressures in water than that of the surrounding air. Consequently, as the waters flow downstream of the spring the pH increases, the waters become supersaturated with respect to calcite, and travertine is deposited. The preferential release of ¹²CO₂ to the atmosphere results in a progressive increase of travertine ¹³C downstream. This is concluded with a preliminary discussion of variation in travertine-forming water temperatures, according to differences in stable oxygen isotopic compositions of the travertine formed in different epochs at Baishuitai. It was found that the change in water temperature is as high as 13 °C, i.e., from 23 °C at about 2500 years b.p., to 10 °C at present. This may mainly reflect that the effect of geothermal source on water temperature is decreasing. The problems involved in paleoenvironmental reconstruction with endogene travertine are also discussed. They are the impacts of "dead carbon" in radiocarbon dating and the enrichment in ¹³C of travertine by endogenic CO₂ and degassing of CO₂ from water, which has to be considered in paleovegetation reconstruction when using ¹³C data of the endogene carbonate deposits.     

Determination of horizontal extension from fissure-ridge travertines: a case study from the Denizli Basin,southwestern Turkey

Travertine deposits reflect some aspects of the regional tectonics because of the close association between travertine deposits and active fractures, that later of which provide conduits along which travertine-depositing waters may rise. Fissure-ridge travertines form above extensional fissures which are located in the hanging walls of normal faults, in step-over zones between fault segments, or in active or recently active) volcanic provinces. Numerous active and inactive fissure-ridge travertines are located in the hanging walls of normal faults in the Denizli Basin. A typical fissure-ridge comprises a central fissure along its long axis and flanking bedded travertines dipping away from the fissure. Central fissures of travertine ridges have been dilating since the initiation of the fissures. Samples from both the margins and centres of banded travertine deposits were dated by Th/U methods in order to determine dilation rates. Individual fissures have been dilating at average rates of between 0.008 and 0.1 mm yr^–1 during travertine deposition, and ~ 0.001 and 0.007 mm yr^–1 after cessation of travertine deposition. There is a noticable decrease in dilation rate from west to east in the Denizli Basin, and this decrease in dilation rate may be related to decrease in overall extension in southwest Turkey, which decreases eastward.     

Depositional system and palaeoclimatic interpretations of Middle to Late Pleistocene travertines: Kocabaş, Denizli,south‐west Turkey

Travertine deposits in western Turkey are very well‐exposed in the area of Kocaba?, in the eastern part of the Denizli Basin. The palaeoclimatic significance of these travertines is discussed using U/Th dates, stable isotope data and palynological evidence. The Kocaba? travertine occurrences are characterized by successions of depositional terraces associated with palaeosols and karstic features. The travertines have been classified into eight lithotypes and one erosional horizon, namely: laminated, coated bubble, reed, paper‐thin raft, intraclasts, micritic travertine with gastropods, extra‐formational pebbles and a palaeosol layer. The analysed travertines mostly formed between 181 ka and 80 ka (Middle to Late Pleistocene) during a series of climatic changes including glacial and interglacial intervals; their δ¹³C and δ¹⁸O values indicate that the depositional waters were mainly of basinal thermal origin, occasionally mixed with surficial meteoric water. Palynological results obtained from the palaeosols showed an abundance of non‐arboreal percentage and xerophytic plants (Oleaceae and Quercus evergreen type) indicating that a drought occurred. Marine Isotope Stage 6 is represented by grassland species but Marine Isotope Stage 5 is represented by Pinaceae–Pinus and Abies, Quercus and Oleaceae. Uranium/thorium analyses of the Kocaba? travertines show that deposition began in Marine Isotope Stage 6 (glacial) and continued to Marine Isotope Stage 4 (glacial), but mostly occurred in Marine Isotope Stage 5 (interglacial). The travertine deposition continued to ca 80 ka in the south‐west of the study area, in one particular depression depositional system. Palaeoenvironmental indicators suggest that the travertine depositional evolution was probably controlled by fault‐related movements that influenced groundwater flow. Good correlation of the stable isotope values and dates of deposition of the travertines and palynological data of palaeosols in the Kocaba? travertines serve as a starting point for further palaeoclimate studies in south‐west Turkey. Additionally, the study can be compared with other regional palaeoclimate archives.     

Biotic and inorganic control on travertine deposition at Bullicame 3 spring (Viterbo, Italy): A multidisciplinary approach

A multidisciplinary characterization of an active thermal spring in central Italy has been undertaken with the aim of (i) ascertaining whether microbiological activity plays a relevant role in hot-depositing travertines and (ii) establishing an experimental protocol able to identify similar effects in fossil travertines. Water, gas, and travertine samples were investigated by chemical (ICP/MS, SEM/EDS), physical (DTA-DTG), isotopic (δ¹⁸O, δD, and δ¹³C), mineralogical (XRPD), and spectroscopic (EPR) techniques. Twenty-four samples (three for each phase) were collected every 5 °C temperature drop, along a ∼100 m long artificial channel near Viterbo (Bullicame 3, Latium, central Italy). A microbiological characterization was carried out in parallel, sampling the channel every 10 °C temperature drop.The Bullicame 3 system is revealed to be composed of two markedly different subsystems: a water/gas interface, where a kinetically fast exchange allows equilibrium of components both in water and in gases; a solid/water interface, where travertine precipitation occurs, influenced by microbiological activity. A peculiar lattice shrinking of calcite was identified, as well as an anomalous value of the zero-field splitting parameter from the EPR measurements. The interpretation of these anomalies is confirmed by the identification of calcifying cyanobacteria throughout the channel path.Our results point out that microbiological activity can play a significant role in travertine deposition from hot springs. Furthermore, the proposed approach, representing a tool to identify crystal chemical remnants of past microbiological activity, could be applicable to fossil travertines.     

Long-term analog of carbonation in travertine from Uleimat Quarries, Central Jordan

Quaternary travertine capping the metamorphic (cement) zones in Uleimat Quarries, central Jordan, has been precipitated from hyperalkaline paleogroundwaters. Such waters are similar to the cement pore water and to the present day hyperalkaline seepages (pH 12.5) in Maqarin, north Jordan. The isotopic depletions observed in Uleimat travertine, with δ¹³C values as low as −25.45‰, suggest that they have been precipitated during CO₂ uptake by highly alkaline calcium hydroxide waters. The travertine in Uleimat Quarries indicates a long-term analog of carbonation and remobilization of silica in cementitious barriers for radioactive waste repositories. The presence of Cr-rich smectites and relatively high levels of Cr (4.1%), V (657 ppm), Ni (163 ppm), Zn (634 ppm) and U (34 ppm) in the green travertine and the associated opaline silica phases suggests the use of the Uleimat travertines as analogs with the repository disturbed zone. Smectites and silica phases are expected to be a sink for alteration products in the late stage evolution of a high pH plume. Co-precipitation of these elements in mineral phases is of great importance to control the concentration of these elements in groundwater.     

Fluid inclusion and stable isotope studies of Pb-Zn-fluorite-barite mineralization in the lower and middle Benue Trough,Nigeria

Lead-zinc-fluorite-barite veins in the lower and middle Benue Trough (Nigeria) are located within the Lower Cretaceous (Albian) carbonaceous shales, limestones, and arkosic sandstones of this intracontinental rift structure. The veins in the lower Benue Through consist of sphalerite + galena+marcasite ± chalcopyrite ± barite in a gangue of siderite and quartz hosted by carbonaceous shales, whereas in the middle Benue Trough, fluorite, barite, quartz, and similar sulfide minerals are hosted by limestone and sandstone. Fluid inclusion temperatures in vein minerals range from 95°C to 200°C (without pressure corrections) and salinities range from 14 to 24 equiv. wt% NaCl. Oxygen isotope compositions of limestone wall rocks (middle Benue) have been lowered from premineralization ¹⁸O values of about 25 per mil to approximately 16 per mil. Fluid in equilibrium with vein calcite has a calculated ¹⁸O of +2.6 per mil at 130°C. The ⁸⁷Sr/⁸⁶Sr ratio of this calcite (0.71497) suggests that strontium and calcium had a considerably more radiogenic source than the Cretaceous limestone or evaporite did (⁸⁷Sr/⁸⁶Sr=0.7073–0.7078). Observed strontium data, lead isotope compositions of galena, and REE patterns in fluorite suggest that the Lower Paleozoic basement rocks in the trough or their weathered equivalents are likely sources for the Benue Trough ore components. Sulfur isotope data suggest that the sulfur was probably contributed from the Cretaceous evaporites in the trough.Our data favor a basinal brine source for the ore-forming fluid. Fluid criculation probably resulted from high geothermal gradients accompanying continental rifting. Brine interaction with the clastic, carbonate, and evaporite rocks led to metal and sulfur leaching and later deposition in fractures accompanying the Cenomanian deformation and uplift in the Benue Trough.     

Carbonate alteration associated with talc-chlorite mineralization in the eastern Pyrenees, with emphasis on the St. Barthelemy Massif

Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ¹⁸O values decrease down to values of 12‰ towards the contact with dolostones. This ¹⁸O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from ⁸⁷Sr/⁸⁶Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with ⁸⁷Sr/⁸⁶Sr = 0.7094 near dolomitization fronts. Dolostones have δ¹⁸O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (⁸⁷Sr/⁸⁶Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ¹⁸O values close to dolostones but substantially lower δ¹³C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with ⁸⁷Sr/⁸⁶Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ¹⁸O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.