Identifying low-temperature hydrothermal karst and palaeowaters using stable isotopes: a case study from an alpine cave,Entrische Kirche,Austria

The area south of the prominent east–west trending Salzach Valley at the northern rim of the Central Alps of Austria has long been known to host anomalously warm springs emerging from a highly deformed calcite marble (Klammkalk). This unit also hosts cavities whose shapes suggest a hydrothermal karst origin and which are lined by calcite spar. We report here petrographic and isotopic evidence suggesting that dissolution by ascending low-temperature thermal waters also played an important role in the origin of a large cave in this region, Entrische Kirche. A paleo cave wall, preserved behind a thick flowstone in the interior of this cave, revealed a brownish bleaching zone which contrasts to the medium grey colour of the unaltered marble beneath. Across this zone the C and O isotope values gradually decrease by 3 and 11‰, respectively. These compositions are very different from those of the speleothem above but are similar to phreatic calcite spar from hydrothermal karst cavities in other outcrops in the area, where the absence of two-phase fluid inclusions suggests a low-temperature (less than ca. 50°C) hydrothermal origin. U/Th dating of the flowstone capping the alteration zone yielded a minimum age of the thermal water invasion in Entrische Kirche of ca. 240 kyr. There is no evidence in Entrische Kirche that these palaeowaters reached the point of calcite precipitation, but it is physically conceivable that higher and as yet unexplored parts of this deep (ca. 900 m) cave contain cavities lined by phreatic cave spar.     

Weathering processes in the Indus River Basin: implications from riverine carbon, sulfur, oxygen, and strontium isotopes

This study deals with the major ions and isotope systematics for C, O, S, and Sr in the Indus River Basin (IRB). Major ion chemistry of the Indus, and most of its headwater tributaries, follow the order Ca²⁺>Mg²⁺>(Na⁺+K⁺) and HCO₃⁻>(SO₄²⁻+Cl⁻)>Si. In the lowland tributaries and in some of the Punjab rivers, however, (Na⁺+K⁺) and (SO₄²⁻+Cl⁻) predominate. Cyclic salts, important locally for Na⁺ in dilute headwater tributaries, constitute about 5% of the annual solutes transported by the Indus. Weathering of two lithologies, sedimentary carbonates and crystalline rocks, controls the dissolved inorganic carbon (DIC) concentrations and its carbon isotope systematics throughout the Indus, but turbulent flow and lower temperatures in the headwaters, and storage in reservoirs in the middle and lower Indus promote some equlibration with atmospheric carbon dioxide. Combined evidence from sulfur and oxygen isotopic composition of sulfates refutes the proposition that dissolution of these minerals plays a significant role in the IRB hydrochemistry and suggests that any dissolved sulfates were derived by oxidation of sulfide minerals.

In the upper Indus, silicate weathering contributes as much as 75% (or even higher in some tributaries) of the total Na⁺ and K⁺, declining to less than 40% as the Indus exits the orogen. In contrast, about two-thirds of Ca²⁺ and Mg²⁺ in the upper Indus (over 70% in some tributaries) and three-fourth in the lower Indus, are derived from sedimentary carbonates. The ⁸⁷Sr/⁸⁶Sr ratios tend to rise with increasing proportions of silicate derived cations in the headwater tributaries and in the upper and middle Indus, but are out of phase or reversed in the lower Indus. Finally, close to the river mouth, the discharge weighted average contribution of silicate derived Ca²⁺+Mg²⁺ and silicate derived Na⁺+K⁺ are, respectively, about one-fourth and two-thirds of their total concentrations.     

Diagenesis, palaeoclimate and tectono-sedimentary influences on clay mineralogy and stable isotopes from Upper Cretaceous marine successions of the Basque-Cantabrian Basin (N Spain)

Clay mineralogy and whole-rock stable isotopes (δ¹⁸O and δ¹³C) of Upper Cretaceous marly sediments on the Basque-Cantabrian Basin have been integrated to determine the main effects of diagenesis, palaeoclimate and tectono-sedimentary factors in sections belonging to deep- (Barrika) and platform-marine (Isla de Castro, Villamartín and Olazagutía) settings.The mean values for the clay assemblages and δ¹⁸O exhibit notable differences among the sections, partially explainable by the influence of diagenesis. The Barrika sediments, with more diagenetically advanced illite-smectite (I-S) mixed-layer (R1, 70% illite), authigenic chlorite, and low δ¹⁸O (−4.05‰ PDB), experienced higher diagenetic grade than Isla de Castro and Olazagutía, which have R0 I-S (20% illite) and heavier δ¹⁸O. Villamartín was also affected by higher diagenesis than Isla de Castro and Olazagutía, given the occurrence of R1 I-S (60% illite) and low δ¹⁸O (−4.11‰ PDB). However, the absence of other clays in Villamartín (e.g. authigenic chlorite) is indicative of less diagenetic grade than Barrika. These results show the useful integration of clay mineralogy and stable isotopes to detect different diagenetic grades in distinct marine successions of the same basin.Despite being influenced by diagenesis, the clay mineralogy partially preserves its inherited signature. This allows detection of major contents of I-S and mica, and minor kaolinite, interpreted as indicative of warm palaeoclimatic conditions. High kaolinite content in Villamartín and absence of kaolinite in Isla de Castro, though, are considered to be a product of neither diagenesis nor palaeoclimatic influences. Instead, tectono-sedimentary causes, related to unsuitable conditions for clay formation and transport from the local source areas, contributed to original clay differences. The inferred effects of diagenesis, palaeoclimate and tectono-sedimentary factors make this work important to show the potentially great variety of controls on the clay mineralogy of marine sections, which are often uncritically treated in studies concerning the Late Cretaceous.     

Use of hydrogeochemistry and environmental isotopes for evaluation of groundwater in Qingshuihe Basin,northwestern China

Hydrogeochemistry and environmental isotope data were utilized to understand origin, geochemical evolution, hydraulic interconnection, and renewability of groundwater in Qingshuihe Basin, northwestern China. There are four types of groundwater: (1) shallow groundwater in the mountain front pluvial fans, originating from recent recharge by precipitation, (2) deep paleo-groundwater of the lower alluvial plains, which was formed long ago, (3) shallow groundwater in the lower alluvial plains, which has undergone evaporation during the recharge process, and (4) mixed groundwater (shallow and deep groundwater in the plain). The main water types are Na–HCO₃, which dominates type (1), and Na–SO₄, which dominates types (2) and (3). Geochemical evolution in the upper pluvial fans is mainly the result of CO₂ gas dissolution, silicates weathering and cation exchange; in the lower alluvial plains, it is related to mineral dissolution. The evaporative enrichment only produces significant salinity increases in the shallow groundwater of the lower alluvial plains. Shallow groundwater age in the upper plain is 10 years or so, showing a strong renewability. Deep groundwater ages in the lower plain are more than 200 years, showing poor renewability. In the exploitation areas, the renewability of groundwater evidently increases and the circulation period is 70–100 years.     

Tracking paleoecological and isotopic changes through the K-Pg boundary from marine ostracodes: The Poty quarry section,northeastern Brazil

Ostracode assemblages of the Poty quarry, Pernambuco-Paraíba Basin, northeastern Brazil, record an abrupt faunal change near the Cretaceous-Paleogene (K-Pg) boundary. Paleoecological and stable isotope analyses of ostracode carapaces were used to interpret the paleoenvironmental changes that took place from the Late Maastrichtian to the Early Danian. Ostracode distribution demonstrates substantial changes at and around the boundary with the last occurrences of most species and appearance of new ones. Stable isotope analyses carried out for four ostracode species distributed along the entire succession exhibit oscillations in the isotopic composition before the K-Pg boundary, thus suggesting that environmental changes may have begun slightly prior the boundary event itself. These changes may have triggered the extinctions that culminated at the K-Pg boundary, marked by positive δ¹⁸O and negative δ¹³C excursions. The K-Pg boundary is marked by cooling of bottom seawaters and a decrease in productivity, as well as the beginning of an extensive marine regression.     

Early Holocene climate signals from stable isotope composition of ice wedges in the Chara Basin,northern Transbaikalia,Russia

Stable isotope composition of syngenetic and epigenetic ice wedges, radiocarbon age, and pollen spectra of the surrounding deposits were studied during long term investigations at the "Belyi Klyuch" site on the first(6-8 m height) terrace of the Chara River(720 m.a.s.l.) in northern Transbaikalia to assess climatic conditions during ice-wedge formation. It was revealed that Holocene ice wedges had been formed from 10 to 7.5 ka 14 C BP. The isotope composition(δ~(18)O, δ~2 H) of relict ice wedges is the lightest and amounts-23‰ and-185‰, correspondingly. The isotopic compositions of ice lenses from sandy loam above ice wedges are-15.7‰, and-133‰; of small ice wedge in peat and sand are-15.3‰ and-117.9‰, accordingly.Interpretation of the ice wedge isotope composition has yielded that mean winter temperatures during cold stages of Holocene optimum were lower than today, during warm stages they were close to modern ones. During the coldest stages of Holocene optimum the total annual freezing index varied from-5100 to-5700 ℃ degree days, i.e. 300-600 ℃ degree days colder than during extremely severe modern winters. The total annual thawing index varied from 1300 to 1800 ℃ degree days, which was slightly higher than modern ones.     

Hydrologic and climatic implications of stable isotope and minor element analyses of authigenic calcite silts and gastropod shells from a mid-Pleistocene pluvial lake, Western Desert, Egypt

Authigenic calcite silts at Wadi Midauwara in Kharga Oasis, Egypt, indicate the prolonged presence of surface water during the Marine Isotope Stage 5e pluvial phase recognized across North Africa. Exposed over an area of  4.25 km², these silts record the ponding of water derived from springs along the Libyan Plateau escarpment and from surface drainage. The δ¹⁸O values of these lacustrine carbonates (− 11.3‰ to − 8.0‰ PDB), are too high to reflect equilibrium precipitation with Nubian aquifer water or water of an exclusively Atlantic origin. Mg/Ca and Sr/Ca of the silts have a modest negative covariance with silt δ¹⁸O values, suggesting that the water may have experienced the shortest residence time in local aquifers when the water δ¹⁸O values were highest. Furthermore, intra-shell δ¹⁸O, Sr/Ca, and Ba/Ca analyses of the freshwater gastropod Melanoides tuberculata are consistent with a perennially fresh water source, suggesting that strong evaporative effects expected in a monsoonal climate did not occur, or that dry season spring flow was of sufficient magnitude to mute the effects of evaporation. The input of a second, isotopically heavier water source to aquifers, possibly Indian Ocean monsoonal rain, could explain the observed trends in δ¹⁸O and minor element ratios.     

Petrological, geochemical, and stable isotope constraints on the genesis of the Miocene igneous rocks of Chetaibi and Cap de Fer (NE Algeria)

Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ³⁴S and δ¹⁸O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ³⁴S values (−5.4‰ to −12.2‰) and high δ¹⁸O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ³⁴S and δ¹⁸O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ³⁴S, between −33.2‰ and +25.7‰. Massive andesites with δ³⁴S between +6.8‰ and +7.6‰ preserve a ³⁴S-enriched mantle signature. The δ³⁴S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ³⁴S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ¹⁸O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ¹⁸O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ¹⁸O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ¹⁸O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].     

Study of stable isotopes for highly deformed aquifers in the Hsinchu-Miaoli area, Taiwan

This study was based on the analysis of isotopic compositions of hydrogen and oxygen in samples from precipitation, groundwater and stream water. In addition, parts of groundwater samples were dated by carbon-14 and tritium. These data are integrated to provide other views of the hydrologic cycle in the Hsinchu-Miaoli groundwater district. The groundwater district is principally composed of Pleistocene and Holocene aquifers. The Pleistocene aquifers are highly deformed by folding and faults into small sub-districts with areas of only tens of square kilometers. These aquifers are exclusively recharged by local precipitation. The Holocene aquifers cover narrow creek valleys, only tens of meters in thickness. The local meteoric water line (LMWL), constructed from rainfall samples in the Hsinchu Science Park, is described by the equation δD=8.02δ¹⁸O+10.16, which agrees with the global meteoric water line. In addition, the precipitation isotopic compositions can be categorized into two distinct end members: typhoon type and monsoon type. The groundwater isotopic compositions are perfectly located on an LMWL and can be considered a mixture of precipitations. Based on the mass balance of isotopic compositions of oxygen and hydrogen, infiltration is more active in the rainy season with depleted isotopic compositions. The amount of infiltration during May–September is roughly estimated to comprise at least 55% of the whole year’s recharge. The isotopic compositions of stream water are expressed by a regression equation: δD=7.61δ¹⁸O+9.62, which is similar to the LMWL. Although precipitation isotopic compositions are depleted during summer time, the isotopic compositions contrarily show an enriched trend in the upstream area. This is explained by the opposite altitude effect on isotopic compositions for typhoon-related precipitations.     

Monitoring Cenozoic climate evolution of northeastern Tibet: stable isotope constraints from the western Qaidam Basin,China

Carbon and oxygen stable isotopic composition of Cenozoic lacustrine carbonates from the intramontane Qaidam Basin yields cycles of variable length and shows several distinct events driven by tectonics and climate changes. From Eocene to Oligocene, the over-all trend in the δ¹³C composition of lacustrine carbonates shows a shift toward higher values, possibly related to higher proportions of dissolved inorganic carbon transported to the lake or lower input of soil derived CO₂. At the same time, the δ¹⁸O composition of lacustrine carbonates is decreasing in accordance with the global cooling trend and northwards drifting of the whole region. During the Miocene, distinct isotopic events can be recognized, although their interpretation and linkage to a certain tectonic event remains difficult. These events may be related to uplift in the Himalayas, to the strongest phase of uplift in the Altyn Mountains, to pronounced subsidence of the Qaidam Basin or to the expansion of C4 plants on land. Generally cold, highly evaporative conditions can be deduced from enrichment of δ¹⁸O isotopic compositions during Pliocene and Quaternary times.     

Paleoceanography and climate of the Badenian (Middle Miocene, 16.4–13.0 Ma) in the Central Paratethys based on foraminifera and stable isotope (δ18O and δ13C) evidence

Benthic foraminifera and stable isotopes analyses revealed changes emerging in the paleoceanographic scenery in the Paratethys. The percentage of inbenthic, oxyphylic taxa and diversity in the benthic foraminiferal assemblage showed increasing food supply (organic matter), decreasing oxygen level and growing stress on the sea floor. Oxygen isotopes measured in planktonic and benthic foraminifera pointed to strengthening stratification during the Badenian period. The carbon isotopes indicated intensified accumulation of light marine organic matter. This increasing stratification trend is especially pronounced by Late Badenian (13.5–13 Ma) when surface water oxygen isotope values are rather negative. A simple two-layer circulation model was worked out for the Badenian Paratethys explaining these characteristic environmental changes. An antiestuarine (lagoonal) circulation is assumed for the Central Paratethys during the Early (16.4–15 Ma) and mid Badenian (15–13.5 Ma). The mid Badenian period of time comprises the short episode of evaporite formation in the Carpathian Foredeep and the Transylvanian Basin. Evidence presented here supported a reversal of circulation to estuarine type after the deposition of salts by Late Badenian (13.5–13 Ma). The Early Badenian antiestuarine circulation is suggested to associate with the high temperatures of the Mid-Miocene Climatic Optimum, and the Late Badenian estuarine circulation with the cooler period following it.     

滇西北铜厂沟Mo-Cu矿床成矿流体和成矿物质来源:矽卡岩矿物学与稳定同位素证据

义敦地体位于三江特提斯成矿域中北段,晚三叠世和晚白垩世斑岩-矽卡岩型Mo-Cu多金属成矿作用强烈。铜厂沟Mo-Cu矿床位于义敦地体最南端,是近年来该区新探明的Mo-Cu矿床之一,已探明资源量142.5Mt。矽卡岩在铜厂沟矿区广泛出露,是该矿区最主要的赋矿岩石。根据矿物组合及共生关系,可将矽卡岩划分为石榴子石矽卡岩、透辉石矽卡岩和透闪石矽卡岩三种类型。通过详细的地质填图和钻孔岩心编录,发现铜厂沟矿区矽卡岩矿物组合受花岗闪长斑岩体与大理岩空间分布的控制:(1)由大理岩向外依次发育透辉石矽卡岩→透闪石矽卡岩→石榴子石矽卡岩;(2)由浅至深,石榴子石粒度逐渐变大;③矿化与透闪石、绿帘石等退化蚀变矿物密切相关,矿体多形成于外接触带。矽卡岩中最主要的矿物是石榴子石,多呈自形粒状或粒状集合体产出,颜色较深,均质性,以钙铝榴石为主(62.2%~78.3%),其次为钙铁榴石(16.7%~34.2%),少量锰铝榴石、铁铝榴石和镁铝榴石,属于钙铝榴石-钙铁榴石固溶体系列(Gro62-78And17-34Spe+Pyr+Alm2-6)。石榴子石Fe~(2+)/Fe~(3+)比值变化范围为0.00~0.20,平均值为0.06,指示石榴子石形成于酸性的氧化环境。石榴子石的δ~(18)OSMOW变化范围为5.2‰~9.5‰,反映矽卡岩可能直接继承斑岩体的氧同位素组成;金属硫化物具有较为均一的S-Pb同位素范围(δ~(34)S(CDT)=-0.7‰~1.4‰;~(206)Pb/~(204)Pb=18.332~18.694,~(208)Pb/~(204)Pb=38.454~39.088,~(207)Pb/~(204)Pb=15.588~15.663),表明成矿流体和成矿物质均来源于壳源的长英质岩浆。     

Constraints of stable isotopes on the origin of alunite from advanced argillic alteration systems in Bulgaria

Voluminous areas of advanced argillic alteration (AAA) constitute major exploration targets for surficial Cu–Au epithermal and potentially underlying porphyry-type deposits. In Bulgaria, more than 30 alunite occurrences are recognised, few of them being associated with a mineralised system. A mineralogical study combined with a stable isotopic (O, H, S) study has been carried out on nine alunite occurrences of advanced argillic zones hosted by volcanic rocks of Late Cretaceous age in the Srednogorie belt and of Oligocene age in the Rhodopes belt. This work was realised in order to constrain the origin of alunite and to define criteria to discriminate alunite from ore deposits and alunite from large barren alteration systems.Mineralogy of the nine occurrences consists of alunite + quartz + minor alumino-phospho-sulphates, associated with more or less kaolinite, dickite, pyrophyllite, diaspore and zunyite, depending on formation temperature. Alunite generally occurs as tabular crystals but is also present as fine-crystalline pseudocubic phases at Boukovo and Sarnitsa, in Eastern Rhodopes. In the advanced argillic alterations associated with economic ore, the presence of zunyite in the deeper parts indicates acid–fluorine–sulphate hydrothermal systems, whereas it is absent in uneconomic and barren advanced argillic alteration. All occurrences are formed at temperatures between 200 and 300 °C.(H, O, S) isotopic signatures of alunite combined with mineralogical features from all the studied occurrences, whatever their type, show characteristics of magmatic-hydrothermal systems. Sulphur data indicate essentially a magmatic origin for sulphur. Oxygen and hydrogen data suggest that hydrothermal fluids result from a mixing between magmatic fluids and an external component, which is identified as seawater-derived fluids or meteoric water in the vicinity of a sea. In most of the alunite occurrences, magmatic fluids are dominant and H₂S/SO₄ ratios are estimated to be higher than 2. Two exceptions exist in the Rhodopes. At Boukovo and Sarnitsa, where the estimated formation temperatures of alunite are the lowest, the external fluids are dominant and H₂S/SO₄ratios are estimated to be lower than or close to 1.At this stage of the work, the mineralogical and isotopic criteria do not enable a clear distinction between economic and uneconomic systems. However, some features are common in the economic ore deposits: the presence of zunyite in the deeper part of the system, the relatively high temperatures suggested by the zunyite + pyrophyllite + alunite + diaspore assemblages, the (O, H, S) signature of alunite, which is characteristic of dominant magmatic–hydrothermal acid–sulphate–fluorine systems.     

Palaeoclimate indicators (clay minerals,calcareous nannofossils,stable isotopes) compared from two successions in the late Jurassic of the Volga Basin (SE Russia)

A study of clay mineral and calcareous nannofossil abundances in late Jurassic–early Cretaceous sediments from the Volga Basin, SE Russia, is presented. From these results, we are able to compare some general patterns of mineralogical and palaeontological change for the Volga Basin to the palaeoclimate models developed for northern Europe and beyond. The two successions examined comprise calcareous mudstones with black organic‐rich shale horizons, overlain by a series of phosphatic silty sands. Clay mineralogical results show a progressive decrease in kaolinite and the concomitant increase of smectite and illite through the middle Volgian, followed by an abrupt increase in kaolinite in the late Volgian. The clay mineral evidence suggests increasing aridity at the end of the Jurassic, similar, in part, to many western European successions. Because of differential settling of clay minerals, superimposed upon this possible climatic signature is likely to be the effect of relative sea‐level change. Calcareous nannofossil analysis from a single section reveals a shift through the middle Volgian from low nutrient, warm water assemblages dominated by Watznaueria to cooler surface water and high nutrient assemblages dominated by Biscutum constans. These observations suggest that increased aridity is also associated with climatic cooling. Black shales are associated with increased productivity, higher sea levels and increases in smectite content. Hence, periods of low (chemical) hinterland weathering during semi‐arid conditions are paradoxically associated with relatively nutrient‐rich waters, and organic‐rich shales. Comparison of published carbon and oxygen stable isotope results from this and other sections to the clay mineral and nannofossil data confirms the palaeoclimatic interpretation. This study significantly improves the published biostratigraphically constrained clay mineral database for this time period, because other European and North American successions are either non‐marine (and thus poorly dated), absent (through penecontemporaneous erosion) or condensed. Copyright © 2002 John Wiley & Sons, Ltd.     

Drowning history of a Miocene carbonate platform (Zhujiang Formation, South China Sea)

The identification and interpretation of drowning events in the geologic record can aid significantly to the reconstruction of the depositional, tectonic and eustatic history of a study area and often improve reservoir and seal prediction in carbonate rocks. The differentiation between drowned platforms showing a record of continuous deepening and those with a record of exposure followed by rapid deepening remains, however, problematic. The Zhujiang carbonate platform (Liuhua 11-1 field, South China Sea) study shown here provides an example of an integrated approach combining high-resolution geochemistry, microfacies analyses and foraminiferal biostratigraphy in order to improve the reconstruction of environmental conditions prior, during and after platform demise and drowning. The Zhujiang carbonate platform displays the following vertical succession of four facies types i) skeletal grain facies with a miogypsinid/lepidocyclinid-dominated fauna deposited in a moderately deep (< 50 m), oligotrophic back-reef setting; ii) in situ corals in patch-reef facies in an oligotrophic lagoon (< 10 m); iii) rhodoid facies with in situ red algal crusts, dominated by Heterostegina sp. and spiroclypeids, possibly capped by a subaerial exposure surface. Well-rounded rhodoids representing a mesotrophic lagoon dominate the upper portions of the rhodoid facies; iv) pelagic marine shales of the Hanjiang Formation burying the carbonate platform after drowning. This facies succession, in combination with geochemical evidence suggests a deepening-upward trend. This trend might have been interrupted by transient subaerial exposure but no evidence for meteoric diagenesis was found at the drowning unconformity topping the carbonate platform. Instead, microfacies analyses suggest that platform demise may be related to progressive changes in environmental conditions, including increasing nutrient-levels and/or decreasing temperature up-core towards the drowning unconformity. These findings are of significance for those concerned with Miocene carbonate factories and, more specifically, the demise of carbonate platforms in general.     

Spatio-temporal variation of stable isotopes of river waters, water source identification and water security in the Heishui Valley (China) during the dry-season

Spatial variations of δD and δ¹⁸O among seven tributaries and their water sources were investigated in the Heishui Valley of the Yangtze River, China during the dry-season in 2004. A one-way ANOVA (analysis of variation) test showed that both δD (p?18O (p?=?0.045) spatially varied among the seven tributaries. The plot of δ¹⁸O versus δD for the river water collected at different locations showed that isotopic fractionation occurred during the snow and glacial melting process. The depleted δ¹⁸O and δD in the tributary waters distributed above the local meteoric water line (LMWL) suggested that the glacial and early snowpack meltwater largely recharged these streams during the early spring. The meltwater was isotopically distinguishable from the precipitation and river water, which had been evaporated during warmer and drier times. If glaciers and snow accumulation diminish with future climate warming, the recharge of these tributaries’ baseflow will decline and the security of the water resource in this watershed will be threatened.     

Magmatic hydrothermal origin of the Hadamengou-Liubagou Au-Mo deposit,Inner Mongolia,China: Constrains on geology,stable and Re-Os isotopes

The Hadamengou-Liubagou Au-Mo deposit is the largest gold deposit in Inner Mongolia of North China. It is hosted by amphibolite to granulite facies metamorphic rocks of the Archean Wulashan Group. To the west and north of the deposit, there occur three alkaline intrusions, including the Devonian-Carboniferous Dahuabei granitoid batholith, the Triassic Shadegai granite and the Xishadegai porphyritic granite with molybdenum mineralization. Over one hundred subparallel, sheet-like ore veins are confined to the nearly EW-trending faults in the deposit. They typically dip 40° to 80° to the south, with strike lengths from hundreds to thousands of meters. Wall rock alterations include potassic, phyllic, and propylitic alteration. Four distinct mineralization stages were identified at the deposit, including K-feldspar-quartz-molybdenite stage (I), quartz-pyrite-epidote/chlorite stage (II), quartz-polymetallic sulfide-gold stage (III), and carbonate-sulfate-quartz stage (IV). Gold precipitated mainly during stage III, while Mo mineralization occurred predominantly in stage I. The δD_H2O and δ¹⁸O_H2O values of the ore-forming fluids range from −125‰ to −62‰ and from 1.4‰ to 7.5‰, respectively, indicating that the fluids were dominated by magmatic water with a minor contribution of meteoric water. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal carbonate minerals vary from −10.3‰ to −3.2‰ and from 3.7‰ to 15.3‰, respectively, suggesting a magmatic carbon origin. The δ³⁴S_CDT values of sulfides from the ores vary from −21.7‰ to 5.4‰ and are typically negative (mostly −20‰ to 0‰). The wide variation of the δ³⁴S_CDT values, the relatively uniform δ¹³C values of carbonates (typically −5.5‰ to −3.2‰), as well as the common association of barite with sulfides suggest that the minerals were precipitated under relatively high fo₂ conditions, probably in a magmatic fluid with δ³⁴S_ƩS ≈ 0‰. The Re-Os isotopic dating on molybdenite from Hadamengou yielded a weighted average age of 381.6 ± 4.3 Ma, indicating that the Mo mineralization occurred in Late Devonian. Collectively, previous ⁴⁰Ar-³⁹Ar and Re-Os isotopic dates roughly outlined two ranges of mineralizing events of 382–323 Ma and 240–218 Ma that correspond to the Variscan and the Indosinian epochs, respectively. The Variscan event is approximately consistent with the Mo mineralization at Hadamengou-Liubagou and the emplacement of the Dahuabei Batholith, whereas the Indosinian event roughly corresponds to the possible peak Au mineralization of the Hadamengou-Liubagou deposit, as well as the magmatic activity and associated Mo mineralization at Xishadegai and Shadegai. Geologic, petrographic and isotopic evidence presented in this study suggest that both gold and molybdenum mineralization at Hadamengou-Liubagou is of magmatic hydrothermal origin. The molybdenum mineralization is suggested to be associated with the magmatic activity during the southward subduction of the Paleo-Asian Ocean beneath the North China Craton (NCC) in Late Devonian. The gold mineralization is most probably related to the magma-derived hydrothermal fluids during the post-collisional extension in Triassic, after the final suturing between the Siberian and NCC in Late Permian.     

Hydrogeochemical processes,mixing and isotope tracing in hard rock aquifers and surface waters from the Subarnarekha River Basin, (east Singhbhum District,Jharkhand State,India)

Geochemical observations, including major ion and trace element analysis, and isotopic tracing have been carried out in the Subarnarekha River system (northeastern India) during a surface-water- and groundwater-monitoring program aimed at evaluating impacts of mining. The aquifer is of fracture type. Groundwater flow conditions and pollutant transfer were observed through a network of 69 wells. δ¹⁸O and δ²H results suggest that transfer from rainfall towards groundwater storage through soils and the unsaturated zone is fast, without any major transformation like evaporation. The scatter of ⁸⁷Sr/⁸⁶Sr signatures in surface water and groundwater are explained by three end-members. One is compatible with rainwater inputs. The most mineralised end-member represents anthropogenic inputs (agricultural practices and ore processing). The third end-member, characterised by a high ⁸⁷Sr/⁸⁶Sr signature, is believed to be controlled by natural geochemical processes, although affected by human activities (e.g. drainage of mine waste). Potential flow paths, investigated north of the area, reveal that all groundwater types seem to evolve more in pockets than along a flow path. The limited extent of transfer and the predominance of natural phenomena help to explain the moderate level of groundwater contamination and the characteristics of surface water contamination by mining and the metallurgy industry.     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.     

Stable isotope study of cave percolation waters in subtropical Brazil: Implications for paleoclimate inferences from speleothems

We analyze the interannual monthly variability of oxygen isotope ratios in data from IAEA stations along the Atlantic coast of South America between 23° and 34° S to evaluate the influence of parameters such as temperature, rainfall amount and moisture source contribution on meteoric water recharging two karst systems in subtropical Brazil. In addition, a 2 year monitoring program performed on soil and cave drip and rimstone pool waters from sampling sites with contrasting discharge values and located at 100 and 300 m below the surface in the Santana Cave System (24°31′ S; 48°43′ W), is used to test the influence of hydrologic and geologic features on the temporal variations of seepage water δ¹⁸O.

Interannual monthly variations in δ¹⁸O of rainfall reflect primarily regional changes in moisture source contribution related to seasonal shifts in atmospheric circulation from a more monsoonal regime in summer (negative values of δ¹⁸O) to a more extratropical regime in winter (positive values of δ¹⁸O). Variations in groundwater δ¹⁸O indicate that the climatic signal of recent rainfall events is rapidly transmitted through the relatively deep karst aquifer to the cave drip waters, regardless of location of collection in the cave. In addition, the data also suggest that water replenishment in the system is triggered by the increase in hydraulic head during periods when recharge exceeds the storage capacity of the soil and epikarst reservoirs. Significant perturbations in the groundwater composition, characterized by more positive values of δ¹⁸O, are probably connected to an increased Atlantic moisture contribution associated with extratropical precipitation. This implies that the δ¹⁸O of speleothems from caves in this region may be a suitable proxy for studying tropical–extratropical interactions over South America, a feature that is intrinsically related to the global atmospheric circulation.