Lower Miocene gypsum palaeokarst in the Madrid Basin (central Spain): dissolution diagenesis, morphological relics and karst end-products

Abstract The Miocene sedimentary record of the Madrid Basin displays several examples of palaeokarstic surfaces sculpted within evaporite formations. One of these palaeokarstic surfaces represents the boundary between two main lithostratigraphic units, the Miocene Lower and Intermediate units of the Madrid Basin. The palaeokarst formed in lacustrine gypsum deposits of Aragonian age and corresponds to a surface palaeokarst (epikarst), further buried by terrigenous deposits of the overlying unit. Karst features are recognized up to 5·5 m beneath the gypsum surface. Exokarst and endokarst zones are distinguished by the spatial distribution of solution features, i.e. karren, dolines, pits, conduits and caves, and collapse breccias, sedimentary fills and alteration of the original gypsum across the karst profiles. The development of the gypsum palaeokarst began after drying out of a saline lake basin, as supported by recognition of root tubes, later converted to cylindrical and funnel‐shaped pits, at the top of the karstic profiles. The existence of a shallow water table along with low hydraulic gradients was the main factor controlling the karst evolution, and explains the limited depth reached by both exokarst and endokarst features. Synsedimentary fill of the karst system by roughly laminated to massive clay mudstone with subordinate carbonate and clastic gypsum reflects a punctuated sedimentation regime probably related to episodic heavy rainfalls typical of arid to semi‐arid climates. Duration of karstification is of the order of several thousands of years, which is consistent with previous statements that gypsum karstification can develop rapidly over geologically short time periods.     

Can stable isotopes be used to monitor landfill leachate impact on surface waters?

Bacterially mediated methanogenesis in municipal solid waste landfills has been shown to cause an enrichment of carbon stable isotope ratios of dissolved inorganic carbon and hydrogen stable isotope ratios of water in landfill leachate. In the present study, we investigate the universality of this enrichment in leachate obtained from four diverse landfill sites in New Zealand. At each site, surface water samples upstream and downstream of landfills were analysed to examine the applicability of stable isotope ratios as a tool for monitoring leachate contamination in landfill-associated streams. The design of leachate collection systems, operational history, and landfill location appeared to strongly influence leachate isotopic values and the effectiveness of isotope ratios as an environmental monitoring tool for surface water.     

Miocene silcretes in argillaceous playa deposits, Madrid Basin, Spain: petrological and geochemical features

Four regressive sequences are present in the opaline rocks and related deposits of the Miocene Intermediate Unit of the Madrid Basin. The sequences consist of silty mudstones and argillaceous opals, separated by transitional facies. The silty mudstone consists mainly of dioctahedral smectites, whereas the argillaceous opal is principally opal-CT and variable amounts of sepiolite. In the transitional facies, lamina of dioctahedral smectite co-exist with neoformed opal-CT and sepiolite. Petrological and geochemical features (major, trace and REE elements) indicate that the opaline levels and the transitional facies are related and are a consequence of silcrete formation in an argillaceous playa deposit. The isocon method was used to calculate changes in element concentration associated with silcrete formation. The geochemical data suggest silicification in an arid environment. The silcrete profile occurs four times, possibly as a result of highstand–lowstand fluctuations of the lake level caused by climatic changes. Structures and cements in the silcretes indicate that, although silicification may have commenced at the top of a groundwater table, it continued in the unsaturated zone above the water table.     

Chemical composition of landfill leachate in a karst area with a Mediterranean climate (Marbella, southern Spain)

 Between March 1994 and April 1997, the physical and chemical parameters and chemical composition of the urban solid waste leachate of the Marbella landfill (southern Spain) were determined. The data obtained show an ammonium and sodium chloride and bicarbonate type, a pH>7 and high mineralization, effectively described by the following parameters: Na⁺, K⁺, NH₄ ⁺, Cl^– and alkalinity. The chemical composition depends on the rainfall: in dry years, the mineralization and component concentrations have values as much as double those found in normal rainfall years. After storm events, a major and rapid dilution (within several hours) is seen in the leachate. Received: 28 January 1998 · Accepted: 2 June 1998     

Removal of trace elements from landfill leachate by calcite precipitation

Spontaneous precipitation of secondary calcite (CaCO₃) has been observed in 25 samples of landfill leachate-polluted stream waters. During the 6-month precipitation experiment, the formation of calcite acts as a principal trace-element scavenging process. The concentrations of Fe, Sr, Ba and Mn and other trace elements in solution significantly decreased as calcite formed during the experiments. The PHREEQC-2 geochemical code indicated high supersaturation of the initial leachate-polluted waters with respect to calcite. The chemical/mineralogical study (SEM/EDS, XRD, ICP MS) revealed that this newly formed calcite contains considerable amounts of metals and metalloids removed from solution. Such a geochemical process can be considered to be important for spontaneous decontamination in landfill-affected environments (stream sediments, soils) or landfill technical facilities (settling basins). This removal takes place especially during dry periods with low rain precipitation, when the landfill waters exhibit both higher alkalinity and higher trace element concentrations.     

Hydrogeological studies on the mechanical behavior of landfill gases and leachate of the Nanjido Landfill in Seoul, Korea

 The Nanjido Landfill is the largest uncontrolled landfill in Korea and it causes various kinds of environmental problems. Landfill gases and leachate are recognized as the most serious environmental problems associated with the landfill. This study employs a series of numerical models and uses test data to interpret the distribution and flow of landfill gases and leachate. Leachate seepage appears about 40–60 m higher than the estimated basal groundwater table. Thus, seepage data indicate that perched or floating leachate layers are formed in the unsaturated zone of the landfill. The leachate production rate is estimated using infiltration test data and a model for unsaturated groundwater flow. Geochemical data indicate that the landfill leachate degrades the basal groundwater quality along the downgradient zone. The environmental impact of the leachate on river water is estimated. Received: 17 June 1996 · Accepted: 2 October 1996     

Iron isotopes in acid mine waters and iron-rich solids from the Tinto–Odiel Basin (Iberian Pyrite Belt, Southwest Spain)

The isotopic composition of Fe was determined in water, Fe-oxides and sulfides from the Tinto and Odiel Basins (South West Spain). As a consequence of sulfide oxidation in mine tailings both rivers are acidic (1.45 < pH < 3.85) and display high concentrations of dissolved Fe (up to 420 mmol l^− 1) and sulphates (up to 1190 mmol l^− 1).The δ⁵⁶Fe of pyrite-rich samples from the Rio Tinto and from the Tharsis mine ranged from − 0.56 ± 0.08‰ to + 0.25 ± 0.1‰. δ⁵⁶Fe values for Fe-oxides precipitates that currently form in the riverbed varied from − 1.98 ± 0.10‰ to 1.57 ± 0.08‰. Comparatively narrower ranges of values (− 0.18 ± 0.08‰ and + 0.21 ± 0.14‰) were observed in their fossil analogues from the Pliocene–Pleistocene and in samples from the Gossan (the oxidized layer that formed through exposure to oxygen of the massive sulfide deposits) (− 0.36 ± 0.12‰ to 0.82 ± 0.07‰). In water, δ⁵⁶Fe values ranged from − 1.76 ± 0.10‰ to + 0.43 ± 0.05‰.At the source of the Tinto River, fractionation between aqueous Fe(III) and pyrite from the tailings was less than would be expected from a simple pyrite oxidation process. Similarly, the isotopic composition of Gossan oxides and that of pyrite was different from what would be expected from pyrite oxidation. In rivers, the precipitation of Fe-oxides (mainly jarosite and schwertmannite and lesser amounts of goethite) from water containing mainly (more than 99%) Fe(III) with concentrations up to 372 mmol l^− 1 causes variable fractionation between the solid and the aqueous phase (− 0.98‰ < Δ⁵⁶Fe_{solid–water} < 2.25‰). The significant magnitude of the positive fractionation factor observed in several Fe(III) dominated water may be related to the precipitation of Fe(III) sulphates containing phases.     

Metal speciation and attenuation in stream waters and sediments contaminated by landfill leachate

The degree of metal contamination (Zn, Pb, Cu, Ni, Cd) has been investigated in the vicinity of an old unmonitored municipal landfill in Prague, Czech Republic, where the leachate is directly drained into a surface stream. The water chemistry was coupled with investigation of the stream sediment (aqua regia extract, sequential extraction, voltammetry of microparticles) and newly formed products (SEM/EDS, XRD). The MINTEQA2 speciation-solubility calculation showed that the metals (Zn, Pb, Cu, Ni) are mainly present as carbonate complexes in leachate-polluted surface waters. These waters were oversaturated with respect to Fe(III) oxyhydroxides, calcite (CaCO₃) and other carbonate phases. Three metal attenuation mechanisms were identified in leachate-polluted surface waters: (i) spontaneous precipitation of metal-bearing calcite exhibiting significant concentrations of trace elements (Fe, Mn, Mg, Sr, Ba, Pb, Zn, Ni); (ii) binding to Fe(III) oxyhydroxides (mainly goethite, FeOOH) (Pb, Zn, Cu, Ni); and (iii) preferential bonding to sediment organic matter (Cu). These processes act as the key scavenging mechanisms and significantly decrease the metal concentrations in leachate-polluted water within 200 m from the direct leachate outflow into the stream. Under the near-neutral conditions governing the sediment/water interface in the landfill environment, metals are strongly bound in the stream sediment and remain relatively immobile.     

Pilot-scale field model tests for detecting landfill leachate intrusion into the subsurface using a grid-net electrical conductivity measurement system

The grid-net electrical conductivity measurement system for detecting exact locations of landfill leachate intrusion in the subsurface was developed in this study. Laboratory and pilot-scale field model tests were performed to evaluate the direct application of a grid-net electrical conductivity measurement system for the detection of landfill leachate. A significant increase in electrical conductivity of soil was observed by adding landfill leachate. This can be explained as an increase in electrical conductivity of pore fluid due to an increase in leachate constituents as charge carriers. In pilot-scale field model tests, leachate intrusion locations were accurately identified at the initial stage of landfill leachate release by the grid-net electrical conductivity measurement system. The electrical conductivity of the subsurface before leachate injection lay within a small range of 24.8–43.0 S/cm. The electrical conductivity values in detected points were approximately ten times more than the conductivity values of the subsurface without landfill leachate intrusion. The results in this study indicate that the grid-net electrical conductivity measurement method has a possible application for detecting locations of landfill leachate intrusion into the subsurface at the initial stage, and thus has great potential in monitoring leachate leakage at waste landfills.     

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.     

右江盆地北山MVT铅锌矿床黄铁矿Re-Os同位素体系及其对定年的启示

密西西比河谷型（MVT）铅锌矿作为一种重要的矿床类型,其成矿时代的精确厘定一直是该类矿床研究的重点。中国西南右江盆地是我国重要的MVT铅锌成矿带,本次研究选取了右江盆地东部北山铅锌矿作为研究对象,对成矿期内黄铁矿开展了LA-ICP-MS微量元素分布分析和Re-Os同位素定年。8件黄铁矿样品Re-Os等时线年龄为443.2±3.3Ma（MSWD=320）,明显早于赋矿的泥盆系碳酸盐岩地层,且数据点具有较高的离散性,表明黄铁矿Re-Os同位素年龄不能够有效约束北山Pb-Zn矿床成矿时代。其中,2件黄铁矿样品具有较高的Re含量,分别是107.1×10^-9和260.0×10^-9,结合对应薄片LA-ICP-MS微量元素面扫描分析结果,表明黄铁矿裂隙有机充填物具有较高的Re含量,对黄铁矿Re-Os测试结果存在显著的干扰。年代学结果显示,裂隙较发育的具有较高Re含量的2件黄铁矿样品模式年龄分别为399.0Ma和402.0Ma,这与富含有机质的泥盆系赋矿地层的年代基本一致,初步表明黄铁矿中高Re含量的充填物质可能来自于围岩地层。基于北山Pb-Zn矿床黄铁矿Re-Os定年及硫化物面微量元素分析结果,本次研究认为复杂的矿石结构及其所影响的样品物质不纯是阻碍MVT矿床高精度定年的重要因素。

     

Sulphur and carbon isotopic composition of power supply coals in the Pannonian Basin, Hungary

The present work is an attempt to establish the stable isotope database for Mesozoic to Tertiary coals from the Pannonian Basin, Hungary. Maceral composition, proximate analysis, sulphur form, sulphur isotopes (organic and pyritic), and carbon isotopes were determined. This database supports the assessment of the environmental risks associated with energy generation, the characterization of the formation and the distribution of sulphur in the coals used.The maceral composition, the sulphur composition, the C, S isotopic signatures, and some of the geological evidences published earlier show that the majority of these coals were deposited in freshwater and brackish water environments, despite the relatively high average sulphur content. However, the Upper Cretaceous, Eocene, and Lower Miocene formations also contain coal seams of marine origin, as indicated by their maceral composition and sulphur and carbon chemistry.The majority of the sulphur in these coals occurs in the organic form. All studied sulphur phases are relatively rich in ³⁴S isotopes (δ³⁴S_organic = + 12.74‰, δ³⁴S_pyrite = + 10.06‰, on average). This indicates that marine bacterial sulphate reduction played a minor role in their formation, in the sense that isotopic fractionation was limited. It seems that the interstitial spaces of the peat closed rapidly during early diagenesis due to a regime of high depositional rate, leading to a relative enrichment of the heavy sulphur isotopes.     

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.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Late Miocene nonmarine sedimentation and formation of magnesites in the Acıgöl Basin, southwestern Anatolia, Turkey

The Late Miocene lacustrine Acıgöl Basin, SW Turkey, formed as an orogen-top, extensional half-graben, with the subaqueous accommodation controlled by the lake level and the bulk accommodation provided by active subsidence along a WSW-trending normal fault at the basin's southern margin. The basin-fill sedimentary succession consists of terminal alluvial-fan facies overlain by ephemeral lake-margin facies and perennial lake facies, with widespread fluvial facies at the top. The distal alluvial-fan facies include massive to stratified sandstones and massive mudstones with intervening nodular dolostones and incipient pedogenic horizons. The lake-margin facies are micritic magnesites passing laterally into peloidal, irregularly laminated magnesites towards the palaeolake margin and overlain by marlstones and dolostones, all with abundant evidence of episodic subaerial exposure (desiccation cracks, pedogenic features, and tepee structures). The perennial lake facies are micritic magnesites passing upwards into clayey dolostones and dolomitic or clayey marlstones. The fluvial facies capping the succession include planar cross-stratified conglomerates (channel-fill deposits), planar parallel-stratified, planar cross-stratified and rippled cross-laminated sandstones (crevasse-fill and crevasse splay deposits), and assemblages of mudstones intercalated with thin sandstone beds (overbank floodplain deposits).The sedimentological, mineralogical and geochemical data reveal large variations in the basin's hydrological regime, including short-term oscillations and bulk rise of the lake level, periodical changes in the Mg/Ca ratio and terrigenous mud supply, and a negative covariance of δ¹⁸O and δ¹³C fluctuations. The composition of terrigenous sediment and the chemistry of water supplied to the lake were controlled by the weathering, chemical leaching and erosion of the ultramafic–dolomitic bedrock in the catchment area. The bedrock yielded Mg-rich carbonate solutions that caused the deposition of Mg-carbonates in the lake.Despite short-term lake-level fluctuations, the lake's net water budget remained positive. It is suggested that the region's present-day climate and Mg-rich alkaline lakes can serve as an analogue for the climatic and hydrological conditions in the Late Miocene Acıgöl Basin.     

上黑龙江盆地砂宝斯金矿黄铁矿地球化学特征及其成矿意义

砂宝斯金矿床是上黑龙江盆地内唯一的大型岩金矿床,但其成矿物质来源和矿床成因仍然存在争议。为此,在详细的矿相学和黄铁矿显微结构研究基础上,对不同世代黄铁矿开展LA-ICP-MS微量元素和S、Pb同位素分析。结果表明,砂宝斯金矿床从成矿早期到主成矿阶段,黄铁矿可划分为3个世代,不同世代黄铁矿微量元素组成差异明显。PyⅠI为金的主成矿期,其中Au、Ag、Cu、Pb、Zn、Bi、Co、Ni、As、Mn、Sb、Sn、Ga等元素含量较高。Co、Ni、As以类质同象的形式进入黄铁矿晶格, Cu、Pb、Zn、Sb、Bi元素以金属硫化物矿物包裹体的形式赋存于黄铁矿中。Au元素以Au+、银金矿、铜金矿矿物包裹体微粒和亚微米的包体金形式存在于黄铁矿中。As–置换S–,形成Au(HAs)–,对Au的迁移及沉淀具有重要的作用。砂宝斯金矿床黄铁矿Co/Ni比值大多数小于1,大部分点落入沉积成因范围,少部分落入火山成因和热液成因范围,表明黄铁矿并非单一来源。综合S、Pb同位素及黄铁矿微量元素特征,砂宝斯金矿床成矿物质既来源于具上地壳和地幔混源特征的深部岩浆,又来源于二十二站组围岩。结合区域成矿构造背景,认为蒙古—鄂...     

First Reliable Re–Os Ages of Pyrite and Stable Isotope Compositions of Fe(‐Cu) Deposits in the Hami Region,Eastern Tianshan Orogenic Belt,NW China

The Eastern Tianshan Orogenic Belt (ETOB) in NW China is composed of the Dananhu–Tousuquan arc belt, the Kanggurtag belt, the Aqishan–Yamansu belt and the Central Tianshan belt from north to south. These tectonic belts have formed through arc–continent or arc–arc collisions during the Paleozoic. A number of Fe(‐Cu) deposits in the Aqishan–Yamansu belt, including the Heifengshan, Shuangfengshan and Shaquanzi Fe(‐Cu) deposits, are associated with Carboniferous–Early Permian volcanic rocks and are composed of vein‐type magnetite ores. Metallic minerals are dominated by magnetite and pyrite, with minor chalcopyrite. Calcite, chlorite, and epidote are the dominant gangue minerals. Pyrite separates of ores from those three deposits have relatively high and variable Re contents ranging from 3.7 to 184 ppb. All pyrite separates have very low common Os, allowing us calculation of single mineral model ages for each sample. Pyrite separates from the Heifengshan Fe deposit have an ¹⁸⁷Re–¹⁸⁷Os isochron age of 310 ± 23 Ma (MSWD = 0.04) and a weighted mean model age of 302 ± 5 Ma (MSWD = 0.17). Those from the Shuangfengshan Fe deposit have an isochron age of 295 ± 7 Ma (MSWD = 0.28) and a weighted mean model age of 292 ± 5 Ma (MSWD = 0.33). The Shaquanzi Fe‐Cu deposit has pyrite with an isochron age of 295 ± 7 Ma (MSWD = 0.26) and a weighted mean model age of 295 ± 6 Ma (MSWD = 0.23). Pyrite separates from these Fe(‐Cu) deposits have δ³⁴S_CDT ranging from ?0.41‰ to 4.7‰ except for two outliers. Calcite from the Heifengshan Fe deposit and Shaquanzi Fe‐Cu deposit have similar C and O isotope compositions with δ¹³C_PDB and δ¹⁸O_SMOW ranging from ?5.5‰ to ?1.0‰ and from 10‰ to 12.7‰, respectively. These stable isotopic data suggest that S, C, and O are magmatic‐hydrothermal in origin. The association of low‐Ti magnetite and Fe/Cu‐sulfides resembles those of Iron–Oxide–Copper–Gold (IOCG) deposits elsewhere. Our reliable Re–Os ages of pyrite suggest that the Fe(‐Cu) deposits in the Aqishan–Yamansu belt formed at ～296 Ma, probably in a back‐arc extensional environment.     

Palaeoceanographic controls on reef deposition: the Messinian Cariatiz reef (Sorbas Basin, Almería, SE Spain)

The Cariatiz section lies at the toe of the palaeoslope of the Messinian Cariatiz fringing reef, at the northern margin of the Neogene Sorbas Basin in SE Spain. Distal-slope reef deposits in the upper part of the section can be traced laterally to the reef core of the last episodes of reef progradation. The underlying deposits are alternating diatomitic marl, marl and silty marl that intercalate with sandstone beds. Combined lithological changes, variations in proportions of warm-water planktic foraminifera and δ 18O values suggest that at least seven, probably precessional, cycles are recorded throughout the Cariatiz section. The correlation of seven cycles in the pelagic deposits to seven reef progradation cycles, and associated vertical shifts in reef facies, indicates relative sea-level oscillations of several tens of metres. Biostratigraphic and palaeomagnetic data suggest that both the Cariatiz section and the fringing reef formed during the reverse polarity Chron C3r. Surface-water temperatures seem to be the major factor controlling carbonate production in the reef system. Deposition of bioclastic calcirudite and calcarenite, with no active coral growth, took place at the lowest sea-level within each reef cycle during temperature minima within each precessional cycle. Porites framework and reef-slope deposits with Halimeda gravel, in contrast, formed during temperature rises and thermal maxima within precessional cycles.     

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.     

Environmental isotopic study on the recharge and residence time of groundwater in the Heihe River Basin, northwestern China

The recharge and origin of groundwater and its residence time were studied using environmental isotopic measurements in samples from the Heihe River Basin, China. δ¹⁸O and δD values of both river water and groundwater were within the same ranges as those found in the alluvial fan zone, and lay slightly above the local meteoric water line (δD=6.87δ¹⁸O+3.54). This finding indicated that mountain rivers substantially and rapidly contribute to the water resources in the southern and northern sub-basins. δ¹⁸O and δD values of groundwater in the unconfined aquifers of these sub-basins were close to each other. There was evidence of enrichment of heavy isotopes in groundwater due to evaporation. The most pronounced increase in the δ¹⁸O value occurred in agricultural areas, reflecting the admixture of irrigation return flow. Tritium results in groundwater samples from the unconfined aquifers gave evidence for ongoing recharge, with mean residence times of: less than 36 years in the alluvial fan zone; about 12–16 years in agricultural areas; and about 26 years in the Ejina oasis. In contrast, groundwater in the confined aquifers had ¹⁴C ages between 0 and 10 ka BP.