The significance of 24-norcholestanes, 4-methylsteranes and dinosteranes in oils and source-rocks from East Sirte Basin (Libya)

The present paper involves a detailed evaluation of specific steroid biomarkers by gas chromatography–mass spectrometry (GC–MS) and GC-metastable reaction monitoring (MRM) analyses of several crude oils and source rocks from the East Sirte Basin. 24-Norcholestanes, dinosteranes, 4α-methyl-24-ethylcholestanes and triaromatic steroids have been identified in both source-rocks and crude oils of the East Sirte Basin. Diatoms, dinoflagellates (including those potentially associated with corals) and/or their direct ancestors are amongst the proposed sources of these biomarkers. These biomarker parameters have been used to establish a Mesozoic oil–source correlation of the East Sirte Basin. Hydropyrolysis of an extant coral extract revealed a similar distribution (although immature) of dinosteranes and 4α-methyl-24-ethylcholestanes also observed in the Sirte oils and source-rocks. This is consistent with the presence of dinoflagellates present during the deposition of the Mesozoic aged East Sirte Basin Formations.A good data correlation for the rock extracts revealed a similar distribution of 3,24-dimethyl triaromatic steroids, 3-methyl-24-ethylcholestanes, 4-methyl-24-ethylcholestanes and 2-methyl-24-ethylcholestanes observed in one of the oil families and associated source-rocks for the East Sirte Basin.     

Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbon and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin,Pakistan

The stable hydrogen isotopic compositions (δD) of selected aliphatic hydrocarbons (n-alkanes and isoprenoids) in eight crude oils of similar source and thermal maturity from the Upper Indus Basin (Pakistan) were measured. The oils are derived from a source rock deposited in a shallow marine environment. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker and aromatic hydrocarbon distributions. A plot of pristane/n-C₁₇ alkane (Pr/n-C₁₇) and/or phytane/n-C₁₈ alkane (Ph/n-C₁₈) ratios against American Petroleum Institute (API) gravity shows an inverse correlation. High Pr/n-C₁₇ and Ph/n-C₁₈ values and low API gravity values in some of the oils are consistent with relatively low levels of biodegradation. For the same oils, δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). The data are consistent with the removal of D-depleted low molecular weight (LMW) n-alkanes (C₁₄–C₂₂) from the oils. The δD values of isoprenoids do not change with progressive biodegradation and are similar for all the samples. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. For example, the moderately biodegraded oils show an unresolved complex mixture (UCM), loss of LMW n-alkanes (<C₁₅) and moderate changes in the alkyl naphthalene distributions. The relative susceptibility of alkyl naphthalenes at low levels of biodegradation is discussed. The alkyl naphthalene biodegradation ratios were determined to assess the effect of biodegradation. The dimethyl, trimethyl and tetramethyl naphthalene biodegradation ratios show significant differences with increasing extent of biodegradation.     

The evolution characteristics and fractionation mechanism of carbon isotopes in the process of "multi-stage hydrocarbon generation"

The Jiyang Sag and the Liaohe Basin are the two important areas where immature oil resources are distributed in China. From these two areas immature-low mature to mature oil samples were collected for carbon isotopic analysis. The extracts of source rocks are dominant in the Jiyang Sag while crude oils are dominant in the Liaohe Basin. The maturity index, R., for source rocks varies from 0.25%(immature) to 0.65% (mature). Studies have shown that within this range of R. values the extracts of source rocks and crude oils, as well as their fraction components, have experienced observable carbon isotope fractionation. The carbon isotopic values tend to increase with burial depth, the oils become from immature-low mature to mature, and the rules of evolution of oils show a three-stage evolution pattern, i. e. ,light→heavy→light→heavy oils. Such variation trend seems to be related to the occurrence of two hydrocarbon-generating processes and the main hydrocarbon-forming materials being correspondingly non-hydrocarbons and possessing MAB characteristics, lower thermodynamic effects and other factors. In the process towards the mature stage, with increasing thermodynamic effects, the thermal degradation of kerogens into oil has become the leading factor, and correspondingly the bond-breaking ratio of 12 C-13C also increases,making the relatively 12C-rich materials at the low mature stage evolve again towards 13C enrichment.     

松辽盆地徐深1井气藏气源的氢、碳同位素特征

选取松辽盆地内泥岩样品和煤样进行热模拟实验,建屯了两个样品成甲烷的氢、碳同位素分馏动力学模型并标定了动力学参数.分别以徐深1井区、沉降中心地质资料为例进行研究,表明两处源岩均有短期内大量生气的特点,气源岩生气期分别为距今95.5～73 Ma和距今0～73 Ma.计算得到两处源岩沙河子组暗色泥岩和煤、火石岭组暗色泥岩和煤所生天然气单独运聚成藏（自开始生烃到现今累积成藏）所对应的δDCH4 和δ13C1,进而定量计算出徐深1井区源岩所生甲烷的δDCH4 为-237.3‰,δ13C1为-28.8‰,沉降中心气源岩所生甲烷的δDCH4 为-2.5‰,δ13C1为-24.8‰.以各区域天然气混合后的δDCH4 作为来源气体的端元同位素值,根据物质平衡原理计算得到：徐深1井区源岩对该区气藏的贡献比例约占72%,沉降中心源岩的贡献比例约为28%.同理以δ13C1.方法得到徐深1井区源岩对该区气藏的贡献比例约占66%,沉降中心源岩的贡献比例约为34%.氢、碳同位素分馏的化学动力学地质应用结果存在的差异与同位素分馏模型标定所用热模拟实验为不加水实验有关.     

东北漠河盆地甲烷碳氢稳定同位素异常及形成机制

东北漠河盆地是我国陆域多年冻土区天然气水合物聚集成藏及勘探的潜在区域。近几年,在漠河盆地实施天然气水合物钻探实验井和气源探井的过程中发现,该区甲烷碳、氢同位素δ^13 CCH4、δDCH4值明显偏低,负向偏移特征明显:碳同位素δ^13 CCH4 值多数小于-60‰,最低达-82.9‰;氢同位素δDCH4 值绝大多数低于-350‰,最低达-450‰。通常,埋深小于1 500m的范围,甲烷碳同位素δ^13 CCH4 值随深度增大,氢同位素δDCH4 值随深度减小;深度大于1 500m,甲烷碳、氢同位素δ^13CCH4 、δDCH4 值随深度同步增大。研究表明:漠河盆地的甲烷碳稳定同位素负向偏移,主要与甲烷的微生物成因有关;甲烷氢稳定同位素负向偏移,则是盆地所处较高纬度独特气候引起的地表水蒸发或大气冷凝降水过程的瑞利蒸馏和乙酸发酵的甲烷生成方式共同作用的结果。     

新疆准噶尔盆地南缘二叠系芦草沟组烃源岩生物标志化合物特征及意义

通过地球化学分析测试技术对准噶尔盆地南缘芦草沟组烃源岩生物标志化合物特征进行研究,探讨其有机质的母质来源、沉积环境、有机质演化程度等方面的信息。芦草沟组烃源岩正构烷烃的轻碳优势和甾烷的C27-29含量关系等参数表明,母质来源主要为藻类等低等水生生物。平均1.0 左右的烃源岩Pr/Ph 值表明,弱氧化-弱还原的沉积环境,平均值为0.15 的伽马蜡烷指数及较高含量的孕甾烷和升孕甾烷表明,沉积环境盐度较高,该沉积环境有利于有机质的富集。对甾烷的C2920S(20S+20R)和C29αββ/(αββ+ααα)值和C31藿烷αβ22S/(22S+22R)值等成熟度参数进行分析表明,研究区烃源岩处于低成熟-成熟阶段。烃源岩有机质中四环萜烷的出现及较小的规则甾烷/17α(H)-藿烷比值等参数表明,烃源岩成岩早期有机质受到一定程度的生物降解作用。     

Palaeovalleys and fault-controlled depocentres in the Late-Ordovician glacial record of the Murzuq Basin (central Libya)

In the Gargaf area, the stratigraphic architecture of the Late-Ordovician glacial drift results from successive glacial erosion events, with the location of the main glacial valleys partly controlled by inherited Panafrican structural trends, and by the existence of glacio-isostatically induced fault-related depocentres. Four laterally discontinuous, depositional units correspond to the filling of palaeovalleys. Each of the corresponding basal bounding surfaces was incised during a major ice front advance, reaching at least the northern Gargaf (>28°S). The bulk of the glacial record is made up of fluvial to shallow-marine sediments deposited in relatively distal glacial environments. Each unit, which recorded a glacial-interglacial climatic cycle, can be used for correlation throughout the Murzuq Basin and even at the scale of the North Gondwana platform. To cite this article: J.-F. Ghienne et al., C. R. Geoscience 335 (2003).     

Use of sinkhole and specific capacity distributions to assess vertical gradients in a karst aquifer

The carbonate-rock aquifer in the Great Valley, West Virginia, USA, was evaluated using a database of 687 sinkholes and 350 specific capacity tests to assess structural, lithologic, and topographic influences on the groundwater flow system. The enhanced permeability of the aquifer is characterized in part by the many sinkholes, springs, and solutionally enlarged fractures throughout the valley. Yet, vertical components of subsurface flow in this highly heterogeneous aquifer are currently not well understood. To address this problem, this study examines the apparent relation between geologic features of the aquifer and two spatial indices of enhanced permeability attributed to aquifer karstification: (1) the distribution of sinkholes and (2) the occurrence of wells with relatively high specific capacity. Statistical results indicate that sinkholes (funnel and collapse) occur primarily along cleavage and bedding planes parallel to subparallel to strike where lateral or downward vertical gradients are highest. Conversely, high specific capacity values are common along prominent joints perpendicular or oblique to strike. The similarity of the latter distribution to that of springs suggests these fractures are areas of upward-convergent flow. These differences between sinkhole and high specific capacity distributions suggest vertical flow components are primarily controlled by the orientation of geologic structure and associated subsurface fracturing.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Indication of hydrogen and oxygen stable isotopes on the characteristics and circulation patterns of medium-low temperature geothermal resources in the Guanzhong Basin,China

Guanzhong Basin is a typical medium-low temperature geothermal field mainly controlled by geo-pressure in the west of China.The characteristics of hydrogen and oxygen isotopes were used to analyze the flow and storage modes of geothermal resources in the basin.In this paper,the basin was divided into six geotectonic units,where a total of 121 samples were collected from geothermal wells and surface water bodies for the analysis of hydrogen-oxygen isotopes.Analytical results show that the isotopic signatures of hydrogen and oxygen throughout Guanzhong Basin reveal a trend of gradual increase from the basin edge areas to the basin center.In terms of recharge systems,the area in the south edge belongs to the geothermal system of Qinling Mountain piedmont,while to the north of Weihe fault is the geothermal system of North mountain piedmont,where the atmospheric temperature is about 0.2℃-1.8℃in the recharge areas.The main factors that affect the geothermal waterδ18O drifting include the depth of geothermal reservoir and temperature of geothermal reservoir,lithological characteristics,water-rock interaction,geothermal reservoir environment and residence time.Theδ18O-δD relation shows that the main source is the meteoric water,together with some sedimentary water,but there are no deep magmatic water and mantle water which recharge the geothermal water in the basin.Through examining the distribution pattern of hydrogen-oxygen isotopic signatures,the groundwater circulation model of this basin can be divided into open circulation type,semi-open type,closed type and sedimentary type.This provides some important information for rational exploitation of the geothermal resources.     

中国萤石矿床锶同位素、氢氧同位素地球化学特征

通过对前人所做典型萤石矿床和区域萤石矿床锶、氢氧同位素地球化学资料的综合研究,从锶、氢氧同位素地球化学特征角度分析了中国萤石矿床的物质来源和萤石矿形成时成矿流体的性质及来源.由锶同位素地球化学资料综合分析得出:以灰岩为主要围岩的沉积改造型及部分热液充填型萤石矿床成矿物质主要来源于其围岩灰岩;以火山岩、火山碎屑岩为主要围...     

Fractionation of hydrogen,oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C₂₁–C₂₅ n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ¹⁸O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C₂₃ n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ¹³C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C₂₃ n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.     

涞源北盆地地下水氢氧同位素特征及北海泉形成模式

拒马源泉群作为拒马河的源头,受到了较多专家和学者的关注。但这些研究多集中在地下水的水化学、水位动态、泉流量等特征上,对地下水氢氧同位素特征的分析几乎没有,且对北海泉的成因解释多为粗略的定性概述。为了说明涞源北盆地地下水的氢氧同位素特征,详细揭示北海泉的形成模式,首次系统地采集了不同含水岩组的地下水样品,测定了水样的氢氧同位素组分。结果表明:样品点δD和δ18O值均落在区域大气降水线上或附近,大气降水是研究区地下水的主要补给来源;白云岩、灰岩含水岩组高程效应较明显,径流途径长,松散含水层径流途径短,受蒸发作用较强;白云岩、灰岩含水岩组和松散含水层氘盈余d值分别为6.0‰～11.6‰、4.2‰～11.2‰、3.8‰～8.0‰,较大气降水大部分偏小,表明岩溶水和松散孔隙水经历了不同的流动过程;白云岩、灰岩含水岩组从补给区向排泄区各自流动过程中,在小西庄、香炉屯村附近断裂带发生沟通混合,然后在向盆地中心径流过程中受断层阻水上升,上升过程中又接受了松散孔隙水的补给,最后在松散岩层中出露成泉,形成北海泉。在孔隙水混入前,两者的平均补给比例大约为48.4%～57.6%和42.4%～51.6%。     

Sedimentary formations of the Cretaceous Sakhalin Basin (Far East Asia)

The marine sedimentary formations of the Middle Albian to Maastrichtian in the Cretaceous Sakhalin Basin (CSB) were investigated. These successions of strata consist of interbedded sandy, clayey and calcareous rocks which are underlain by heterogeneous metamorphosed (up to greenschist facies) Paleozoic to Mesozoic (pre-Aptian) rocks. The studied sections display several different facies reflecting geological settings ranging from an inner shelf to a continental slope. Three depositional complexes bound by regional subaerial unconformities are recognized within the marine successions. Since the Albian, the CSB has been a rapidly subsiding marginal part of the Okhotsk Sea plate. The Naiba Valley succession, corresponding to a sublittoral zone, shows extremely high sedimentation rates up to 190 m/Ma. The stratigraphic distribution of lithofacies indicates that the CSB became shallower from the Middle Albian to the Maastrichtian.     

Use of biological marker distributions to study thermal history of the Permian Kupferschiefer of the Lower Rhine Basin

In the Central European Zechstein Basin, the Permian Kupferschiefer has been deposited under marine anoxic conditions. From a lagoon at the southwest border of the Zechstein Sea, today part of the Lower Rhine Basin, 30 core samples have been studied by means of organic geochemical methods. Within the area investigated, the depth of the Kupferschiefer horizon increases from about 350 m in the south to about 1000 m in the north. Furthermore, the Kupferschiefer has been thermally affected in the western part by the intrusive body of the so-called Krefeld High. This geological situation opens the possibility to investigate differences of short term and long term temperature effects on the biological marker distribution within a sediment layer of a largely uniform faciès type. Depth related changes in the hopane, sterane and diasterene/diasterane distributions are compared to those changes induced by the Krefeld High. The composition of aromatic steroid hydrocarbons is used to discuss time-temperature effects. It is shown that depth related values of maturation parameters can only be interpreted by taking into account post-depositional tectonic events. Samples from tectonic horst structures show higher maturation values than one would expect from the present day depth.

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Zusammenfassung Aus dem Bereich der heutigen Niederrheinischen Bucht wurden an 30 Kernproben des Kupferschiefers organischgeochemische Untersuchungen durchgeführt. Innerhalb des Untersuchungsgebiets nimmt die Teufe des Kupferschieferhorizonts von 350 m im Süden auf über 1000 m im Norden zu. Organisch-geochemische Reifeparameter zeigen an, daß der Kupferschiefer im Westen durch den Intrusivkörper des Krefelder Gewölbes thermisch beeinflußt worden ist. Aufgrund dieser Situation bietet sich die Möglichkeit, Unterschiede im Einfluß von kurzzeitigen und langzeitigen Temperatureinwirkungen auf die Verteilung von Chemofossilien in einem faziell einheitlichen Horizont zu studieren. Teufenabhängige Variationen der Hopan-, Steran-, Diasteran- und Diasterenverteilungen lassen sich mit den zusätzlich durch den Intrusivkörper verursachten Veränderungen vergleichen. Die Verteilungsmuster der aromatischen Steroide werden zur Deutung von Zeit-Temperatur-Effekten im Verlauf der Diagenese herangezogen. Die ermittelten Meßwerte der Reifeparameter lassen sich nur interpretieren, wenn postsedimentäre tektonische Bewegungen nach der Ablagerung des Kupferschiefers in Betracht gezogen werden. Die aus Horsten stammenden Proben zeigen höhere Reifegrade an als entsprechend ihrer heutigen Teufe zu erwarten.

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Résumé Dans le bassin du Zechstein d'Europe Centrale, les Kupferschiefer permiens ont été déposés dans des conditions marines anoxiques. Dans un paléo-lagon situé à la bordure sud-ouest de la mer du Zechstein, et qui fait partie aujourd'hui du Bassin du Bas-Rhin, 30 échantillons, provenant de carottes, ont fait l'objet d'une étude de géochimie organique. Dans la région ainsi étudiée, la profondeur de l'horizon des Kupferschiefer augmente, du sud au nord, de 350 m à 1.000 m. D'autre part, les Kupferschiefer ont subi, dans leur partie ouest, l'influence thermique du corps intrusif du «Dôme de Krefeld». Cette situation géologique fournit la possibilité d'étudier les effets à long terme et à court terme de la température sur la distribution des marqueurs biologiques au sein d'un niveau sédimentaire de faciès uniforme. Les modifications dans la répartition de l'hopane, du stérane et du diastérène/diasterane en fonction de la profondeur sont comparées à celles qui sont provoquées par le Dôme de Krefeld. Les effets temps-température sont discutés à partir de la composition des hydrocarbures stéroïdes aromatiques. Les auteurs montrent que la valeur des paramètres de maturation liés à la profondeur ne peuvent être interprétés sans que l'on prenne en considération les événements tectoniques postsédimentaires. Des échantillons provenant de structures en horst montrent un degré d'évolution plus élevé que celui auquel on s'attend d'après leur profondeur actuelle.

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准噶尔盆地南缘安集海河组烃源特征及成藏条件

通过应用地球化学分析、油源对比及盆地模拟等手段对准噶尔盆地南缘古近系安集海河组烃源岩进行了评价,认为该区为一套以Ⅱ型干酪根为主的中等丰度烃源岩,生烃的门限深度为3500 m,时间是8 Ma±。第三系的油藏与其具有密切关系,同时侏罗系煤系烃源岩也为第三系的生油做出了贡献。造成该套烃源岩评价较低的主要原因是地层内发育的异常高压降低了烃源岩的成熟度指标,但由于长期构造挤压的力化学作用还是促进了烃源岩的生排烃,并且位于向斜部位的烃源岩其埋深大多超过生烃门限深度,也可以生成大量油气,因此认为还是有效的烃源岩。其生排烃时间与该区构造大规模形成时间相匹配,在背斜形成过程中,伴随着异常压力的产生、平衡,最终促进了油气在背斜核部聚集成藏。有利的勘探区是南缘中段的第二排、第三排构造古近系的安集海河组以及新近系的沙湾组储层。     

Middle to Late Pleistocene environments based on stable organic carbon and nitrogen isotopes of loess-palaeosol sequences from the Carpathian Basin

Stable organic carbon and nitrogen isotopes can be used to interpret past vegetation patterns and ecosystem qualities. Here we present these proxies for two loess-palaeosol sequences from the southern Carpathian Basin to reconstruct the palaeoenvironment during the past 350 ka and establish regional commonalities and differences. Before now, isotopic studies on loess sequences from this region were only conducted on deposits from the last glacial cycle. We conducted methodological tests involving the complete decalcification of the samples prior to stable isotope analyses. Two decalcification methods (fumigation method and wet chemical acidification), different treatment times, and the reproducibility of carbon isotope analyses were tested. Obtained results indicate that the choice of the decalcification method is important for organic carbon stable isotope analyses of loess-palaeosol sequences because ratios vary by more than 10‰ between the wet chemical and fumigation methods, due to incomplete carbonate removal by the latter. Therefore, we suggest avoiding the fumigation method for studies on loess-palaeosol sequences. In addition, our data show that samples with TOC content <0.2% bear increased potential for misinterpretation of their carbon isotope ratios. For our sites, C₃-vegetation is predominant and no palaeoenvironmental shifts leading to a change of the dominant photosynthesis pathway can be detected during the Middle to Late Pleistocene. Furthermore, the importance of further stable nitrogen isotope studies is highlighted, since this proxy seems to reflect past precipitation patterns and reveals favourable conditions in the southern Carpathian Basin, especially during interstadials.     

Carbon isotopes to constrain the origin and circulation pattern of groundwater in the north-western part of the Bohemian Cretaceous Basin (Czech Republic)

The Bohemian Cretaceous Basin represents a complex hydrogeological system composed of several aquifers with very favourable hydrogeological properties. These aquifers have been exploited for many years. The sustainability of such resources might be guaranteed by well organised water management, which requires a detailed knowledge about the functioning of the hydrogeological system. Although many efforts have previously been made to evaluate groundwater residence time, the many intricate geochemical processes complicate groundwater dating. The current study clarifies the functioning of this complex hydrogeological basin using hydrogeochemical and isotopic investigations. Chemical data and a combination of ¹³C and ¹⁴C isotopes within the Cenomanian and the Turonian layers indicate groundwater interactions with deep-seated CO₂, rock matrix, surface waters and fossil organic matter. Very depleted δ¹³C values (average δ¹³C ∼ −13.4‰) suggest interactions with fossil organic matter, whereas enriched values account for the interaction with deep CO₂ gas ascending from the upper mantle via the numerous faults and fractures, and also, to a lesser extent, from calcite dissolution. Geochemical processes that take place in the system cause a clear depletion in ¹⁴C that greatly complicates groundwater residence time evaluation. Different dilution correction models have been applied considering the different C origins. The stable isotope content, mainly ¹⁸O values, indicates both the contribution of modern precipitation and the partial infiltration of palaeowaters during colder climatic conditions from the end of the Pleistocene. The apparent ¹⁴C groundwater ages range from modern to 11.1 ka BP, which suggests some post glacial infiltration from melting ice sheets. Finally, all the acquired information was used to propose a conceptual model of C origin within the basin.     

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.