Br/Cl ratios and O, H, C, and B isotopic constraints on the origin of saline waters from eastern Canada

Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Cl_molar and δ¹¹B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ¹³C_DIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction.     

Noble gases in six ordinary chondrites: comparison of exposure ages from noble gases with 26Al ages

Noble gases were redetermined in six ordinary chondrites in order to clarify some discrepancies between cosmic-ray exposure ages from noble gas isotopes and ²⁶Al activity. Generally, samples used for noble-gas analyses were from the same specimen which earlier had been used for ²⁶Al determinations in this laboratory. The high ²¹Ne ages (> 3 × 10⁶ y) for Dimmitt, Menow and Pierceville are consistent with ²⁶A1 activity at saturation level. Variations in both ²¹Ne_c age and ²⁶Al activity, in earlier measurements on Dimmitt, were due to “shielding”; very low noble-gas ages in earlier analyses on Menow and Pierceville were due to mis-labelling of samples. Earlier observation of very low noble-gas ages for Seres, which is inconsistent with its saturation activity of ²⁶Al, is confirmed. Ladder Creek yields consistent ages both from noble gases and ²⁶Al. Malotas contains a substantial excess of ²¹Ne, as revealed by a higher ²¹Ne age, compared to its ²⁶Al age; the excess ²¹Ne is probably due to “pre-irradiation”. Isotopic compositions for trapped Kr and Xe in these chondrites, excepting Seres, are very similar to compositions determined earlier for ordinary chondrites. The Xe in Seres is enriched in light isotopes and is similar to solar Xe.     

Dating ultra-deep mine waters with noble gases and Cl, Witwatersrand Basin, South Africa

Concentrations and isotopic ratios of dissolved noble gases, ³⁶Cl, δD and δ¹⁸O in water samples from the ultra-deep gold mines (0.718 to 3.3 km below the surface) in the Witwatersrand Basin, South Africa, were investigated to quantify the dynamics of these ultra deep crustal fluids. The mining activity has a significant impact on the concentrations of dissolved gases, as the associated pressure release causes the degassing of the fissure water. The observed under saturation of the atmospheric noble gases in the fissure water samples (70-98%, normalized to ASW at 20°C and 1013 mbar) is reproduced by a model that considers diffusive degassing and solubility equilibration with a gas phase at sampling temperature. Corrections for degassing result in ⁴He concentrations as high as 1.55 · 10⁻¹cm³STP⁴He g⁻¹, ⁴⁰Ar/³⁶Ar ranging between 806 and 10331, and ¹³⁴Xe/¹³²Xe and ¹³⁶Xe/¹³²Xe ratios above 0.46 and 0.44, respectively. Corrected ^134(136)Xe/¹³²Xe and ^134(136)Xe/⁴He-ratios are consistent with their production ratios, whereas the nucleogenic ⁴He/⁴⁰Ar, and ^134(136)Xe/⁴⁰Ar ratios generally indicate that these gases are produced in an environment with an average [U + Th]/K-content 2-3 times above that of crustal average. In two scenarios, one considering only accumulation of in situ produced noble gases, the other additionally crustal flux components, the model ages for 14 individual water samples range from 13 to 168 Ma and from 1 to 23 Ma, respectively.The low ³⁶Cl-ratios of (4-37) · 10⁻¹⁵ and comparatively high ³⁶Cl-concentrations of (8-350) · 10⁻¹⁵ atoms ³⁶Cl l⁻¹ reflect subsurface production in secular equilibrium indicating an age in excess of 1.5 Ma or 5 times the half-life of ³⁶Cl.In combination, the results suggest residence times of the fluids in fissures in this region (up to 3.3 km depth) are of the order of 1-100 Ma. We cannot exclude the possibility of mixing and that small quantities of younger water have been mixed with the very old bulk.     

河套平原沉积物中铀的赋存形态及其与地下水铀浓度的关系

采用Tessier的五步提取法,对位于河套平原杭锦后旗沙海乡四个钻孔沉积物进行铀的五个赋存形态(包括可交换态、碳酸盐吸附态、铁锰氧化物吸附态、有机物或硫化物吸附态和基质态)分布特征研究。结果发现,铁锰氧化物结合态铀含量为0.140~0.328 mg/kg,占总铀量的34.7%;基质态中铀的含量为0.256~0.405 mg/kg,占44.0%。对于铁锰氧化物结合态,铀含量与铁、锰含量呈正相关性,其中铀与铁线性相关系数0.311~0.482,铀与锰线性相关系数0.506~0.642。表明,沉积物中锰氧化物对铀含量的影响大于铁氧化物对铀含量的影响。进一步研究发现,沉积物岩性对铀含量的影响较大,总铀在细砂中平均含量为0.088 mg/kg,在黏土中平均量为0.260 mg/kg。不同深度地下水中铀浓度和沉积物铀含量的研究表明,随深度增加,地下水中铀浓度与含水层沉积物中铀含量均呈降低的趋势。地下水中铀浓度受含水层中可交换态铀含量的直接影响。     

水溶天然气运移地球化学示踪——以塔里木盆地和田河气田为例

文中选择田河气田作为研究实例,对气田东、西部天然气进行系统的天然气地球化学对比研究,结合气田成藏的地质背景,认为和田河气田具有较好的水溶气运移成藏地质条件和明显的水溶气运移地球化学证据,提出了天然气是水溶气成因的新观点。寒武系烃源岩生成的天然气在高温、高压状态下大量溶解于水,在压力的驱使下,水溶气自寒武系运移至气田东部圈闭,然后再由气田东部的高压区沿不整合面往西部的低压区运移。根据气田天然气地球化学横向变化特征,提出了ln(C1/C2)、ln(C2/C3)、CO2/CH4、CH4/N2、N2/C2H6等一系列操作性较强的水溶气运移的地球化学示踪新指标,对研究天然气成藏机理和成藏过程都有重要意义。     

How basin model results enable the study of multi-layer aquifer response to pumping: the Paris Basin, France

The Albian aquifer of the Paris Basin (France) has been exploited since 1841 and shows drastic drawdown. A three-dimensional (3D) groundwater flow model is used to study the hydrodynamic response of the multi-layered aquifers to pumping activity in the Albian, at basin scale over 167 years. This 3D flow model uses geometry and hydrodynamic parameter distributions that are inherited from a genetic approach through basin modelling, the basin model creating a geometric pattern of hydrodynamic properties constrained by geological history. The paper aims to promote the use of the basin model approach (long time scale, 248 Ma) for the study of deep-aquifer response to anthropogenic perturbation (short time scale, 167 years) in situations for which hydrodynamic data are scarce but geological data are numerous. The results show that parameter distribution is insufficient to reproduce the Albian aquifer behaviour, notably highlighting a different meaning of the specific storage coefficient between basin modelling and groundwater-flow modelling. Dividing the storage coefficient by 100 and including available transmissivity data significantly improved the model/data comparison. The potential impact on a deep aquitard is then discussed. This study sheds light on the advantages and limitations of the basin model approach for groundwater-flow modelling in 3D.     

Intercomparison of tritium and noble gases analyses, 3H/3He ages and derived parameters excess air and recharge temperature

Groundwater age dating with the tritium–helium (³H/³He) method has become a powerful tool for hydrogeologists. The uncertainty of the apparent ³H/³He age depends on the analytical precision of the ³H measurement and the uncertainty of the tritiogenic ³He component. The goal of this study, as part of the groundwater age-dating interlaboratory comparison exercise, was to quantify the analytical uncertainty of the ³H and noble gas measurements and to assess whether they meet the requirements for ³H/³He dating and noble gas paleotemperature reconstruction.Samples for the groundwater dating intercomparison exercise were collected on 1 February, 2012, from three previously studied wells in the Paris Basin (France). Fourteen laboratories participated in the intercomparison for tritium analyses and ten laboratories participated in the noble gas intercomparison. Not all laboratories analyzed samples from every borehole.The reproducibility of the tritium measurements was 13.5%. The reproducibility of the ³He/⁴He ratio and ⁴He, Ne, Ar, Kr and Xe concentrations was 1.4%, 1.8%, 1.5%, 2.2%, 2.9%, and 2.4% respectively.The uncertainty of the tritium and noble gas measurements results in a typical ³H/³He age precision of better than 2.5 years in this case. However, the measurement uncertainties for the noble gas concentrations are insufficient to distinguish the appropriate excess air model if the measured helium concentration is not included. While the analytical uncertainty introduces an unavoidable source of uncertainty in the ³H/³He apparent age estimate, other sources of uncertainty are often much greater and less well defined than the analytical uncertainty.     

Regional groundwater focusing of nitrogen and noble gases into the Hugoton-Panhandle giant gas field, USA

The Hugoton-Panhandle giant gas field, located across SW Kansas and the Texas and Oklahoma panhandles in the USA, is the case type example of high nitrogen concentrations in a natural gas being linked with high helium concentrations. We collected 31 samples from producing wells in a north-south traverse of the 350-km-long field. The samples reflect the previously observed north-south change in ⁴He/N₂, with values changing from 0.020 to 0.049 respectively. ³He/⁴He, ²¹Ne/²²Ne, and ⁴⁰Ar/³⁶Ar vary between 0.14-0.25 Ra, 0.0373-0.0508, and 818-1156 respectively, and are caused by quantifiable contributions from mantle, crustal, and atmosphere-derived sources. The atmosphere-derived ²⁰Ne/³⁶Ar ratios are indistinguishable from groundwater values. The crustal ⁴He/²¹Ne* and ⁴He/⁴⁰Ar* ratios show a 60% excess of ⁴He compared to predicted production ratios in the crust and are typical of noble gases released from the shallow crust. The mantle ³He/N₂ and groundwater-recharge ³⁶Ar/N₂ ratios enable us to rule out significant magmatic or atmosphere contributions to the gas field N₂, which is dominantly crustal in origin.Correlated ²⁰Ne/N₂ and ⁴He/N₂ shows mixing between two distinct crustal N₂ components. One N₂ component (N₂*) is associated with the crustal ⁴He and groundwater-derived ²⁰Ne, and the other with no resolvable noble gas contribution. Measured δ¹⁵N_N2 values vary from +2.7‰ to +9.4‰. The N₂* and non-He-associated N₂ endmembers are inferred to have δ¹⁵N_N2 = −3‰ and +13‰ and contribute from between 25-60% and 75-40% of the nitrogen respectively. The non-He-associated nitrogen is probably derived from relatively mature organic matter in the sedimentary column. The δ¹⁵N_N2* value is not compatible with a crystalline or high-grade metamorphic source and, similar to the ⁴He, is inferred to be from a shallow or low metamorphic-grade source rock. ⁴He mass balance requires a regional crustal source, its association with significant magmatic ³He pointing to a tectonically active source to the west of the Hugoton system. The volume of groundwater required to source the ²⁰Ne in the gas field demonstrates the viability of the groundwater system in providing the collection, transport, and focusing mechanism for the ⁴He and N₂*. The N₂*/²⁰Ne ratio shows that the N₂* transport must be in the aqueous phase, and that the degassing mechanism is probably contact between the regional groundwater system and the preexisting reservoir hydrocarbon gas phase.     

A paleotemperature record derived from dissolved noble gases in groundwater of the Aquia Aquifer (Maryland, USA)

Low ¹⁴C activities in groundwater of the confined part of the Aquia aquifer in southeastern Maryland suggest that most of this water infiltrated at least 30,000 years ago. However, radiocarbon contents of the dissolved inorganic carbon seem to be affected by isotopic exchange, possibly with secondary calcite deposits in the formation, leading to overestimated ¹⁴C ages. Whereas the geochemistry of the Aquia aquifer complicates the application of the widely used ¹⁴C dating method, the accumulation of radiogenic He seems to provide a viable alternative for establishing a chronology. The quasi-linear increase of He concentrations with flow distance observed in the Aquia aquifer can be explained entirely by accumulation of in situ produced radiogenic He. U and Th concentrations in Aquia sand were measured in order to determine the accumulation rate of ⁴He with sufficient confidence to establish a He time scale.Concentrations of dissolved atmospheric noble gases were used to derive mean annual ground temperatures at the time of infiltration. These noble gas temperatures (NGTs) clearly show the presence of water that infiltrated under much cooler conditions than at present. NGTs are correlated with chloride concentrations, corroborating the hypothesis that chloride variations in this aquifer constitute a climate signal. In contrast, the stable isotope ratios δ¹⁸0 and δD do not provide a clear record of past climatic changes in the Aquia aquifer and the correlation between NGTs and stable isotope ratios is weak. The NGT record suggests that mean annual temperatures in this midlatitude coastal site during the last glacial maximum (LGM) were (9.0 ± 0.6) °C colder than during the Holocene. This difference is slightly lower than estimates derived from pollen data for this region, but considerably larger than the rather uniform cooling of about 5°C indicated by noble gas studies in more southern locations of North America. The larger cooling is ascribed to the influence of the Laurentide ice sheet, which at its maximum extension came as close as 250 km to our study site.     

Laser microprobe for the study of noble gases and nitrogen in single grains: A case study of individual chondrules from the Dhajala meteorite

A laser microprobe capable of analysing nitrogen and noble gases in individual grains with masses less than a milligram is described. It can be used in both continuous wave (CW) mode, useful for stepwise heating of an individual grain, as well as in pulsed mode, useful for ablating material from a small selected area of a sample, for gas extraction. We could achieve low blanks (in ccSTP units) for 4He(4.8 x 10{-12}),²²Ne(1.0 x 10{-12}),³⁶Ar(1.0 x10 ^-13),⁸⁴Kr(2.9 x 10{-14}),¹³² Xe(2.6 x 10{-14}), and N (87 pg), using this system. Preliminary data for individual chondrules from the Dhajala meteorite show that noble gases and nitrogen from grains as small as 170 microgram can be analysed using the present laser microprobe setup. The amount of trapped neon in Dhajala chondrules is very small, and nitrogen in the chondrules is isotopically heavier as compared to the bulk meteorite.     

Effect of the thermal gradient variation through geological time on basin modeling; a case study: The Paris basin

Many studies investigated the thermal modeling of the Paris basin for petroleum interests during the 1970s. Most of the softwares developed by oil companies or research centers were based on the assumption of a constant thermal gradient. In order to take into consideration the variation of the thermal gradient during basin evolution, we developed the TherMO's Visual Basic 1D program. We applied our model to twenty boreholes located along a cross-section roughly running EW over 150 km in the center of the Paris basin. The numerical results were calibrated with organic matter maturity data. TherMO's simulates the amount of heat provided to the sedimentary organic matter. The heat parameter simulated shows lateral variation along the cross-section. It decreases from Rambouillet to Trou Aux Loups boreholes (87–66 mW/m²) at about 100 km more to the east whereas the heat flux value simulated is 73 mW/m² in St. Loup borehole. The mean thermal gradient calculated for liassic horizons at 87 My for the Rambouillet well is 50.4 °C/km. This value is similar to previously published results. By integrating the calculation of the thermal gradients and conductivities related to the burial of each stratigraphic sequence, our approach points out variations in the thermal regimes the sedimentary organic matter (SOM) has been subjected to through geological time.     

Chlorine transfer out of a very low permeability clay sequence (Paris Basin, France): Cl and Cl evidence

The marine Callovo-Oxfordian clay formation is found at a depth around 410m in the eastern part of the Paris Basin (France). It is a very low permeability formation investigated by the French agency for nuclear waste management (ANDRA) to study the feasibility of a radioactive waste disposal. Examining hydrogeological and geochemical characteristics of the clay sequence may test confinement properties of this formation. This study uses chlorine isotopes to investigate long-term transport processes which may carry chemical elements out of the clay layer to the surrounding rocks. Detailed chlorine concentration and δ³⁷Cl depth profiles are examined using pore waters and aquifer waters sampled in the clay formation and its surrounding aquifers (the Dogger at the bottom and the Oxfordian/Kimmeridgian/Tithonian unit at the top). They are discussed in terms of chlorine budget and hydrogeological processes.Clay pore waters and aquifer waters show strong chlorine concentration depletion (<3000 mg/L) relative to the original marine interstitial water (∼19000 mg/L). This probably results from an early dilution by meteoric water in limestones (as also indicated by oxygen and hydrogen isotopes).A steep Cl-concentration gradient from the Dogger at ∼500m in depth (∼2500 mg/L) to the Oxfordian/Kimmeridgian/Tithonian aquifer near the surface (≈ 10 mg/L) is associated to a ‘v-shaped’ profile of the δ³⁷Cl values. Modelling Cl transport shows that a hydrodynamic dispersion process explains Cl concentration and δ³⁷Cl profiles in Oxfordian Limestone. This process implies a mean upward flux of chloride in the 2.6 10⁻⁸-8.2 10⁻⁸ mole/m²/yr range from the clay formation towards upper limestones where a westward advective flow disperses the chloride. The modelling and knowledge of underground water transfer suggest a maximum effective Cl-hydrodynamic vertical dispersion coefficient (= vertical Cl-transport coefficient) of ∼7.6 10⁻¹⁰ m²/s.Chlorine transfer through the Callovo-Oxfordian clay, since deposition 160My ago, can be mainly described by the interplay of an early dilution and a later hydrodynamic dispersion event which has apparently erased most of the isotopic effects of diagenetic events (such as early diffusion, ion filtration etc.).     

大同盆地地下水砷异常及其成因研究

大同盆地是中国典型的原生高砷地下水分布区。笔者对大同盆地高砷地下水的分布特征、水化学演化过程、砷的来源以及控制高砷地下水形成的地球化学过程等近期研究成果进行了总结。盆地周边石炭—二叠纪煤系地层是盆地高砷环境的主要原生物源,含水层系统中铁磁性矿物为砷的主要载体,盆地内富含有机质的湖相沉积物是次生富砷介质。在盆地中心,地下水径流受阻,蒸发成为主要的排泄方式,浓缩作用使得地下水中TDS含量增大。在富含有机质的地层中,有机质在细菌或微生物作用下不断发生分解,使得地下水环境呈还原性。在高pH、低Eh条件下,由于铁锰氧化物或氢氧化物等水合物或粘土矿物对砷的吸附性降低,一部分被吸附的砷从这些矿物表面解吸;同时部分铁锰氧化物可被还原为低价态可溶性铁锰,从而使与其结合的砷也得以释放进入地下水中。在还原条件下,水中的SO24-和有机碳可被还原成H2S和CH4等低价态化合物,尽管生成的硫化物达到一定浓度时可与水中的亚铁离子和砷反应生成FeAsS沉淀,降低了地下水中砷含量,但由于地下水中Fe和硫酸盐含量有限,Fe普遍含量较低,硫酸盐耗尽后,CH4生成细菌就会成为主导力量,砷就会继续在地下水中积聚。此外,由于pH的升高,还可引起其他不同的酸根离子的解吸,如磷酸根、钒酸根、铀酰和钼酸根等也趋向于在溶液中积累,这些被吸附的阴离子以竞争吸附方式,进一步促进砷的解吸。     

A case study on changes in quality of groundwater with seasonal fluctuations of Pageru river basin, Cuddapah District, Andhra Pradesh, India

A study was conducted at Pageru river basin, Cuddapah District, Andhra Pradesh, to monitor seasonal fluctuations of groundwater and to determine how the fluctuation in the water levels will affect the groundwater quality. Groundwater levels were found to be influenced by rainfall and pumping of water from the wells for irrigation and domestic uses. Ninety-nine water samples were collected from different wells and analysed for major chemical constituents both in pre- and post-monsoon seasons to determine the quality variation. All major chemical constituents, such as Ca, Mg, Na, K etc., are significantly increased after post-monsoon recharge. According to the overall assessment of the basin, water quality was found to be useful both for drinking and irrigation.     

Artificial groundwater recharge to a semi-arid basin: case study of Mujib aquifer,Jordan

Mujib watershed is an important groundwater basin which is considered a major source for drinking and irrigation water in Jordan. Increased dependence on groundwater needs improved aquifer management with respect to understanding deeply recharge and discharge issues, planning rates withdrawal, and facing water quality problems arising from industrial and agricultural contamination. The efficient management of this source depends on reliable estimates of the recharge to groundwater and is needed in order to protect Mujib basin from depletion. Artificial groundwater recharge was investigated in this study as one of the important options to face water scarcity and to improve groundwater storage in the aquifer. A groundwater model based on the MODFLOW program, calibrated under both steady- and unsteady-state conditions, was used to investigate different groundwater management scenarios that aim at protecting the Mujib basin. The scenarios include variations of abstraction levels combined with different artificial groundwater recharge quantities. The possibilities of artificial groundwater recharge from existing and proposed dams as well as reclaimed municipal wastewater were investigated. Artificial recharge options considered in this study are mainly through injecting water directly to the aquifer and through infiltration from reservoir. Three scenarios were performed to predict the aquifer system response under different artificial recharge options (low, moderate, and high) which then compared with no action (recharge) scenario. The best scenario that provides a good recovery for the groundwater table and that can be feasible is founded to be by reducing current abstraction rates by 20% and implementing the moderate artificial recharge rates of 26 million(M)m³/year. The model constructed in this study helps decision makers and planners in selecting optimum management schemes suitable for such arid and semi-arid regions.     

Multi-tracer investigation of river and groundwater interactions: a case study in Nalenggele River basin,northwest China

Environmental tracers (such as major ions, stable and radiogenic isotopes, and heat) monitored in natural waters provide valuable information for understanding the processes of river–groundwater interactions in arid areas. An integrated framework is presented for interpreting multi-tracer data (major ions, stable isotopes (²H, ¹⁸O), the radioactive isotope ²²²Rn, and heat) for delineating the river–groundwater interactions in Nalenggele River basin, northwest China. Qualitative and quantitative analyses were undertaken to estimate the bidirectional water exchange associated with small-scale interactions between groundwater and surface water. Along the river stretch, groundwater and river water exchange readily. From the high mountain zone to the alluvial fan, groundwater discharge to the river is detected by tracer methods and end-member mixing models, but the river has also been identified as a losing river using discharge measurements, i.e. discharge is bidirectional. On the delta-front of the alluvial fan and in the alluvial plain, in the downstream area, the characteristics of total dissolved solids values, ²²²Rn concentrations and δ¹⁸O values in the surface water, and patterns derived from a heat-tracing method, indicate that groundwater discharges into the river. With the environmental tracers, the processes of river–groundwater interaction have been identified in detail for better understanding of overall hydrogeological processes and of the impacts on water allocation policies.     

Integrated study of the thermoluminescence,noble gases,tracks, and radionuclides in the fresh-fallen Ash Creek L6 and Tamdakht H5 chondrites

Thermoluminescence, noble gases, and the tracks of iron-group elements and cosmogenic radionuclides of various half-lives were examined in the fresh-fallen Ash Creek (L6) and Tamdakht (H5) chondrites. The experimental information thus obtained and theoretical simulations were used to study the shock-thermal and exposure histories of the chondrites, to evaluate their preatmospheric sizes and masses, values of ablation, the sizes of their orbits, and to monitor the distribution and variations in cosmic radiation in the heliosphere during the transitional period of minimum between solar cycles 23 and 24.     

Isotopic and noble gas study of Chalk groundwater in the London Basin, England

The chemical and isotopic composition of groundwater from 52 sites in the London (U.K.) area was determined as part of a project aimed at assessing the spatial variation in the age of Chalk groundwater, and in determining the relationship between fracture and matrix groundwater in this dual porosity system.Systematic changes in groundwater chemistry take place in the downgradient direction in response to several chemical processes. These processes include early concentration by evaporation and congruent dissolution of calcite followed by widespread incongruent dissolution and ion exchange in addition to local oxidation-reduction reactions, gypsum dissolution and saline intrusion. As a result of the above processes, Chalk groundwater follows an evolutionary path from Ca bicarbonate type to Na bicarbonate type.The age of Chalk groundwater was modelled using¹⁴C, δ¹³C,³H, δ²H and δ¹⁸0. There is a general increase in the groundwater age in a downgradient direction with the oldest water found in N central areas of the basin. Groundwater in the unconfined zones and in areas S of the Greenwich fault is almost entirely of unevolved, modem composition. Carbon-14 modelling suggests that Chalk groundwater in the S basin is generally less than 10000 a old while that in the north is generally between 10000 and 25000 a old. The presence of³H in concentrations of up to 7 TU in groundwater which yields ages of several 1000 a, however, indicates that mechanisms exist for the rapid introduction of recent groundwater to the confined aquifer. Results of palaeorecharge temperature determinations using δ²H, δ¹⁸0 and noble gas analytical results suggest that significant Devensian recharge did indeed occur in the aquifer.A model of the development of the Chalk recognizes that it is a classic dual porosity aquifer in which groundwater flow occurs predominantly in the fracture system. The upper 50 m of the aquifer was flushed with fresh water during the 2–3 × 10⁶ a of the Quaternary and therefore meteoric water largely replaced the Tertiary and Cretaceous marine water that previously saturated the system. Most processes which control the chemistry of the groundwater occur in the matrix where the surface area is exceptionally high. Although fracture flow dominates the flow regime, diffusion from the matrix into the fracture porosity controls the chemistry of Chalk groundwater.     

Effects of sulphate reduction and geogenic CO2 incorporation on the determination of 14C groundwater ages – a case study of the Palaeogene groundwater system in north-eastern Syria

Groundwater from the Palaeogene aquifer system in north-eastern Syria has been studied using chemical and isotopic methods to determine the effects of carbonate dissolution, sulphate reduction and geogenic CO₂ incorporation in the dilution of ¹⁴C activity, and later to correct the conventional ¹⁴C water ages. The reason for this non-classical approach of correction is because the groundwater in this karstified and Nummulitic carbonate aquifer occurs under confined and partly confined conditions, and is located in an area very close to deep faults and fractures. Furthermore, the interconnection with the Upper Cretaceous formations, which commonly contain gypsum and hydrocarbons, can facilitate the processes of sulphate reduction and geogenic CO₂ incorporation, which should not be excluded. The dilution factor related to carbonate dissolution was estimated to be about 0.60–0.75. The dilution factor associated with sulphate reduction, which only depends on H₂S content, was rather low (about 0.95). However, as a result of the local tectonic setting in this area, the influence of geogenic CO₂ incorporation was clearly high. The dilution factor associated with this effect ranges between 0.24–0.64. Consequently, the corrected ¹⁴C ages are considerably reduced compared with those determined by classical models. Accordingly, the groundwater in the study area can be divided into three main groups: (1) fresh, shallow and cold water of less than 1 ka age; (2) brackish, deep and thermal water of rather old age (10.9–12.3 ka B.P.); and (3) an admixed groundwater of intermediate quality and age (1.9–6.7 ka B.P.). Electronic Publication