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1.
A 4-yr study of spatial and temporal variability in the geochemistry of vadose groundwaters from caves within the Edwards aquifer region of central Texas offers new insights into controls on vadose groundwater evolution, the relationship between vadose and phreatic groundwaters, and the fundamental influence of soil composition on groundwater geochemistry. Variations in Sr isotopes and trace elements (Mg/Ca and Sr/Ca ratios) of dripwaters and soils from different caves, as well as phreatic groundwaters, provide the potential to distinguish between local variability and regional processes controlling fluid geochemistry, and a framework for understanding the links between climatic and hydrologic processes.The Sr isotope compositions of vadose cave dripwaters (mean 87Sr/86Sr = 0.7087) and phreatic groundwaters (mean 87Sr/86Sr = 0.7079) generally fall between values for host carbonates (mean 87Sr/86Sr = 0.7076) and exchangeable Sr in overlying soils (mean 87Sr/86Sr = 0.7088). Dripwaters have lower Mg/Ca and Sr/Ca ratios, and higher 87Sr/86Sr values than phreatic groundwaters. Dripwater 87Sr/86Sr values also inversely correlate with both Mg/Ca and Sr/Ca ratios. Mass-balance modeling combined with these geochemical relationships suggest that variations in fluid compositions are predominantly controlled by groundwater residence times, and water-rock interaction with overlying soils and host aquifer carbonate rocks. Consistent differences in dripwater geochemistry (i.e., 87Sr/86Sr, Mg/Ca, and Sr/Ca) between individual caves are similar to compositional differences in soils above the caves. While these differences appear to exert significant control on local fluid evolution, geochemical and isotopic variations suggest that the controlling processes are regionally extensive. Temporal variations in 87Sr/86Sr values and Mg/Ca ratios of dripwaters from some sites over the 4-yr interval correspond with changes in both aquifer and climatic parameters. These results have important implications for the interpretation of trace element and isotopic variations in speleothems as paleoclimate records, as well as the understanding of controls on water chemistry for both present-day and ancient carbonate aquifers.  相似文献   

2.
《Applied Geochemistry》2005,20(4):749-766
A synthesis of Sr isotope data from shallow and deep groundwaters, and brines from the Fennoscandian and Canadian Shields is presented. A salinity gradient is evident in the water with concentrations varying from approximately 1–75 g L−1 below 1500 m depth in the Fennoscandian Shield and from 10 up to 300 g L−1 below 650 m depth in the Canadian Shield. Strontium isotope ratios were measured to assess the origin of the salinity and evaluate the degree of water–rock interaction in the systems. In both shields, the Sr concentrations are enriched relative to Cl, defining a positive trend parallel to the seawater dilution line and indicative of Sr addition through weathering processes. The depth distribution for Sr concentration increases strongly with increasing depth in both shields although the variation in Sr-isotope composition does not mirror that of Sr concentrations. Strontium-isotope compositions are presented for surface waters, and groundwaters in several sites in the Fennoscandian and Canadian Shields. Numerous mixing lines can be drawn reflecting water–rock interaction. A series of calculated lines links the surface end-members (surface water and shallow groundwater) and the deep brines; these mixing lines define a range of 87Sr/86Sr ratios for the deep brines in different selected sites. All sites show a specific 87Sr/86Sr signature and the occurrence of large 87Sr/86Sr variations is site specific in both shields. In Canadian Shield brines, the Sr isotope ratios clearly highlight large water rock interaction that increases the 87Sr/86Sr ratio from water that could have been of marine origin. In contrast to the Canadian Shield, groundwater does not occur in closed pockets in the Fennoscandian, and the well-constrained 87Sr/86Sr signatures in deep brines should correspond to a large, well-mixed and homogeneous water reservoir, whose Sr isotope signature results from water–rock interaction.  相似文献   

3.
Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, 87Sr/86Sr ratios range from 0.7080 to 0.7090, and δ34S-SO4 values range from +10 to 30‰. A few waters have elevated δ13CDIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ18O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ18O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ18O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ13CDIC = −14.7 to−11.1‰ and 87Sr/86Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.  相似文献   

4.
The Nandong Underground River System (NURS) is located in a typical karst area dominated by agriculture in SE Yunnan Province, China. Groundwater plays an important role in the social and economical development in the area. The effects of human activities (agriculture and sewage effluents) on the Sr isotope geochemistry were investigated in the NURS. Seventy-two representative groundwater samples, which were collected from different aquifers (calcite and dolomite), under varying land-use types, both in summer and winter, showed significant spatial differences and slight seasonal variations in Sr concentrations and 87Sr/86Sr ratios. Agricultural fertilizers and sewage effluents significantly modified the natural 87Sr/86Sr ratios signature of groundwater that was otherwise dominated by water-rock interaction. Three major sources of Sr could be distinguished by 87Sr/86Sr ratios and Sr concentrations in karst groundwater. Two sources of Sr are the Triassic calcite and dolomite aquifers, where waters have low Sr concentrations (0.1-0.2 mg/L) and low 87Sr/86Sr ratios (0.7075-0.7080 and 0.7080-0.7100, respectively); the third source is anthropogenic Sr from agricultural fertilizers and sewage effluents with waters affected having radiogenic 87Sr/86Sr ratios (0.7080-0.8352 for agricultural fertilizers and 0.7080-0.7200 for sewage effluents, respectively), with higher Sr concentrations (0.24-0.51 mg/L). Due to the overlapping 87Sr/86Sr ratios, it is difficult to distinguish the sources of Sr in groundwater samples contaminated by agricultural fertilizers or sewage effluents based only on their 87Sr/86Sr ratios. However, 87Sr/86Sr ratios do provide key information for natural and anthropogenic sources in karst groundwater.  相似文献   

5.
Thermal water samples and related young and fossil mineralization from a geothermal system at the northern margin of the Upper Rhine Graben have been investigated by combining hydrochemistry with stable and Sr isotope geochemistry. Actively discharging thermal springs and mineralization are present in a structural zone that extends over at least 60 km along strike, with two of the main centers of hydrothermal activity being Wiesbaden and Bad Nauheim. This setting provides the rare opportunity to link the chemistry and isotopic signatures of modern thermal waters directly with fossil mineralization dating back to at least 500–800 ka. The fossil thermal spring mineralization can be classified into two major types: barite-(pyrite) fracture filling associated with laterally-extensive silicification; and barite, goethite and silica impregnation mineralization in Tertiary sediments. Additionally, carbonatic sinters occur around active springs. Strontium isotope and trace element data suggest that mixing of a hot (>100 °C), deep-sourced thermal water with cooler groundwater from shallow aquifers is responsible for present-day thermal spring discharge and fossil mineralization. The correlation between both Sr and S isotope ratios and the elevation of the barite mineralization relative to the present-day water table in Wiesbaden is explained by mixing of deep-sourced thermal water having high 87Sr/86Sr and low δ34S with shallow groundwater of lower 87Sr/86Sr and higher δ34S. The Sr isotope data demonstrate that the hot thermal waters originate from an aquifer in the Variscan crystalline basement at depths of 3–5 km. The S isotope data show that impregnation-type mineralization is strongly influenced by mixing with SO4 that has high δ34S values. The fracture style mineralization formed by cooling of the thermal waters, whereas impregnation-type mineralization precipitated by mixing with SO4-rich groundwater percolating through the sediments.  相似文献   

6.
The Quaternary coastal plain aquifer down gradient of the Wadi Watir catchment is the main source of potable groundwater in the arid region of south Sinai, Egypt. The scarcity of rainfall over the last decade, combined with high groundwater pumping rates, have resulted in water-quality degradation in the main well field and in wells along the coast. Understanding the sources of groundwater salinization and amount of average annual recharge is critical for developing sustainable groundwater management strategies for the long-term prevention of groundwater quality deterioration. A combination of geochemistry, conservative ions (Cl and Br), and isotopic tracers (87/86Sr, δ81Br, δ37Cl), in conjunction with groundwater modeling, is an effective method to assess and manage groundwater resources in the Wadi Watir delta aquifers. High groundwater salinity, including high Cl and Br concentrations, is recorded inland in the deep drilled wells located in the main well field and in wells along the coast. The range of Cl/Br ratios for shallow and deep groundwaters in the delta (∼50–97) fall between the end member values of the recharge water that comes from the up gradient watershed, and evaporated seawater of marine origin, which is significantly different than the ratio in modern seawater (228). The 87/86Sr and δ81Br isotopic values were higher in the recharge water (0.70,723 < 87/86Sr < 0.70,894, +0.94 < δ81Br < +1.28‰), and lower in the deep groundwater (0.70,698 < 87/86Sr < 0.70,705, +0.22‰ < δ81Br < +0.41‰). The δ37Cl isotopic values were lower in the recharge water (−0.48 < δ37Cl < −0.06‰) and higher in the deep groundwater (−0.01 < δ37Cl < +0.22‰). The isotopic values of strontium, chloride, and bromide in groundwater from the Wadi Watir delta aquifers indicate that the main groundwater recharge source comes from the up gradient catchment along the main stream channel entering the delta. The solute-weighted mass balance mixing models show that groundwater in the main well field contains 4–10% deep saline groundwater, and groundwater in some wells along the coast contain 2–6% seawater and 18–29% deep saline groundwater.A three-dimensional, variable-density, flow-and-transport SEAWAT model was developed using groundwater isotopes (87Sr/86Sr, δ37Cl and δ81Br) and calibrated using historical records of groundwater level and salinity. δ18O was used to normalize the evaporative effect on shallow groundwater salinity for model calibration. The model shows how groundwater salinity and hydrologic data can be used in SEAWAT to understand recharge mechanisms, estimate groundwater recharge rates, and simulate the upwelling of deep saline groundwater and seawater intrusion. The model indicates that most of the groundwater recharge occurs near the outlet of the main channel. Average annual recharge to delta alluvial aquifers for 1982 to 2009 is estimated to be 2.16 × 106 m3/yr. The main factors that control groundwater salinity are overpumping and recharge availability.  相似文献   

7.
《Applied Geochemistry》2005,20(11):2063-2081
This paper deals with chemical and isotope analyses of 21 springs, which were monitored 3 times in the course of 2001; the monitoring program was focused on the groundwater of the Gran Sasso carbonate karst aquifer (Central Italy), typical of the mountainous Mediterranean area.Based on the hydrogeological setting of the study area, 6 groups of springs with different groundwater circulation patterns were distinguished. The hydrogeochemistry of their main components provided additional information about groundwater flowpaths, confirming the proposed classification. The spatial distribution of their ion concentrations validated the assumptions underlying the hydrogeological conceptual model, showing diverging groundwater flowpaths from the core to the boundaries of the aquifer. Geochemical modelling and saturation index computation elucidated water–carbonate rock interaction, contribution by alluvial aquifers at the karst aquifer boundaries, as well as impacts of human activities.The analysis of 18O/16O and 2H/H values and their spatial distribution in the aquifer substantiated the hydrogeology-based classification of 6 groups of springs, making it possible to trace back groundwater recharge areas based on mean isotope elevations; the latter were calculated by using two rain monitoring stations. 87Sr/86Sr analyses showed seasonal changes in many springs: in winter–spring, the changes are due to inflow of new recharge water, infiltrating into younger rocks and thus increasing 87Sr/86Sr values; in summer–autumn, when there is no recharge and spring discharge declines, changes are due to base flow groundwater circulating in more ancient rocks, with a subsequent drop in 87Sr/86Sr values.The results of this study stress the contribution that spatio-temporal isotope monitoring can give to the definition of groundwater flowpaths and hydrodynamics in fissured and karst aquifers, taking into account their hydrogeological and hydrogeochemical setting.  相似文献   

8.
《Applied Geochemistry》2005,20(4):767-787
The supergiant Pb–Zn–Ag Broken Hill orebody and numerous other minor mineral deposits occur within the limited outcrop of the Proterozoic Curnamona Province of Australia. The vast majority of this Province is concealed by up to 200 m of transported regolith, hampering conventional exploration strategies. Approximately 300 groundwater samples were collected over the southern Curnamona Province to test whether this medium could be helpful in the search for hidden mineral deposits. Sulphur, Sr and Pb isotope composition of the groundwaters were determined and S excess (SXS), i.e., the amount of S that can be ascribed neither to evaporation nor to mixing, was calculated. Many samples were recognised to have undergone an addition of 34S-depleted S, which can be attributed to oxidation of sulfides with a Broken Hill type δ34S signature (average ∼0‰ V-CDT). Furthermore, Sr isotopes identify the broad types of bedrock that the groundwater has been interacting with, from the less radiogenic Adelaidean rocks (and minerals) in the west (groundwater 87Sr/86Sr ratio as low as 0.708) to the highly radiogenic Willyama Supergroup in the east (87Sr/86Sr ratio up to 0.737). The groundwaters have 207Pb/204Pb and 206Pb/204Pb ratios comparable to, or intermediate between, various mineralisation types recognised in the area (Broken Hill, Rupee, Thackaringa, etc., types). The few samples taken in the vicinity of known mineralisation yield positive indicators (positive SXS, low δ34S, 87Sr/86Sr signature of bedrock type and Pb isotope fingerprinting of mineralisation type). This study also highlights several new locations under sedimentary cover where these indicators suggest interaction with mineralisation.  相似文献   

9.
《Applied Geochemistry》2005,20(2):295-316
A confined aquifer system has developed in argillaceous marine and freshwater sediments of Pliocene–Holocene age in the northeastern Osaka Basin (NEOB) in central Japan. The shallow groundwater (<100 m) in the system is recharged in a northern hilly to mountainous area with dominantly Ca-HCO3 type water, which changes as it flows toward the SW to Mg-HCO3 type and then to Na-HCO3 type water. Comparison of the chemical and Sr isotopic compositions of the groundwater with those of the bulk and exchangeable components of the underground sediments indicates that elements leached from the sediments contribute negligibly to the NEOB aquifer system. Moreover, model calculations show that contributions of paleo-seawater in the deep horizon and of river water at the surface are not major factors of chemical change of the groundwater. Instead, the zonal pattern of the HCO3-dominant groundwater is caused by the loss of Ca2+ from the water as it is exchanged for Mg2+ in clays, followed by loss of Mg + Ca as they are exchanged for Na + K in clays between the Ca-HCO3 type recharge water and the exchangeable cations in the clay layers, which were initially enriched in Na+. Part of this process was reproduced in a chromatographic experiment in which Na type water with high 87Sr/86Sr was obtained from Mg type water with low 87Sr/86Sr by passing it through marine clay packed in a column. The flux of recharge water into the confined aquifer system according to this chromatographic model is estimated to be 0.99 mm/day, which is compatible with the average recharge flux to unconfined groundwater in Japan (1 mm/day).  相似文献   

10.
《Applied Geochemistry》1998,13(4):463-475
Strontium isotope ratios were measured on 13 rock, 18 leachate and 28 pore-water samples from the Milk River aquifer, the confining argillaceous formations, and the glacial till mantling the recharge area. Strontium isotope ratios (87Sr/86Sr) of pore waters from the aquifer, confining units, and the glacial till ranged from 0.7069 to 0.7082. The 87Sr/86Sr ratios in aquifer pore waters decrease with increasing distance from the aquifer recharge area, and this is interpreted to be the result of mixing and water–rock interaction within the aquifer.The solute composition of the recharging groundwater is modified by the local lithology, causing distinct geochemical patterns along different flow paths within the aquifer. Whole-rock 87Sr/86Sr ratios indicate that the shales and till are generally more radiogenic than the aquifer sandstone. The authigenic carbonate cements and rock-forming minerals comprising the major lithologic units had little apparent influence on the pore-water Sr chemistry. Carbonate cement leachates from the till and the aquifer sandstone are more radiogenic than those from the confining shale formations. Feldspar separates from the aquifer sandstone have relatively radiogenic Sr isotope ratios, whereas bentonites from the Milk River and Colorado Shale Formations have whole-rock and leachate Sr isotope ratios that are relatively unradiogenic. Ratios of most Milk River aquifer pore waters are lower than those of any leachates or whole rocks analyzed, except the bentonites.The 87Sr/86Sr ratios of exchangeable Sr in the bentonites are similar to ratios found in the more evolved pore waters. Simple rock–water interaction models calculated for the whole-rock, leachate, and exchangeable-ion/pore-water pairs indicate that ion exchange with bentonite clays within the Milk River and Colorado Shale Formations appears to influence the isotopic evolution of the pore-water Sr in each of these units.  相似文献   

11.
Hydrogeochemistry and environmental tracers (2H, 18O, 87Sr/86Sr) in precipitation, river and reservoir water, and groundwater have been used to determine groundwater recharge sources, and to identify mixing characteristics and mineralization processes in the Manas River Basin (MRB), which is a typical mountain–oasis–desert ecosystem in arid northwest China. The oasis component is artificial (irrigation). Groundwater with enriched stable isotope content originates from local precipitation and surface-water leakage in the piedmont alluvial–oasis plain. Groundwater with more depleted isotopes in the north oasis plain and desert is recharged by lateral flow from the adjacent mountains, for which recharge is associated with high altitude and/or paleo-water infiltrating during a period of much colder climate. Little evaporation and isotope exchange between groundwater and rock and soil minerals occurred in the mountain, piedmont and oasis plain. Groundwater δ2H and δ18O values show more homogeneous values along the groundwater flow direction and with well depths, indicating inter-aquifer mixing processes. A regional contrast of groundwater allows the 87Sr/86Sr ratios and δ18O values to be useful in a combination with Cl, Na, Mg, Ca and Sr concentrations to distinguish the groundwater mixing characteristics. Two main processes are identified: groundwater lateral-flow mixing and river leakage in the piedmont alluvial–oasis plain, and vertical mixing in the north oasis plain and the desert. The 87Sr/86Sr ratios and selected ion ratios reveal that carbonate dissolution and mixing with silicate from the southern mountain area are primarily controlling the strontium isotope hydrogeochemistry.  相似文献   

12.
In groundwater of the Trans-Pecos region of West Texas, unexpectedly high levels of nitrate (NO3 ?) are documented in four basins: Red Light Draw, Eagle Flats, Wild Horse and Michigan Flats, and Lobo and Ryan Flats. NO3 ? concentrations are changing over time in the majority (82.8 %) of wells and are increasing in most (69.8 %). The temporal change raises questions about the potential sources of NO3 ? and about flow dynamics in these basins. Presence of NO3 ? and temporal variability in concentration has implications beyond contamination risk because it indicates relatively rapid recharge (<60 years) to the basin groundwaters which was not expected based on previous estimates from chloride mass balance models and groundwater age-dating techniques. This research combines existing data ranging back to the 1940s with data collected in 2011 to document a multi-decadal trend of overall increasing NO3 ? concentration in deep basin groundwaters. Chlorofluorocarbon analyses of groundwater collected during 2011 indicate the presence of young (<70 years) water in the basins. The authors infer from these data that there are mechanism(s) by which relatively rapid and widespread recharge occurs on the basin floors; that recharge is spatially and temporally variable and that it results from both anthropogenic (irrigated agriculture) and natural (precipitation) sources. In light of these observations, fundamental conceptual models of flow in these basins should be re-evaluated.  相似文献   

13.
Despite the fact that porphyry Cu deposits contain large amounts of Cu in one or more small stocks, few studies have discussed evidence for significant magma recharge in porphyry Cu deposits. A systematic elemental and Sr isotopic study of plagioclase crystals from mineralized diorite and granodiorite porphyry constrains the processes of crystallization and magma recharge at the Baogutu reduced porphyry copper deposit, western Junggar, NW-China. Large compositional changes in An (12–24 mol%) are observed along with strong positive correlations between An and FeO. Significant resorption textures are also preserved in plagioclase crystals as well as repeated oscillatory zoning in An and FeO, and complex Sr isotope variations. Three types of crystals with different core-to-rim Sr isotope variations are recognized. Type I crystals have core-to-rim increases in (87Sr/86Sr)i that could be explained by diffusion. For example, Sr isotope variations recorded in BCK2-1-2 crystal could be generated by diffusion with simulated maximum crystal residence times of 100–500 years with the proximate value of ∼300 years. Type II crystals with different variation trends in (87Sr/86Sr)i on opposite sides of the core could be produced either by multi-stage crystallization or by analytical uncertainty. Whereas, type III crystals with complex core-to-rim variations in (87Sr/86Sr)i, may record repeated magma recharge events. All these results suggest repeated recharging of the magma chamber by hotter, more mafic and less radiogenic Sr isotope melts. Therefore, more mafic melt injection recorded in plagioclase profiles may provide significant metal contributions to the magma chamber, which ultimately results in Cu mineralization at the Baogutu reduced porphyry copper deposit.  相似文献   

14.
Groundwater quality in karst regions is largely controlled by natural processes and anthropogenic activities. Over the past 10?years, dissolved Sr and its radiogenic isotope, 87Sr/86Sr, were widely used to trace the sources of solutes in groundwater. However, there is little research about hydrogeochemistry and Sr isotopic compositions of the karst groundwater in Chongqing karst area. In this paper, thirty-five representative karst groundwater samples were collected from different aquifers (limestone and dolomite) and various land use types. Hydrochemical types of karst groundwater in Chongqing were mainly of the Ca-HCO3 type or Ca(Mg)-HCO3 type. The dissolved Sr concentrations of the studied groundwater ranged from 0.57 to 15.06???mmol/L, and the 87Sr/86Sr varied from 0.70751 to 0.71627. The groundwater samples from different aquifers and land use types showed distinctive dissolved Sr concentrations and 87Sr/86Sr. The very positive relationship between Ca/Sr and Mg/Sr in dolomite and limestone aquifers suggests that Ca, Mg and Sr element come mainly from the release of carbonate rock under the groundwater?Crock?CCO2 gas interaction. According to the 87Sr/86Sr ratio, the Sr element in karst groundwater in Chongqing was controlled by the weathering of limestone, dolomite and silicate rock (allogenic water in a non-karst area). The relationship 87Sr/86Sr versus Sr2+/[K+?+?Na+] shows that the anthropogenic inputs also obviously contribute to the Sr contents. The research results show that the karst groundwater in Chongqing is facing serious crisis of water quality, and needs to be protected further.  相似文献   

15.
Petrographic and geochemical studies of an Upper Eocene reef and associated basinal sediments from the mixed carbonate–siliciclastic fill of the south‐eastern Pyrenean foreland basin near Igualada (NE Spain) provide new insights into the evolution of subsurface hydrology during the restriction of a marine basin. The reef deposits are located on delta‐lobe sandstones and prodelta marls, which are overlain by hypersaline carbonates and Upper Eocene evaporites. Authigenic celestite (SrSO4) is an important component in the observed diagenetic sequences. Celestite is a significant palaeohydrological indicator because its low solubility constrains transportation of Sr2+ and SO42? in the same diagenetic fluid. Stable isotopic analyses of carbonates in the reef indicate that meteoric recharge was responsible for aragonite stabilization and calcite cementation. Sulphur and oxygen isotope geochemistry of the celestite demonstrates that it formed from residual sulphate after bacterial sulphate reduction, but also requires that there was a prior episode of sulphate recycling. Meteoric water reaching the reef and basinal areas was most probably charged with SO42? from the dissolution of younger Upper Eocene marine evaporites. This sulphate, combined with organic matter present in the sediments, fuelled bacterial sulphate reduction in the meteoric palaeoaquifer. Strontium for celestite precipitation was partly derived in situ from dissolution of aragonite corals in the reef and basinal counterparts. However, 87Sr/86Sr data also suggest that Sr2+ was partly derived from dissolution of overlying evaporites. Mixing of these two fluids promoted celestite formation. The carbonate stable isotopic data suggest that the local meteoric water was enriched in 18O compared with that responsible for stabilization of other reefs along the basin margin. Furthermore, meteoric recharge at Igualada post‐dated evaporite deposition in the basin, whereas other parts of the same reef complex were stabilized before evaporite formation. This discrepancy resulted from the spatial distribution of continental siliciclastic units that acted as groundwater conduits.  相似文献   

16.
Sixty-eight groundwater samples from the Ganges-Brahmaputra floodplain in the Bengal Basin were analyzed to assess the groundwater geochemistry, the subsurface hydrology, the buffering effects of sediments on trace metal concentrations and their isotopic compositions, and the magnitude of the subsurface trace element flux to the Bay of Bengal and to the global ocean. Samples obtained from depths of 10 to 350 m were measured for major and trace elements, dissolved gas, and tritium. On the basis of the 3He/3H ages, the groundwater at depth (30-150 m) appears to be continually replenished, indicating that this recharge of groundwater to depth must ultimately be balanced by a significant quantity of submarine discharge into the Bay of Bengal. Using the 3He/3H groundwater age-depth relationship to calculate a recharge rate of 60 ± 20 cm/yr, we estimate a subsurface discharge into the Bay of Bengal of 1.5 ± 0.5 × 1011 m3/yr, or 15% of the surface Ganges-Brahmaputra river (GBR) flux. Several trace elements, especially Sr and Ba, display elevated concentrations averaging 7 to 9 times the surface GBR water values. The submarine groundwater fluxes of Sr and Ba to the oceans are 8.2 ± 2 × 108 and 1.5 ± 0.3 × 108 mol/yr, or 3.3 and 1.2%, respectively, of the world total, or equal to the surface GBR Sr and Ba estimated fluxes. Our groundwater flux for Ba agrees with the estimate of Moore (1997) (3 × 108-3 × 109 mol/yr), on the basis of measured Ba and Ra excesses in the Bay of Bengal. Other trace metals, such as U and Mo, are at low but measurable levels and are not major contributors to the global flux in this river system. A comparison of the Sr and Ba concentrations, plus 87Sr/86Sr ratios in groundwater to the oxalate extractable fractions of a coastal sediment core, suggests that weathering of carbonates and minor silicates, coupled with cation exchange plus adsorption and desorption reactions, controls the trace element concentrations and 87Sr/86Sr isotopic compositions in both the groundwater and river water. Our data also imply that other coastal floodplains (e.g., the Mekong and the Irrawaddy rivers) that have high precipitation rates and rapid accumulation of immature sediments are likely to make significant contributions to the global oceanic trace metal budgets and have an impact on the Sr isotopic evolution in seawater.  相似文献   

17.
The Trigonodus Dolomit is the dolomitized portion of the homoclinal ramp sediments of the Middle Triassic Upper Muschelkalk in the south‐east Central European Basin. Various dolomitizing mechanisms, followed by recrystallization, have been previously invoked to explain the low δ18O, high 87Sr/86Sr, extensive spatial distribution and early nature of the replacive matrix dolomites. This study re‐evaluates the origin, timing and characteristics of the dolomitizing fluids by examining petrographic and isotopic trends in the Trigonodus Dolomit at 11 boreholes in northern Switzerland. In each borehole the ca 30 m thick unit displays the same vertical trends with increasing depth: crystal size increase, change from anhedral to euhedral textures, ultraviolet‐fluorescence decrease, δ18OVPDB decrease from ?1·0‰ at the top to ?6·7‰ at the base and an 87Sr/86Sr increase from 0·7080 at the top to 0·7117 at the base. Thus, dolomites at the top of the unit record isotopic values similar to Middle Triassic seawater (δ18OVSMOW = 0‰; 87Sr/86Sr = 0·70775) while dolomites at the base record values similar to meteoric groundwaters from the nearby Vindelician High (δ18OVSMOW = ?4·0‰; 87Sr/86Sr = >0·712). According to water–rock interaction modelling, a single dolomitizing or recrystallizing fluid cannot have produced the observed isotopic trends. Instead, the combined isotopic, geochemical and petrographic data can be explained by dolomitization via seepage‐reflux of hypersaline brines into dense, horizontally‐advecting groundwaters that already had negative δ18O and high 87Sr/86Sr values. Evidence for the early groundwaters is found in meteoric calcite cements that preceded dolomitization and in fully recrystallized dolomites with isotopic characteristics identical to the groundwaters following matrix dolomitization. This study demonstrates that early groundwaters can play a decisive role in the formation and recrystallization of massive dolomites and that the isotopic and textural signatures of pre‐existing groundwaters can be preserved during seepage‐reflux dolomitization in low‐angle carbonate ramps.  相似文献   

18.
Hydrochemistry and well hydrographs are coupled to assess groundwater recharge in the regional catchment of Samail, Oman. The complex geology comprises three aquifers: limestones of the Hajar Supergroup (HSG) at the highlands of North Oman Mountains (NOM); fractured/weathered ophiolites; and Quaternary alluvium. Groundwater flows south–north from the NOM to the coast. Samples from groundwater wells and springs (38) were analyzed for isotopes and major ions. Corrected 14C dating reveals modern groundwater across the entire catchment, while 87Sr/86Sr (0.70810–0.70895) shows greater homogeneity. Groundwater in the upper catchment is depleted in 2H and 18O, indicating a high-altitude recharge source (NOM), and becomes enriched downstream, with a slope indicating an evaporation effect. The hydrographs of nested piezometers located in the upper, middle and lower catchment show different recharge responses between deep and shallower depths. Head difference in response to recharge is observed upstream, suggesting a lateral recharge mechanism, contrary to vertical recharge downstream reflected in identical recharge responses. The homogeneous 87Sr/86Sr ratio, head changes, downstream enrichment of 2H and 18O, and the presence of modern groundwater throughout the catchment suggest that groundwater recharge takes place across the entire catchment and that the three aquifers are hydraulically connected. The recharge estimated using the chloride mass balance method is in the range of 0–43% of the mean annual rainfall.  相似文献   

19.
Groundwater from karst subterranean streams is among the world’s most important sources of drinking water supplies, and the hydrochemical characteristics of karst water are impacted by both natural environment and people. Therefore, the study of hydrochemistry and its solutes’ sources is very important to ensure the normal function of life support systems. In this paper, thirty?five representative karst groundwater samples were collected from different aquifers (limestone and dolomite) and various land use types in Chongqing to trace the sources of solutes and relative hydrochemical processes. Hydrogeochemical types of karst groundwater in Chongqing were mainly of the Ca?HCO3 type or Ca (Mg)?HCO3 type. However, some hydrochemical types of karst groundwater were the K+Na+Ca?SO4 type (G25 site) or Ca?HCO3+SO4 type (G26 and G14 site), indicating that the hydrochemistry of these sites might be strongly influenced by anthropogenic activities or unique geological characteristics. The dissolved Sr concentrations of the studied groundwater ranged from 0.57 to 15.06 μmmol/L, and the 87Sr/86Sr varied from 0.70751 to 0.71627. The δ34S?SO42? fell into a range of ?6.8‰?21.5‰, with a mean value of 5.6‰. The variations of both 87Sr/86Sr and Sr values of the groundwater samples indicated that the Sr element was controlled by the weathering of limestone, dolomite and silicate rock. However, the figure of 87Sr/86Sr vs. Sr2+/[K++Na+] showed that the anthropogenic inputs also obviously contributed to the Sr contents. For tracing the detailed anthropogenic effects, we traced the sources of solutes collected karst groundwater samples in Chongqing according to the δ34S value of potential sulfate sources. The variations of both δ34S and 1/SO42? values of the groundwater samples indicated that the atmospheric acid deposition (AAD), dissolution of gypsum (GD), oxidation of sul?de mineral (OS) or anthropogenic inputs (SF: sewage or fertilizer) have contributed to solutes in karst groundwater. The influence of oxidation of sul?de mineral, atmospheric acid deposit and anthropogenic inputs to groundwater in Chongqing karst areas was much widespread.  相似文献   

20.
《Applied Geochemistry》1998,13(5):593-606
The comparative geochemical and isotopic study of confined and unconfined Chalk groundwaters of the Paris Basin and the N German Basin proves a significant chemical evolution during groundwater flow from the recharge zones to the deep confined aquifer. Different time dependent geochemical parameters have been tested as dating tools: Cation ratios (Sr2+/Ca2+, Mg2+/Ca2+), N–NO−3, noble gas contents as paleotemperature indicators (Ne, Ar, Kr, Xe), radiogenic He, 13C, 14C, 18O, 2H, 3H. Cation ratios and 13C show the importance of incongruent dissolution processes in the Chalk aquifer. Water–rock interactions were taken into account in a multi-step dissolution model to determine radiocarbon groundwater ages. The oldest waters in the confined part of the Paris basin Chalk with maximum 14C ages of 14,000 a B.P. contain pleistocene recharge components as can be shown by a stable isotope depletion and noble gas temperatures significantly lower than in recent groundwaters. Chalk waters at the Lägerdorf site in Northern Germany show a distinct stratification with respect to residence times and hydrochemistry.  相似文献   

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