Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

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 δ¹³C_DIC 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 (δ¹³C_DIC = −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.     

Using geochemical indicators to investigate groundwater mixing and residence time in the aquifer system of Djeffara of Medenine (southeastern Tunisia)

Stable isotopes (??²H, ??¹⁸O and ??¹³C) and radiocarbon (¹⁴C) have been used in conjunction with chemical data to evaluate recharge mechanisms and groundwater residence time, and to identify inter-aquifer mixing in the Djeffara multi-aquifer in semi-arid southeastern Tunisia. The southern part of this basin, the Djeffara of Medenine aquifer system, is comprised of two main aquifers of Triassic and Miocene sandstone. The Triassic aquifer presents two compartments; the first one (west of the Medenine fault system) is unconfined with a well-defined isotope fingerprint; the second compartment is deeper and confined. Multi-tracer results show groundwater of different origins, ages and salinities, and that tectonic features control groundwater flows. Fresh and brackish groundwater from the unconfined part of the Triassic aquifer was mostly recharged during the Holocene. The recharge rates of this aquifer, inferred by ¹⁴C ages, are variable and could reach 3.5?mm/year. Brackish water of the deep confined part of the Triassic aquifer has stable isotope composition and ¹⁴C content that indicates earlier recharge during late Pleistocene cold periods. Brackish to saline water of the Miocene aquifer presents variable isotope composition. Groundwater flowing through the Medenine fault system is mainly feeding the Miocene aquifer rather than the deep confined part of the Triassic aquifer.     

The hydrogeochemical characterization of groundwater in Gafsa-Sidi Boubaker region (Southwestern Tunisia)

Gafsa region is one of the most productive artesian basins in Southern Tunisia. It is located in the southwestern part of the country, and its groundwater resources are developed for water supply and irrigation. Proper understanding of the geochemical evolution of groundwater is important for sustainable development of water resources in this region. A hydrogeochemical survey was conducted on the Plio-Quaternary shallow and on the Complex Terminal aquifers system using major (Ca, Mg, Na, SO₄, Cl, NO₃ and HCO₃) and minor (Sr) elements, in order to evaluate the groundwater chemistry patterns and the main mineralization processes occurring in this system. Hydrochemical and isotopic data were used in conjunction with hydrogeological characteristics to investigate the groundwater composition in these aquifers. It has been demonstrated that groundwaters acquire their mineralization principally by water–rock interaction, i.e. dissolution of evaporites (halite/gypsum, pyrite, etc.) and return flow of irrigation waters, and by anthropogenic activities due to the use of nitrogen (N) fertilizers–pesticides in agriculture. The isotopic study of “stable isotopes, radiocarbon and tritium” (Yermani 2002) shows that a paleoclimatic recharge is corroborated by the relatively low carbon-14 activities (5–25.3%) of the referred groundwater group samples, which were interpreted as recharge occurring during the late Pleistocene and the early Holocene periods. The water feedings of these aquifers are mainly provided by infiltration of precipitations, infiltration of irrigation water, lateral feeding from Cretaceous relieves from the South and the North and along recent and fossil drainage networks that constitute major freshwater sources in groundwater tables (Hamed et al., J Environ Protect 1:466–474, 2010a).     

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

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

Recharge into Southern High Plains aquifer—possible mechanisms,unresolved questions

The High Plains aquifer in the Southern High Plains (Texas and New Mexico), consisting of Tertiary, Cretaceous, and Triassic formations, has traditionally been considered to be recharged by its uppermost water-bearing unit, the Tertiary Ogallala aquifer. This article provides hydrologic, chemical, and isotopic evidence that in the Southern High Plains: (1) Cretaceous rocks actually contain independent recharge sources; (2) Triassic rocks cannot currently be recharged by the Ogallala aquifer in significant quantities; and (3) in places, both Cretaceous and Triassic aquifers recharge the overlying Ogallala aquifer. On the basis of chemical and isotopic data, playa lakes seem to act as the predominant recharge source of the Ogallala aquifer, suggesting recharge rates greater than 30 mm/yr, as opposed to the much lower rates reported by others. The Cretaceous aquifers are being recharged by cross-formational flow from the Ogallala aquifer but also from overlying Quaternary sands and the underlying Triassic aquifer in eastern New Mexico. Current recharge into the Triassic aquifer may be insignificant.     

Hydrochemical and stable isotopic investigation of groundwater quality and its sustainability for irrigation in the Hammamet-Nabeul basin,northeastern Tunisia

The major ion hydrochemistry, sodium absorption ratio (SAR), sodium percentage, and isotopic signatures of Hammamet-Nabeul groundwaters were used to identify the processes that control the mineralization, irrigation suitability, and origin of different water bodies. This investigation highlights that groundwater mineralization is mainly influenced by water-rock interaction and pollution by the return flow of irrigation water. The comparison of groundwater quality with irrigation suitability standards proves that most parts of groundwater are unacceptable for irrigation and this long-term practice may result in a significant increase of the salinity and alkalinity in the soils. Based on isotopic signatures, the shallow aquifer groundwater samples were classified into (i) waters with depleted δ¹⁸O and δ²H contents, highlighting recharge by modern precipitation, and (ii) waters with enriched stable isotope contents, reflecting the significance of recharge by contaminated water derived from the return flow of evaporated irrigation waters. The deep-aquifer groundwater samples were also classified into (i) waters with relatively enriched isotope contents derived from modern recharge and mixed with shallow-aquifer groundwater and (ii) waters with depleted stable isotope contents reflecting a paleoclimatic origin. Tritium data permit to identify three origins of recharge, i.e., contemporaneous, post-nuclear, and pre-nuclear. Carbon-14 activities demonstrate the existence of old paleoclimatic recharge related to the Holocene and Late Pleistocene humid periods.     

Holocene estuarine sediments as a source of arsenic in Pleistocene groundwater in suburbs of Hanoi,Vietnam

Groundwater pollution by arsenic is a major health threat in suburban areas of Hanoi, Vietnam. The present study evaluates the effect of the sedimentary environments of the Pleistocene and Holocene deposits, and the recharge systems, on the groundwater arsenic pollution in Hanoi suburbs distant from the Red River. At two study sites (Linh Dam and Tai Mo communes), undisturbed soil cores identified a Pleistocene confined aquifer (PCA) and Holocene unconfined aquifer (HUA) as major aquifers, and Holocene estuarine and deltaic sediments as an aquitard layer between the two aquifers. The Holocene estuarine sediments (approximately 25–40 m depth, 9.6–4.8 cal ka BP) contained notably high concentrations of arsenic and organic matter, both likely to have been accumulated by mangroves during the Holocene sea-level highstand. The pore waters in these particular sediments exhibited elevated levels of arsenic and dissolved organic carbon. Arsenic in groundwater was higher in the PCA (25–94 μg/L) than in the HUA (5.2–42 μg/L), in both the monitoring wells and neighboring household tubewells. Elevated arsenic concentration in the PCA groundwater was likely due to vertical infiltration through the arsenic-rich and organic-matter-rich overlying Holocene estuarine sediments, caused by massive groundwater abstraction from the PCA. Countermeasures to prevent arsenic pollution of the PCA groundwater may include seeking alternative water resources, reducing water consumption, and/or appropriate choice of aquifers for groundwater supply.     

Geochemical and isotopic characterization of groundwater from shallow and deep limestone aquifers system of Aleppo basin (north Syria)

Stable isotopes (δ¹⁸O, δ²H and ¹³C) and radioactivity (³H, ¹⁴C) have been used in conjunction with chemical data to evaluate the processes generating the chemical composition, reconstruct the origin of the water and groundwater residence time. The Aleppo basin is comprised of two main limestone aquifers: the first one is unconfined of Paleogene age and the second is confined of Upper Cretaceous age. The chemical data indicate that the dissolution of minerals and evaporation are the main processes controlling groundwater mineralization. The groundwater from the two aquifers is characterized by distinctive stable isotope signatures. This difference in water isotopes is interpreted in terms of difference origin and recharge period. Fresh and brackish shallow groundwater were mostly recharged during the Holocene period. The presence of ³H in several groundwater samples of this aquifer gives evidence that groundwater recharge is going on. Brackish water of the deep confined aquifer has depleted stable isotope composition and very low ¹⁴C activity that indicates recharge during the late Pleistocene cold period.     

A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin,Slovenia

The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃ ^–, Ca²⁺, Mg²⁺ and δ¹³C_DIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³C_DIC values, with low SO₄ ^2– and NO₃ ^– concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in ¹⁸O and ²H, and have ³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.     

Pleistocene recharge to midcontinent basins: effects on salinity structure and microbial gas generation

The hydrogeochemistry of saline-meteoric water interface zones in sedimentary basins is important in constraining the fluid migration history, chemical evolution of basinal brines, and physical stability of saline formation waters during episodes of freshwater recharge. This is especially germane for interior cratonic basins, such as the Michigan and Illinois basins. Although there are large differences in formation water salinity and hydrostratigraphy in these basins, both are relatively quiescent tectonically and have experienced repeated cycles of glaciation during the Pleistocene. Exploration for unconventional microbial gas deposits, which began in the upper Devonian-age Antrim Shale at the northern margin of the Michigan Basin, has recently extended into the age-equivalent New Albany Shale of the neighboring Illinois Basin, providing access to heretofore unavailable fluid samples. These reveal an extensive regional recharge system that has profoundly changed the salinity structure and induced significant biogeochemical modification of formation water elemental and isotope geochemistry.New-formation water and gas samples were obtained from Devonian-Mississippian strata in the Illinois Basin. These included exploration wells in the New Albany Shale, an organic-rich black shale of upper Devonian age, and formation waters from over- and underlying regional aquifer systems (Siluro-Devonian and Mississippian age). The hydrostratigraphic relations of major aquifers and aquitards along the eastern margin of the Illinois Basin critically influenced fluid migration into the New Albany Shale. The New Albany Shale formation water chemistry indicates significant invasion of meteoric water, with δD values as low as −46.05‰, into the shale. The carbon stable isotope system (δ¹³C values as high as 29.4‰), coupled with δ¹⁸O, δD, and alkalinity of formation waters (alkalinity ≤24.08 meq/kg), identifies the presence of microbial gas associated with meteoric recharge. Regional geochemical patterns identify the underlying Siluro-Devonian carbonate aquifer system as the major conduit for freshwater recharge into the fractured New Albany Shale reservoirs. Recharge from overlying Mississippian carbonates is only significant in the southernmost portion of the basin margin where carbonates directly overlie the New Albany Shale.Recharge of dilute waters (Cl⁻ <1000 mM) into the Siluro-Devonian section has suppressed formation water salinity to depths as great as 1 km across the entire eastern Illinois Basin margin. Taken together with salinity and stable isotope patterns in age-equivalent Michigan Basin formation waters, they suggest a regional impact of recharge of δ¹⁸O- and δD-depleted fluids related to Pleistocene glaciation. Devonian black shales at both basin margins have been affected by recharge and produced significant volumes of microbial methane. This recharge is also manifested in different salinity gradients in the two basins because of their large differences in original formation water salinity. Given the relatively quiet tectonic history and subdued current topography in the midcontinent region, it is likely that repeated cycles of glacial meltwater invasion across this region have induced a strong disequilibrium pattern in fluid salinity and produced a unique class of unconventional shale-hosted gas deposits.     

Groundwater recharge and evolution of water quality in China’s Jilantai Basin based on hydrogeochemical and isotopic evidence

We investigated major ions, stable isotopes, and radiocarbon dates in a Quaternary aquifer in semi-arid northwestern China to gain insights into groundwater recharge and evolution. Most deep and shallow groundwater in the Helan Mountains was fresh, with total dissolved solids <1,000 mg L^?1 and Cl^? <250 mg L^?1. The relationships of major ions with Cl^? suggest strong dissolution of evaporites. However, dissolution of carbonates, albite weathering, and ion exchange are also the major groundwater process in Jilantai basin. The shallow desert groundwater is enriched in δ¹⁸O and intercepts the local meteoric water line at δ¹⁸O = ?13.4 ‰, indicating that direct infiltration is a minor recharge source. The isotope compositions in intermediate confined aquifers resemble those of shallow unconfined groundwater, revealing that upward recharge from intermediate formations is a major source of shallow groundwater in the plains and desert. The estimated residence time of 10.0 kyr at one desert site, indicating that some replenishment of desert aquifers occurred in the late Pleistocene and early Holocene with a wetter and colder climate than at present.     

Hydrochemical trends,palaeorecharge and groundwater ages in the fissured Chalk aquifer of the London and Berkshire Basins,UK

The hydrochemical, radiochemical, stable isotope, ¹⁴C and dissolved noble gas composition of groundwaters has been determined along two profiles across the confined, fissured Chalk aquifer of the London Basin of southern England, and for selected sites in the adjacent Berkshire Basin. During downgradient flow in the London Basin aquifer, the groundwater chemistry is modified by water–rock interactions: congruent and incongruent reaction of the carbonate lithology resulting in enhanced Mg/Ca and Sr/Ca ratios and ¹³C contents with increased residence times; redox and ion exchange reactions; and towards the centre of the Basin, mixing with a residual saline connate water stored in the Chalk matrix. There is evidence from anomalous water chemistries for a component of vertical leakage from overlying Tertiary beds into the confined aquifer as a result of historical dewatering of the aquifer. Dissolved noble gas contents indicate the climate was up to 4.5°C cooler than at present during recharge of the waters now found in the centres of both Basins; stable isotope (²H and ¹⁸O) depletions correspond to this recharge temperature change. For evolved waters having δ¹³C > −8‰ PDB a negative linear correlation is demonstrated between derived recharge temperatures and δ¹³C values, which is interpreted as mixing between relatively warm, light isotopic, fracture-borne waters and cooler stored waters of the matrix having a ¹³C signature more or less equilibrated with the Chalk. From geochemical (¹⁴C, ⁴He) age estimates, the abstracted water is interpreted as being either of wholly Holocene/post-Devensian glacial origin, or an admixture of Holocene and Late Pleistocene pre-glacial (cold stage interstadial) recharge. Devensian pleniglacial stage waters of the Last Glacial Maximum are not represented.     

Tracing sources of carbon in urban groundwater using δ<Superscript>13</Superscript>C<Subscript>TDIC</Subscript> ratios

Total dissolved inorganic carbon (TDIC) and its stable isotope ratio δ¹³C_TDIC are used to trace the evolution of the carbon system of groundwater in three UK Permo-Triassic sandstone aquifers. Samples were collected from multilevel piezometers, open boreholes and sewer sampling points in the British Midlands (Nottingham, Birmingham and Doncaster) to evaluate both local and regional variations in δ¹³C_TDIC. δ¹³C samples of matrix and pore water have also been analysed in each aquifer to further constrain the interpretations. Combining δ¹³C_TDIC ratios with measurements of TDIC and pH clearly distinguishes the principal processes underlying the geochemical evolution of groundwater in Triassic sandstone aquifers, where processes can be both natural (e.g. carbonate dissolution) and anthropogenic (sewer-derived recharge). The paper shows that δ¹³C_TDIC resolves ambiguities that arise from the interpretation of TDIC and pH measurements in isolation. Field measurements demonstrate that, under natural conditions, the carbonate system evolves similarly in each aquifer. An open-system evolution during recharge largely saturates the groundwater with carbonate depending upon its availability in the sandstone matrix. The contribution of sewer exfiltration to urban recharge is readily distinguished by lower pH and higher TDIC values without significant changes in δ¹³C_TDIC.     

Hydrogeological and hydrochemical investigation of groundwater using environmental isotopes (18O, 2H, 3H, 14C) and chemical tracers: a case study of the intermediate aquifer,Sfax, southeastern Tunisia

Major element concentrations and stable (δ¹⁸O and δ²H) and radiogenic (³H and ¹⁴C) isotopes in groundwater have proved useful tracers for understanding the geochemical processes that control groundwater mineralization and for identifying recharge sources in the semi-arid region of Sfax (southeastern Tunisia). Major-ion chemical data indicate that the origins of the salinity in the groundwater are the water–rock interactions, mainly the dissolution of evaporitic minerals, as well as the cation exchange with clay minerals. The δ¹⁸O and δ²H relationships suggest variations in groundwater recharge mechanisms. Strong evaporation during recharge with limited rapid water infiltration is evident in the groundwater of the intermediate aquifer. The mixing with old groundwater in some areas explains the low stable isotope values of some groundwater samples. Groundwaters from the intermediate aquifer are classified into two main water types: Ca-Na-SO₄ and Ca-Na-Cl-SO₄. The high nitrate concentrations suggest an anthropogenic source of nitrogen contamination caused by intensive agricultural activities in the area. The stable isotopic signatures reveal three water groups: non-evaporated waters that indicate recharge by recent infiltrated water; evaporated waters that are characterized by relatively enriched δ¹⁸O and δ²H contents; and mixed groundwater (old/recent) or ancient groundwater, characterized by their depleted isotopic composition. Tritium data support the existence of recent limited recharge; however, other low tritium values are indicative of pre-nuclear recharge and/or mixing between pre-nuclear and contemporaneous recharge. The carbon-14 activities indicate that the groundwaters were mostly recharged under different climatic conditions during the cooler periods of the late Pleistocene and Holocene.

     

Strontium isotopic evidence on the chemical evolution of pore waters in the Milk River Aquifer,Alberta, Canada

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.     

The deep Cretaceous aquifer in the Aleppo and Steppe basins of Syria: assessment of the meteoric origin and geographic source of the groundwater

A drilling project was carried out in Syria to assess the potential of the deep groundwater resources of the Cretaceous aquifer, composed of Cenomanian-Turonian limestones and dolomites. In this context, isotope (¹⁴C, ³H, δ¹³C, δ¹⁸O, δ²H) and hydrochemical analyses were performed on wells in and around the Aleppo and Steppe basins. The interpretation includes complementary results from published and unpublished literature. The results provide evidence that many new wells pump mixed groundwater from the Cretaceous aquifer and the overlying Paleogene aquifer. Radiocarbon measurements confirmed dominating Pleistocene groundwater in the Cretaceous aquifer and mainly Holocene groundwater in the Paleogene aquifer. Most groundwater in the Cretaceous aquifer seems to be recharged in the western limestone ridges, stretching from Jebel az Zawiyah (south of Idlep) via Jebel Samane (south of Afrin and A’zaz) to the region north of Aleppo, and in the Northern Palmyrides mountain belt. Some recharge also occurs around the basalt plateau of the Jebel al Hass, south east of Aleppo. It is concluded that the Taurus Mountains and the Euphrates River do not recharge the Cretaceous aquifer. The sources of recharge seem to be occasionally occurring intensive winter storms that approach from Siberia.     

A new groundwater radiocarbon correction approach accounting for palaeoclimate conditions during recharge and hydrochemical evolution: The Ledo-Paniselian Aquifer,Belgium

The particular objective of the present work is the development of a new radiocarbon correction approach accounting for palaeoclimate conditions at recharge and hydrochemical evolution. Relevant climate conditions at recharge are atmospheric pCO₂ and infiltration temperatures, influencing C isotope concentrations in recharge waters. The new method is applied to the Ledo-Paniselian Aquifer in Belgium. This is a typical freshening aquifer where recharge takes place through the semi-confining cover of the Bartonian Clay. Besides cation exchange which is the major influencing process for the evolution of groundwater chemistry (particularly in the Bartonian Clay), also mixing with the original porewater solution (fossil seawater) occurs in the aquifer. Recharge temperatures were based on noble gas measurements. Potential infiltration water compositions, for a range of possible pCO₂, temperature and calcite dissolution system conditions, were calculated by means of PHREEQC. Then the sampled groundwaters were modelled starting from these infiltration waters, using the computer code NETPATH and considering a wide range of geochemical processes. Fitting models were selected on the basis of correspondence of calculated δ¹³C with measured δ¹³C. The ¹⁴C modelling resulted in residence times ranging from Holocene to Pleistocene (few hundred years to over 40 ka) and yielded consistent results within the uncertainty estimation. Comparison was made with the δ¹³C and Fontes and Garnier correction models, that do not take climate conditions at recharge into account. To date these are considered as the most representative process-oriented existing models, yet differences in calculated residence times of mostly several thousands of years (up to 19 ka) are revealed with the newly calculated ages being mostly (though not always) younger. Not accounting for climate conditions at recharge (pCO₂ and temperature) is thus producing substantial error on deduced residence times. The derived ¹⁴C model ages are correlated with He concentrations measured in the groundwater of the aquifer. The obtained residence times show a gap between about 14 and 21 ka indicating possible permafrost conditions which inhibited any groundwater recharge.     

Groundwater circulation and hydrogeochemical evolution in Nomhon of Qaidam Basin,northwest China

In this study, analysis of hydrogeological conditions, as well as hydrochemistry and isotopic tools were used to get an insight into the processes controlling mineralization, recharge conditions, and flow pattern of groundwater in a typical arid alluvial-lacustrine plain in Qaidam Basin, northwest China. Analysis of the dissolved constituents reveals that groundwater evolves from fresh water (TDS =300–1000 mg/l) to saline water (TDS ≥5000 mg/l) along the flow paths, with the water type transiting from HCO ₃?Cl–Na ?Mg to HCO ₃?Cl–Na, and eventually to Cl–Na. Groundwater chemical evolution is mainly controlled by water–rock interaction and the evaporation–crystallization process. Deuterium and oxygen-18 isotopes in groundwater samples indicate that the recharge of groundwater is happened by meteoric water and glacier melt-water in the Kunlun Mountains, and in three different recharge conditions. Groundwater ages, estimated by the radiogenic (³H and ¹⁴C) isotope data, range from present to Holocene (～28 ka). Based on groundwater residence time, hydrogeochemical characteristics, field investigation, and geological structure distribution, a conceptual groundwater flow pattern affected by uplift structure is proposed, indicating that shallow phreatic water is blocked by the uplift structure and the flow direction is turned to the northwest, while high pressure artesian water is formed in the confined aquifers at the axis of the uplift structure.     

Hydrogeological characterization of carbonated Jurassic aquifers in the Gijón-Villaviciosa basin (Asturias,N Spain) by means of geochemical and isotopic techniques

Chemical and isotopic analyses of groundwater from the carbonated Jurassic aquifers in the Gijón-Villaviciosa basin (Asturias, northern Spain) were carried out. Nine springs were sampled to determine major cations and anions, as well as the stable isotopes of the water molecule (δ²H and δ¹⁸O) and sulphate (δ³⁴S) values. Also, δ³⁴S values from gypsum coming both from Triassic rocks and bottom of Jurassic sequence were also determined. The results obtained were used to classify the waters with a genetic criteria in three groups: (1) waters with a high gypsum influence, with sulphate coming from Jurassic gypsum, (2) waters without gypsum influence, where sulphate source could be atmospheric deposition from industrial processes and marine aerosol, and (3) waters with some gypsum influence, in which sulphate origin could be a combination of different sources. In relation to recharge, δ²H and δ¹⁸O values were close to those of Global Meteoric Water Line and fit a local line that suggests a meteoric origin. The estimated elevations for spring recharge are in agreement with those obtained from hydrogeological maps.     

Assessment of recharge to groundwater systems in the arid southwestern part of Northern Territory, Australia, using chlorine-36

 The sustainability of community water supplies drawn from shallow aquifers in the arid southwest of the Northern Territory has been evaluated using the radioactive isotope chlorine-36 (³⁶Cl). These aquifers include fractured sandstones of the Ngalia Basin, fractured metamorphic rocks and Cainozoic sands and gravels. ³⁶Cl/Cl ratios for these shallow, regional groundwaters exhibit a bimodal distribution with peaks at 205 (±7) and 170 (±7)×10^–15. The higher ratio probably represents modern (Holocene) recharge, diluted with windblown salts from local playa lakes, and occurs mostly around the margin of the basin. The lower ratio corresponds to a ³⁶Cl "age", or mean residence time, of 80–100 ka, implying that the last major recharge occurred during the last interglacial interval (Oxygen Isotope Stage 5). These values are mainly observed in the interior of the Ngalia Basin. Lower values of the ³⁶Cl/Cl ratio measured near playa lakes are affected by addition of chloride from remobilised salts. Finite carbon-14 (¹⁴C) data for the groundwaters are at variance with the ³⁶Cl results, but a depth profile suggests low recharge, allowing diffusion of recent atmospheric carbon to the water table. The ³⁶Cl results have important implications for groundwater management in this region, with substantial recharge only occurring during favourable, wet, interglacial climatic regimes; most community water supplies are dependent on these "old" waters. Received, September 1997 · Revised, August 1998, March 1999 · Accepted, March 1999