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.     

Impact of Carbonate Precipitation on Riverine Inorganic Carbon Mass Transport from a Mid-continent, Forested Watershed

Physiochemical controls on the carbonate geochemistry of large river systems are important regulators of carbon exchange between terrestrial and marine reservoirs on human time scales. Although many studies have focused on large-scale river carbon fluxes, there are few investigations of mechanistic aspects of carbonate mass balance and transport at the catchment scale. We determined elemental and carbonate geochemistry and mass balances for net carbonate dissolution fluxes from the forested, mid-latitude Huron River watershed, established on carbonate-rich unconfined glacial drift aquifers. Shallow groundwaters are near equilibrium with respect to calcite at pCO₂ values up to 25 times atmospheric values. Surface waters are largely groundwater fed and exhibit chemical evolution due to CO₂ degassing, carbonate precipitation in lakes and wetlands, and anthropogenic introduction of road salts (NaCl and CaCl₂). Because the source groundwater Mg²⁺/HCO₃ ^? ratio is fairly constant, this parameter permits mass balances to be made between carbonate dissolution and back precipitation after groundwater discharge. Typically, precipitation does not occur until IAP/K calcite values exceed 10 times supersaturation. Stream chemistry changes little thereafter even though streams remain highly supersaturated for calcite. Our data taken together with historical United States Geological Survey (USGS) data show that alkalinity losses to carbonate precipitation are most significant during periods of lowest discharge. Thus, on an annual basis, the large carbon flux from carbonate dissolution in soil zones is only decreased by a relatively small amount by the back precipitation of calcium carbonate.     

Arsenic and Antimony in Groundwater Flow Systems: A Comparative Study

Arsenic (As) and antimony (Sb) concentrations and speciation were determined along flow paths in three groundwater flow systems, the Carrizo Sand aquifer in southeastern Texas, the Upper Floridan aquifer in south-central Florida, and the Aquia aquifer of coastal Maryland, and subsequently compared and contrasted. Previously reported hydrogeochemical parameters for all three aquifer were used to demonstrate how changes in oxidation–reduction conditions and solution chemistry along the flow paths in each of the aquifers affected the concentrations of As and Sb. Total Sb concentrations (Sb_T) of groundwaters from the Carrizo Sand aquifer range from 16 to 198 pmol kg⁻¹; in the Upper Floridan aquifer, Sb_T concentrations range from 8.1 to 1,462 pmol kg⁻¹; and for the Aquia aquifer, Sb_T concentrations range between 23 and 512 pmol kg⁻¹. In each aquifer, As and Sb (except for the Carrizo Sand aquifer) concentrations are highest in the regions where Fe(III) reduction predominates and lower where SO₄ reduction buffers redox conditions. Groundwater data and sequential analysis of the aquifer sediments indicate that reductive dissolution of Fe(III) oxides/oxyhydroxides and subsequent release of sorbed As and Sb are the principal mechanism by which these metalloids are mobilized. Increases in pH along the flow path in the Carrizo Sand and Aquia aquifer also likely promote desorption of As and Sb from mineral surfaces, whereas pyrite oxidation mobilizes As and Sb within oxic groundwaters from the recharge zone of the Upper Floridan aquifer. Both metalloids are subsequently removed from solution by readsorption and/or coprecipitation onto Fe(III) oxides/oxyhydroxides and mixed Fe(II)/Fe(III) oxides, clay minerals, and pyrite. Speciation modeling using measured and computed Eh values predicts that Sb(III) predominate in Carrizo Sand and Upper Floridan aquifer groundwaters, occurring as the Sb(OH)₃⁰ species in solution. In oxic groundwaters from the recharge zones of these aquifers, the speciation model suggests that Sb(V) occurs as the negatively charged Sb(OH)₆⁻ species, whereas in sufidic groundwaters from both aquifers, the thioantimonite species, HSb₂S₄ ⁻ and Sb₂S₄ ²⁻, are predicted to be important dissolved forms of Sb. The measured As and Sb speciation in the Aquia aquifer indicates that As(III) and Sb(III) predominate. Comparison of the speciation model results based on measured Eh values, and those computed with the Fe(II)/Fe(III), S(-II)/SO₄, As(III)/As(V), and Sb(III)/Sb(V) couples, to the analytically determined As and Sb speciation suggests that the Fe(II)/Fe(III), S(-II)/SO₄ couples exert more control on the in situ redox condition of these groundwaters than either metalloid redox couple.     

Groundwater quality variations in glacial drift and bedrock aquifers,Barry County,Michigan, U.S.A.

Groundwater samples from 288 domestic wells in Barry County, Michigan, were analyzed for 33 inorganic chemical parameters. Variations in chemical composition were investigated by considering the possible effects of human impact, aquifer type (bedrock vs glacial drift), chemical evolution along groundwater flow paths, and glacial landform type (moraine vs outwash). Approximately 25 percent of the glacial drift wells were classified as degraded by human impact and were excluded from further analysis of chemical variation. Two-sample tests comparing individual concentrations from drift and bedrock aquifers suggest that groundwater in the Marshall Sandstone aquifer is derived from local recharge through the glacial drift. This conclusion is supported by generalized groundwater flow patterns recognized for the two aquifers.Concentrations in both aquifers were examined in relation to generalized flow paths derived from water level data and also by classification of wells as recharge, transition, and discharge. No spatial concentration trends in major ions were detected, although iron concentrations do appear to increase from recharge to discharge areas. Declining redox potential along groundwater flow paths may explain this trend.The possible influence of glacial landform type was investigated by comparing concentrations of wells in moraines with those in outwash deposits. Wells in moraines have significantly higher concentrations of most parameters, perhaps due to higher content of finer, more chemically reactive sediment grains.     

Strontium isotope geochemistry of groundwaters and streams affected by agriculture,Locust Grove,MD

The effects of agriculture on the isotope geochemistry of Sr were investigated in two small watersheds in the Atlantic coastal plain of Maryland. Stratified shallow oxic groundwaters in both watersheds contained a retrievable record of increasing recharge rates of chemicals including NO₃⁻, Cl, Mg, Ca and Sr that were correlated with increasing fertilizer use between about 1940 and 1990. The component of Sr associated with recent agricultural recharge was relatively radiogenic (⁸⁷Sr/⁸⁶Sr=0.715) and it was overwhelming with respect to Sr acquired naturally by water–rock interactions in the oxidized, non-calcareous portion of the saturated zone. Agricultural groundwaters that penetrated relatively unoxidized calcareous glauconitic sediments at depth acquired an additional component of Sr from dissolution of early Tertiary marine CaCO₃ (⁸⁷Sr/⁸⁶Sr=0.708) while undergoing O₂ reduction and denitrification. Ground-water discharge contained mixtures of waters of various ages and redox states. Two streams draining the area are considered to have higher ⁸⁷Sr/⁸⁶Sr ratios and NO₃⁻ concentrations than they would in the absence of agriculture; however, the streams have consistently different ⁸⁷Sr/⁸⁶Sr ratios and NO₃⁻ concentrations because the average depth to calcareous reducing (denitrifying) sediments in the local groundwater flow system was different in the two watersheds. The results of this study indicate that agriculture can alter significantly the isotope geochemistry of Sr in aquifers and streams and that the effects could vary depending on the types, sources and amounts of fertilizers added, the history of fertilizer use and groundwater residence times.     

Increasing Iron Concentrations in UK Upland Waters

Iron distributions in rainfall, streams, soils and groundwaters are described for the Upper River Severn catchment of mid-Wales. Iron is mainly supplied from within-catchment sources with highest concentrations occurring under reducing conditions. Iron concentrations have doubled over the past 20 years (~5.0 μg yr⁻¹ for the forest and ~3.7 μg yr⁻¹ for the moorland). For the forested sites, the gradients are particularly high post-1993. UK rivers/lakes monitored by the UK Acid Waters Monitoring Network show similar increases. Generally, Fe correlates with dissolved organic carbon (DOC). The greatest rates of Fe increase coincide with those for DOC. Thermodynamic modelling using WHAM/Model VI indicates that Fe(III) is mainly in microparticulate form (probably oxyhydroxides) apart from under reducing conditions. It is proposed that Fe increases for surface waters are associated with increased microparticulate Fe(III) due to stabilisation against aggregation by binding of DOM to its surface. The results relate to acidification declines and deforestation leading to land disturbance and wetter conditions within the soil. There will be greater acidification reversal following tree harvesting due to lowering of atmospheric SO_x scavenging and this may have resulted in the greater increase in Fe in the later years of the study.     

Model for Sr accumulation in the Carboniferous deposits of the Moscow artesian basin

Statistical and thermodynamic analysis of hydrogeochemical information on Sr accumulation in the waters of Carboniferous deposits in the Moscow artesian basin indicates that Sr concentration increases mostly with increasing salinity of the aqueous solution and its Mg and sulfate contents. The highest Sr concentrations are 8–10 mg/l, and Sr accumulation in groundwaters is constrained by the precipitation of strontiantie in the system aqueous solution + dolomite + calcite + strontianite. An increase in Sr concentrations in the Carboniferous waters is symbate with the accumulation of F, and the accumulation of Sr (as well as F) is largely controlled by two factors: a change in the hydrogeochemical type of the groundwaters toward its transition and an overprinted process of the slowing of water filtration from the recharge area of the aquifers (where the Carboniferous deposits are exposed at the surface) down the dips of the water-hosting strata.     

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin,Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l⁻¹ and 1480 μg l⁻¹. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH₄, dissolved organic C (DOC), HCO₃ and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l⁻¹) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO₄ concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO₄ reduction has been an active process. High concentrations of Fe, Mn, NH₄, HCO₃ and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg⁻¹ (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO₃, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l⁻¹) and F⁻ (up to 6.8 mg l⁻¹). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO₃ as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.     

Control of organic and iron colloids on arsenic partition and transport in high arsenic groundwaters in the Hetao basin, Inner Mongolia

Due to the importance of colloids in regulating element transport and mobility in aquifers, As distribution in the colloidal fraction needs to be identified in high As groundwaters. Groundwater samples were filtered in the field through a progressively decreasing pore size (0.45 μm, 100, 30, 10, 5 kDa) using a filtration technique under a N₂ atmosphere. Major and trace elements and organic C (OC) were measured in (ultra)filtrates. The studied groundwater samples have typical physio-chemical characteristics of the basin waters. Declines in concentrations of alkali (Na, K), alkaline-earth (Mg, Ca, Sr, Ba) elements, Mo, Si and Se during ultrafiltration are smaller relative to other elements. Arsenic, Cu, Cr, U and V are generally about 30% lower in 5 kDa ultrafiltrates in comparison with 0.45 μm filtrates. Around 50% of Fe, OC and Al are bound to colloids with grain size between 5 kDa and 0.45 μm. Two types of colloids, including large-size Fe colloids and small-size organic colloids, have been identified. Results indicate that As would be more likely to be associated with small-size organic colloids than Fe colloids. SEM images and EDS analysis and synchrotron XRF analyses confirm the association of As with NOM with molecular weights of 5-10 kDa. The better correlation between As(V) and OC in the 5-10 kDa fraction indicates that the small-size organic colloids have a greater affinity for As(V) than As(III). Arsenic associated with organic complexes may not be immobilized by adsorption, and, therefore, easily transported in the aquifer. Thus, the presence of As-containing colloidal complexes in high As groundwaters must be considered in the modeling of As transport in the aquifers.     

A review of the source,behaviour and distribution of arsenic in natural waters

The range of As concentrations found in natural waters is large, ranging from less than 0.5 μg l⁻¹ to more than 5000 μg l⁻¹. Typical concentrations in freshwater are less than 10 μg l⁻¹ and frequently less than 1 μg l⁻¹. Rarely, much higher concentrations are found, particularly in groundwater. In such areas, more than 10% of wells may be ‘affected’ (defined as those exceeding 50 μg l⁻¹) and in the worst cases, this figure may exceed 90%. Well-known high-As groundwater areas have been found in Argentina, Chile, Mexico, China and Hungary, and more recently in West Bengal (India), Bangladesh and Vietnam. The scale of the problem in terms of population exposed to high As concentrations is greatest in the Bengal Basin with more than 40 million people drinking water containing ‘excessive’ As. These large-scale ‘natural’ As groundwater problem areas tend to be found in two types of environment: firstly, inland or closed basins in arid or semi-arid areas, and secondly, strongly reducing aquifers often derived from alluvium. Both environments tend to contain geologically young sediments and to be in flat, low-lying areas where groundwater flow is sluggish. Historically, these are poorly flushed aquifers and any As released from the sediments following burial has been able to accumulate in the groundwater. Arsenic-rich groundwaters are also found in geothermal areas and, on a more localised scale, in areas of mining activity and where oxidation of sulphide minerals has occurred. The As content of the aquifer materials in major problem aquifers does not appear to be exceptionally high, being normally in the range 1–20 mg kg⁻¹. There appear to be two distinct ‘triggers’ that can lead to the release of As on a large scale. The first is the development of high pH (>8.5) conditions in semi-arid or arid environments usually as a result of the combined effects of mineral weathering and high evaporation rates. This pH change leads either to the desorption of adsorbed As (especially As(V) species) and a range of other anion-forming elements (V, B, F, Mo, Se and U) from mineral oxides, especially Fe oxides, or it prevents them from being adsorbed. The second trigger is the development of strongly reducing conditions at near-neutral pH values, leading to the desorption of As from mineral oxides and to the reductive dissolution of Fe and Mn oxides, also leading to As release. Iron (II) and As(III) are relatively abundant in these groundwaters and SO₄ concentrations are small (typically 1 mg l⁻¹ or less). Large concentrations of phosphate, bicarbonate, silicate and possibly organic matter can enhance the desorption of As because of competition for adsorption sites. A characteristic feature of high groundwater As areas is the large degree of spatial variability in As concentrations in the groundwaters. This means that it may be difficult, or impossible, to predict reliably the likely concentration of As in a particular well from the results of neighbouring wells and means that there is little alternative but to analyse each well. Arsenic-affected aquifers are restricted to certain environments and appear to be the exception rather than the rule. In most aquifers, the majority of wells are likely to be unaffected, even when, for example, they contain high concentrations of dissolved Fe.     

Ge/Si and Sr/Sr tracers of weathering reactions and hydrologic pathways in a tropical granitoid system

Ge/Si and ⁸⁷Sr/⁸⁶Sr data from primary and secondary minerals, soil waters, and stream waters in a tropical granitoid catchment quantitatively reflect mineral alteration reactions that occur at different levels within the bedrock–saprolite–soil zone. Near the bedrock–saprolite interface, plagioclase to kaolinite reaction yields low Ge/Si and 87Sr/86Sr. Higher in the regolith column, biotite weathering and kaolinite dissolution drive Ge/Si and 87Sr/86Sr to high values. Data from streams at base flow sample the bedrock–saprolite interface zone, while at high discharge solutes are derived from upper saprolite–soil zone. Coupled Ge/Si and 87Sr/86Sr can be effective tools for quantifying the importance of specific weathering reactions, and for geochemical hydrograph separation.     

An assessment of the origin and variation of groundwater salinity in southeastern Ghana

Groundwater from the major aquifers in southeastern part of Ghana was sampled to determine the main controls on groundwater salinity in the area. This paper uses multivariate statistical methods, conventional graphical methods and stable isotope data to determine spatial relationships among groundwaters from the different hydrogeologic units in the area on the basis of salinity. Q-mode hierarchical cluster analysis (HCA) was used to spatially classify the samples, whilst R-mode factor analysis was used to reduce the dataset into two major principal components representing the sources of variation in the hydrochemistry. Analysis of the major chemical parameters suggests that the principal component responsible for salinity increment in the area is the weathering of minerals in the aquifers. This factor is especially more significant in the upland areas away from the coast. The second factor responsible for salinity in the area is the combined effects of seawater intrusion, and anthropogenic activities. This study finds that four major spatial groundwater groups exist in the area: low salinity, acidic groundwaters which are mainly derived from the Birimian and Togo Series aquifers; low salinity, moderate to neutral pH groundwaters which are mainly from the Voltaian, Buem and Cape Coast granitoids; very high salinity waters which are not suitable for most domestic and irrigation purposes and are mainly from the Keta aquifers; and intermediate salinity groundwaters comprising groundwater from the Keta basin aquifers with minor contributions from the other major terrains. The major water type identified in this study is the Ca–Mg–HCO₃ type, which degrades into predominantly Na–Cl–SO₄ more saline groundwaters toward the coast. Stable isotope data analyses suggest that groundwater in the Voltaian aquifers is largely of recent meteoric origin. The Birimian and Togo aquifers receive a component of recharge from the tributaries of the Densu and Volta Rivers, after the waters have undergone evaporative enrichment of the heavier isotopes. In the Keta basin, recharge is mainly from precipitation but an observed enrichment of ²H and ¹⁸O isotopes is probably due to seawater and evaporative effects since the water table there is very shallow. An analysis of the irrigation quality of groundwater from the six aquifers in the study area using sodium adsorption ratio and electrical conductivity suggests that most of the aquifers supply groundwater of acceptable quality for irrigation. The only exception is the Keta Basin area, where extremely high salinities and SAR values render groundwater from this basin unsuitable for irrigation purposes.     

Controls on the spatial and temporal variability of vadose dripwater geochemistry: Edwards aquifer, central Texas

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.     

Acidification processes and soil leaching influenced by agricultural practices revealed by strontium isotopic ratios

In natural river systems, the chemical and isotopic composition of stream- and ground waters are mainly controlled by the geology and water-rock interactions. The leaching of major cations from soils has been recognized as a possible consequence of acidic deposition from atmosphere for over 30 years. Moreover, in agricultural areas, the application of physiological acid fertilizers and nitrogen fertilizers in the ammonia form may enhance the cation leaching through the soil profile into ground- and surface waters. This origin of leached cations has been studied on two small and adjacent agricultural catchments in Brittany, western France. The study catchments are drained by two first-order streams, and mainly covered with cambisoils, issued from the alteration and weathering of a granodiorite basement. Precipitations, soil water- and NH₄ acetate-leachates, separated minerals, and stream waters have been investigated. Chemical element ratios, such as Ba/Sr, Na/Sr and Ca/Sr ratios, as well as Sr isotopic ratios are used to constrain the relative contribution from potential sources of stream water elements.Based on Sr isotopic ratio and element concentration, soil water- and NH₄ acetate leaching indicates (1) a dominant manure/slurry contribution in the top soil, representing a cation concentrated pool, with low ⁸⁷Sr/⁸⁶Sr ratios; (2) in subsoils, mineral dissolution is enhanced by fertilizer application, becoming the unique source of cations in the saprolite. The relatively high weathering rates encountered implies significant sources of cations which are not accessory minerals, but rather plagioclase and biotite dissolution.Stream water has a very different isotopic and chemical composition compared to soil water leaching suggesting that stream water chemistry is dominated by elements issued from mineral and rock weathering. Agriculture, by applications of chemical and organic fertilizers, can influence the export of major base cations, such as Na⁺. Plagioclase dissolution, rather than anthropogenically controlled soil water, seems to be the dominant source of Na⁺ in streams. However, Ca²⁺ in streams is mostly derived from slurries and manures deposited on top soils, and transferred into the soil ion-exchange pool and stream waters. Less than 10% of Na⁺, 5-40% of Sr²⁺ and 20-100% of Ca²⁺ found in streams can be directly derived from the application of organic fertilizers.     

Partition of arsenic in soils sediments and the origin of naturally elevated concentrations in groundwater of the southern pampa region (Argentina)

Excessive arsenic concentrations above the Argentinean and WHO guidelines for drinking water (10 μg L⁻¹) affects shallow aquifers of the southern Pampean Plain (Argentina) hosted in the Pampean and the Post Pampean formations (loess and reworked loess; Plio-Pleistocene–Holocene). Health problems related to high As concentrations in drinking waters are known as Endemic Regional Chronic Hydroarsenicism. Hydrochemistry of shallow groundwaters and soil geochemistry were investigated aiming to (1) understand the partition of As in the solid phase and its relationship with unacceptable As concentrations in waters, (2) identify the provision source of As to groundwaters. Only 5% of the samples had As concentrations <10 μg L⁻¹; in 27% As concentrations ranged from 10 to 50 μg L⁻¹ and in 58% it reached 60–500 μg L⁻¹. The coarse fraction (50–2,000 μm) hosts about 27% of the total As in the solid phase, being positively correlated to Ba (p < 0.01; r ² = 0.93). About 70% is included in the <2 μm fraction and had positive correlations of As–Fe (p < 0.05; r ² = 0.85) and As–Cr (p < 0.05; r ² = 0.68). Soils and sediment sand fractions of vadose zones are the primary sources of As in shallow groundwater while adsorption–desorption processes, codisolution–coprecipitation, and evaporation during the dry seasons raise As concentrations in waters exceeding the guideline value for drinking water.     

Hydrogeochemical investigation of surface and groundwater composition in an irrigated land in Central Tunisia

Major element concentrations, stable (δ¹⁸O and δ²H) and radiogenic (³H, ¹⁴C) isotopes determined in groundwater provided useful initial tracers for understanding the processes that control groundwater mineralization and identifying recharge sources in semi-arid Cherichira basin (central Tunisia).Chemical data based on the chemistry of several major ions has revealed that the main sources of salinity in the groundwaters are related to the water–rock interaction such as the dissolution of evaporitic and carbonate minerals and some reactions with silicate and feldspar minerals.The stable isotope compositions provide evidence that groundwaters are derived from recent recharge. The δ¹⁸O and δ²H relationships implied rapid infiltration during recharge to both the Oligocene and Quaternary aquifers, with only limited evaporation occurring in the Quaternary aquifer.Chemical and isotopic signatures of the reservoir waters show large seasonal evolution and differ clearly from those of groundwaters.Tritium data support the existence of recent recharge in Quaternary groundwaters. But, the low tritium values in Oligocene groundwaters are justified by the existence of clay lenses which limit the infiltration of meteoric water in the unsaturated zone and prolong the groundwater residence time.Carbon-14 activities confirm that groundwaters are recharged from the surface runoff coming from precipitation.     

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.     

Mobility of arsenic in a Bangladesh aquifer: Inferences from geochemical profiles, leaching data, and mineralogical characterization

Aquifer geochemistry was characterized at a field site in the Munshiganj district of Bangladesh where the groundwater is severely contaminated by As. Vertical profiles of aqueous and solid phase parameters were measured in a sandy deep aquifer (depth >150 m) below a thick confining clay (119 to 150 m), a sandy upper aquifer (3.5 to 119 m) above this confining layer, and a surficial clay layer (<3.5 m). In the deep aquifer and near the top of the upper aquifer, aqueous As levels are low (<10 μg/L), but aqueous As approaches a maximum of 640 μg/L at a depth of 30 to 40 m and falls to 58 μg/L near the base (107 m) of the upper aquifer. In contrast, solid phase As concentrations are uniformly low, rarely exceeding 2 μg/g in the two sandy aquifers and never exceeding 10 μg/g in the clay layers. Solid phase As is also similarly distributed among a variety of reservoirs in the deep and upper aquifer, including adsorbed As, As coprecipitated in solids leachable by mild acids and reductants, and As incorporated in silicates and other more recalcitrant phases. One notable difference among depths is that sorbed As loads, considered with respect to solid phase Fe extractable with 1 N HCl, 0.2 M oxalic acid, and a 0.5 M Ti(III)-citrate-EDTA solution, appear to be at capacity at depths where aqueous As is highest; this suggests that sorption limitations may, in part, explain the aqueous As depth profile at this site. Competition for sorption sites by silicate, phosphate, and carbonate oxyanions appear to sustain elevated aqueous As levels in the upper aquifer. Furthermore, geochemical profiles are consistent with the hypothesis that past or ongoing reductive dissolution of Fe(III) oxyhydroxides acts synergistically with competitive sorption to maintain elevated dissolved As levels in the upper aquifer. Microprobe data indicate substantial spatial comapping between As and Fe in both the upper and deep aquifer sediments, and microscopic observations reveal ubiquitous Fe coatings on most solid phases, including quartz, feldspars, and aluminosilicates. Extraction results and XRD analysis of density/magnetic separates suggest that these coatings may comprise predominantly Fe(II) and mixed valence Fe solids, although the presence of Fe(III) oxyhydroxides can not be ruled out. These data suggest As release may continue to be linked to dissolution processes targeting Fe, or Fe-rich, phases in these aquifers.     

Heavy metal migration at a landfill site, Sarnia, Ontario, Canada—2: metal partitioning and geotechnical implications

Heavy metal profiles below a 15-year old sanitary landfill overlying a 30 m thick natural clay deposit are presented. Results indicate that unlike soluble species such as Cl⁻ and Na⁺ which have migrated distances up to 130 cm, Cu, Zn and Pb have migrated only up to 10 cm. The extent of Fe migration is estimated to be 20 cm. Highly reducing conditions at the interface (E_h= −130mV), coupled with the alkaline nature of the clay pore waters, have resulted in the precipitation of migrated heavy metals as carbonates. At the clay/waste interface, 88, 84 and 80% of the excess Fe, Zn and Pb, respectively, are present as secondary carbonates. This is confirmed by selective chemical dissolution analyses which also show that Fe, Zn, Pb and, to a greater extent, Cu are present in solid organic forms at the interface. Batch equilibrium studies clearly show that Cu and Pb removal from leachate is significantly increased by the presence of carbonates in the soil. For example, 75% more Pb is removed by the carbonate-rich bulk soil than the carbonate-free soil. The batch studies also show that when thepH> 5.2, removal of metal increases significantly due to precipitation as carbonates. From the results it is concluded that the presence of metal sludges in landfills lined naturally or artifically by a carbonate-rich clayey barrier reduces the rate of migration of numerous toxic transition metals and may also decrease the barrier porosity by precipitation. The decreases in porosity will be beneficial to the performance of the barrier due to reductions in both advection and diffusion.     

Impact of anthropogenic geochemical change and aquifer geology on groundwater phosphorus concentrations

Geologic and geochemical variations across a 4200 km² area of south-central Wisconsin (USA) were used to examine their relationship to phosphorus concentrations in groundwater from more than four hundred private water supply wells. Surficial geology in the study area ranged from Cambrian sandstones to Ordovician dolomites. Groundwater phosphorus concentrations were higher in aquifers of older Cambrian age compared to the concentrations in aquifers of younger Cambrian and Ordovician age. Because iron concentrations were relatively low in these waters and agricultural land use was similar in all geologic regions, we propose that the differences in bedrock phosphorus and anthropogenic geochemical impacts explain the differences in phosphorus concentrations between aquifers. Within the older Cambrian aquifers, groundwater phosphorus concentrations were elevated in groundwater with higher nitrate-nitrogen concentrations. This finding is consistent with the presence of phosphorus within sediment in these strata and geologic conditions that weakly buffered pH reduction from anthropogenic acidification. In contrast, groundwater phosphorus concentrations in younger Cambrian and Ordovician aquifers were not elevated in samples with higher nitrate. Anthropogenic acidification in these carbonate-rich aquifers was neutralized through increased carbonate weathering, which led to higher groundwater calcium and alkalinity and would limit the dissolution of phosphate-rich minerals, such as apatite, where present. Low iron concentrations observed in most samples suggest that the phosphorus release in the Cambrian strata occurs beyond the zone of secondary mineral retention in the soil. These results have important implications for the eutrophication of inland surface waters in areas with bedrock phosphorus and anthropogenic acidity that is not neutralized before it contacts phosphatic rock.