Assessing the solubility controls on vanadium in groundwater,northeastern San Joaquin Valley,CA

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 μg/L to 70 μg/L with a median of 21 μg/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 μg/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 μg/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H₂VO₄⁻. Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V⁵⁺ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH)₃⁺]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH)₃ molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V³⁺- or mixed V³⁺/Fe³⁺-oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions.Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO₃) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO₃ extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.     

Groundwater chemistry and occurrence of arsenic in the Meghna floodplain aquifer,southeastern Bangladesh

Dissolved major ions and important heavy metals including total arsenic and iron were measured in groundwater from shallow (25–33 m) and deep (191–318 m) tube-wells in southeastern Bangladesh. These analyses are intended to help describe geochemical processes active in the aquifers and the source and release mechanism of arsenic in sediments for the Meghna Floodplain aquifer. The elevated Cl⁻ and higher proportions of Na⁺ relative to Ca²⁺, Mg²⁺, and K⁺ in groundwater suggest the influence by a source of Na⁺ and Cl⁻. Use of chemical fertilizers may cause higher concentrations of NH₄⁺ and PO₄³⁻ in shallow well samples. In general, most ions are positively correlated with Cl⁻, with Na⁺ showing an especially strong correlation with Cl⁻, indicating that these ions are derived from the same source of saline waters. The relationship between Cl⁻/HCO₃⁻ ratios and Cl⁻ also shows mixing of fresh groundwater and seawater. Concentrations of dissolved HCO₃⁻ reflect the degree of water–rock interaction in groundwater systems and integrated microbial degradation of organic matter. Mn and Fe-oxyhydroxides are prominent in the clayey subsurface sediment and well known to be strong adsorbents of heavy metals including arsenic. All five shallow well samples had high arsenic concentration that exceeded WHO recommended limit for drinking water. Very low concentrations of SO₄²⁻ and NO₃⁻ and high concentrations of dissolved Fe and PO₄³⁻ and NH₄⁺ ions support the reducing condition of subsurface aquifer. Arsenic concentrations demonstrate negative co-relation with the concentrations of SO₄²⁻ and NO₃⁻ but correlate weakly with Mo, Fe concentrations and positively with those of P, PO₄³⁻ and NH₄⁺ ions.     

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.     

Desalination of a sedimentary rock aquifer system invaded by Pleistocene Champlain Sea water and processes controlling groundwater geochemistry

The objective of this study was to identify geochemical processes and Quaternary geological events responsible for the variations in groundwater geochemistry observed in a sedimentary rock aquifer system, including brackish to saline groundwater. Inorganic constituents and environmental isotopes were analyzed for 146 groundwater samples. Dissolution of carbonates dominates in recharge areas, resulting in Ca-, Mg-HCO₃ groundwater. Further along flow paths, under confined conditions, Ca²⁺–Na⁺ ion exchange causes groundwater evolution to Na-HCO₃ type. Na-Cl groundwater is also found and it falls on a seawater mixing line. Using conservative tracers, Cl⁻ and Br⁻, the original Champlain Sea water is shown to have been, in the region, a mixture of about 34% seawater and 66% freshwater, a composition still retained by some groundwater. Na-Cl groundwater thus results from mixing with former Champlain Sea water and also from solute diffusion from overlying marine clay. The system is thus found to be at different stages of desalinization, from the original Champlain Sea water still present in hydraulically stagnant areas of the aquifer to fully flushed conditions in parts, where more flow occurs, especially in recharge zones. The geochemical processes are integrated within the hydrogeological context to produce a conceptual geochemical evolution model for groundwater of the aquifer system.     

In situ push-pull tests for the determination of TCE degradation and permanganate consumption rates

A simple, single-well push-pull test was conducted at a TCE-contaminated site to estimate the site-specific TCE degradation and permanganate (MnO₄⁻) consumption rate. Known quantities of a conservative tracer (Br⁻) and permanganate were rapidly injected into a saturated aquifer then periodically sampled during extraction from the same well. Concentrations of Br⁻, TCE, and MnO₄⁻ were measured; breakthrough curves (BTCs) for all species of solute were determined. Data analysis of BTCs for bromide and TCE showed that the first-order rate constant of TCE degradation by MnO₄⁻ is 1.67 ± 0.152 h⁻¹. Further, the in situ MnO₄⁻ demand rate by TCE and aquifer materials is estimated to be 0.54 ± 0.371 h⁻¹. This study demonstrates that in situ push-pull tests are useful and economical tools for field investigations to determine contaminant reaction and oxidant consumption rates, which may then be used to optimize groundwater remediation designs.     

Environmental geochemistry of high arsenic groundwater at western Hetao plain, Inner Mongolia

Environmental geochemistry of high arsenic groundwater at Hetao plain was studied on the basis of geochemical survey of the groundwater and a core sediment. Arsenic concentration in groundwater samples varies from 76 to 1093 μg/L. The high arsenic groundwater mostly appears to be weakly alkaline. The concentrations of NO₃⁻ and SO₄²⁻ are relatively low, while the concentrations of DOC, NH₄⁺, dissolved Fe and sulfide are relatively great. Analysis of arsenic speciation in 21 samples shows that arsenic is present in the solution predominantly as As(III), while particulate arsenic constitutes about 10% of the total arsenic. Methane is detected in five samples with the greatest content being 5107 μg/L. The shallow aquifer in Hangjinhouqi of western Hetao plain is of strongly reducing condition. The arsenic content in 23 core sediment samples varies from 7.7 to 34.6 mg/kg, with great value in clay and mild clay layer. The obvious positive relationship in content between Fe₂O₃, Mn, Sb, B, V and As indicates that the distribution of arsenic in the sediments may be related to Fe and Mn oxides, and the mobilization of Sb, B and V may be affected by similar geochemical processes as that of As.     

A Geochemical study of the groundwater in the Misli basin and environmental implications

The aim of this study was to determine geochemical properties of groundwater and thermal water in the Misli Basin and to assess thermal water intrusion into shallow groundwater due to over-extraction. According to isotope and hydrochemical analyses results, sampled waters can be divided into three groups: cold, thermal, and mixed waters. Only a few waters reach water–rock chemical equilibrium. Thermal waters in the area are characterized by Na⁺–Cl⁻–HCO₃⁻, while the cold waters by CaHCO₃ facies. On the basis of isotope results, thermal waters in the Misli basin are meteoric origin. In particular, δ¹⁸O and δ²H values of shallow groundwater vary from −10.2 to −12.2‰ and −71.2 to −82‰, while those of thermal waters range from −7.8 to −10.1‰ and from −67 to −74‰, respectively. The tritium values of shallow groundwater having short circulation as young waters coming from wells that range from 30 to 70 m in depth vary from 10 to 14 TU. The average tritium activity of groundwater in depths more than 100 m is 1.59 ± 1.16, which indicates long circulation. The rapid infiltration of the precipitation, the recycling of the evaporated irrigation water, the influence of thermal fluids and the heterogeneity of the aquifer make it difficult to determine groundwater quality changes in the Misli Basin. Obtained results show that further lowering of the groundwater table by over-consumption will cause further intrusion of thermal water which resulted in high mineral content into the fresh groundwater aquifer. Because of this phenomenon, the concentrations of some chemical components which impairs water quality in terms of irrigation purposes in shallow groundwaters, such as Na⁺, B, and Cl⁻, are highy probably expected to increase in time.     

Processes affecting geochemistry and contaminant movement in the middle Claiborne aquifer of the Mississippi embayment aquifer system

Groundwater chemistry and tracer-based age data were used to assess contaminant movement and geochemical processes in the middle Claiborne aquifer (MCA) of the Mississippi embayment aquifer system. Water samples were collected from 30 drinking-water wells (mostly domestic and public supply) and analyzed for nutrients, major ions, pesticides, volatile organic compounds (VOCs), and transient age tracers (chlorofluorocarbons, tritium and helium-3, and sulfur hexafluoride). Redox conditions are highly variable throughout the MCA. However, mostly oxic groundwater with low dissolved solids is more vulnerable to nitrate contamination in the outcrop areas east of the Mississippi River in Mississippi and west Tennessee than in mostly anoxic groundwater in downgradient areas in western parts of the study area. Groundwater in the outcrop area was relatively young (apparent age of less than 40 years) with significantly (p < 0.05) higher dissolved oxygen and nitrate–N concentrations and higher detections of pesticides and VOCs compared to water samples from wells in downgradient areas. Oxygen reduction and denitrification rates were low compared to other aquifers in the United States (zero order rate constants for oxygen reduction and denitrification were 4.7 and 5–10 μmol/L/year, respectively). Elevated concentrations of nitrate–N, and detections of pesticides and VOCs in some deep public supply wells (>50 m depth) indicated contaminant movement from shallow parts of the aquifer into deeper oxic zones. Given the persistence of nitrate in young oxic groundwater that was recharged several decades ago, and the lack of a confining unit, the downward movement of young contaminated water may result in higher nitrate concentrations over time in deeper parts of the aquifer containing older oxic water.     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.The online version of the original article can be found at     

Nitrogen Sources and Rates of Phytoplankton Uptake in Different Regions of Hong Kong Waters in Summer

Phytoplankton uptake rates of ammonium (NH₄ ⁺), nitrate (NO₃ ⁻), and urea were measured at various depths (light levels) in Hong Kong waters during the summer of 2008 using ¹⁵N tracer techniques in order to determine which form of nitrogen (N) supported algal growth. Four regions were sampled, two differentially impacted by Pearl River discharge, one impacted by Hong Kong sewage discharge, and a site beyond these influences. Spatial differences in nutrient concentrations, ratios, and phytoplankton biomass were large. Dissolved nutrient ratios suggested phosphorus (P) limitation throughout the region, largely driven by high N loading from the Pearl River in summer. NH₄ ⁺ and urea made up generally ≥50% of the total N taken up and the f ratio averaged 0.26. Even at the river-impacted site where concentrations of NO₃ ⁻ were >20 μM N, NH₄ ⁺ comprised >60% of the total N uptake. Inhibition experiments demonstrated that NO₃ ⁻ uptake rates were reduced by 40% when NH₄ ⁺ was >5 μM N. The relationship between the total specific uptake rates of N (sum of all measured substrates, V, per hour) and the chlorophyll a-specific rates (micromolars of N per microgram of Chl a per hour) varied spatially with phytoplankton biomass. Highest uptake rates and biomass were observed in southern waters, suggesting that P limitation and other factors (i.e., flushing rate) controlled production inshore and that the unincorporated N (mainly NO₃ ⁻) was transported offshore. These results suggest that, at the beginning of summer, inshore algal blooms are fueled primarily by NH₄ ⁺ and urea, rather than NO₃ ⁻, from the Pearl River discharge. When NH₄ ⁺ and urea are depleted, then NO₃ ⁻ is taken up and can increase the magnitude of the bloom.     

Spatio-temporal characterization of the Pliocene aquifer conditions in Wadi El-Natrun area,Egypt

Wadi El-Natrun area has recently undergone extensive urban and agricultural expansion. Due to the absence of natural surface irrigation supplies, the only source of water in the area is the Pliocene groundwater aquifer. As a result, secondary salinization from increased abstractions is the major threat to the groundwater aquifer. There is a dire need for efficient strategies to ensure long-term sustainability of the area’s productive agriculture. These strategies should be based on scientific spatio-temporal monitoring and analysis of the groundwater conditions that is also lacking. To capture the spatio-temporal variability in groundwater conditions, field measurements of total dissolved solids, electrical conductivity, pH, temperature, and water level as well as lab-based ionic composition were performed on 47 groundwater samples collected during 2006 and 2007. Determinations of the hydrochemical characteristics, water types, salt assemblages, and the sodium adsorption ratio were carried out on the samples. Reference data sets recorded in 1973 and 1997 were available for the area and were used to monitor the changes occurred in these periods. Geographic information system (GIS) was appraised for mapping and for integrated analysis of the different layers. Remotely sensed change detection techniques were applied to the Landsat TM and the ETM + imageries and used to highlight the extensive reclamation and urbanization and to find key trends for the alterations in the groundwater conditions and their spatial association with land covers. Results revealed a topographic depression-induced flow pattern, predominance of leaching and dissolution processes, the presence of saline lakes, over-pumping from the Pliocene aquifer, and temporal changes in land uses are the main factors combined to control the spatio-temporal variability in the groundwater. Results also clarified the presence of two: northwestern and southeastern zones that varied distinctively in their hydrodynamic and hydrochemical characteristics. The northwestern zone showed an average water level decline of 15 m, the water of which is brackish (av. 2,037 mg/l) with dominant Na⁺, Cl⁻ and SO₄ ²⁻ ions. The groundwater of this zone is characterized by high to very high salinity hazard and high to very high alkali hazard and is not recommended for irrigation on soils with poor drainage and without proper management for salinity control. The southeastern zone showed water level decline less than 2 m, the water of which is fresh (av. 424 mg/l) with major Na⁺, HCO₃ ⁻, Cl⁻, and SO₄ ²⁻ ions, and quality suitable for irrigation with medium to high salinity and low to medium alkali hazards. The article represents the first step towards an integrated management of Wadi El-Natrun groundwater resources within a GIS framework.     

Relations of hydrogeologic factors, groundwater reduction-oxidation conditions, and temporal and spatial distributions of nitrate, Central-Eastside San Joaquin Valley, California, USA

In a 2,700-km² area in the eastern San Joaquin Valley, California (USA), data from multiple sources were used to determine interrelations among hydrogeologic factors, reduction-oxidation (redox) conditions, and temporal and spatial distributions of nitrate (NO₃), a widely detected groundwater contaminant. Groundwater is predominantly modern, or mixtures of modern water, with detectable NO₃ and oxic redox conditions, but some zones have anoxic or mixed redox conditions. Anoxic conditions were associated with long residence times that occurred near the valley trough and in areas of historical groundwater discharge with shallow depth to water. Anoxic conditions also were associated with interactions of shallow, modern groundwater with soils. NO₃ concentrations were significantly lower in anoxic than oxic or mixed redox groundwater, primarily because residence times of anoxic waters exceed the duration of increased pumping and fertilizer use associated with modern agriculture. Effects of redox reactions on NO₃ concentrations were relatively minor. Dissolved N₂ gas data indicated that denitrification has eliminated >5 mg/L NO₃–N in about 10% of 39 wells. Increasing NO₃ concentrations over time were slightly less prevalent in anoxic than oxic or mixed redox groundwater. Spatial and temporal trends of NO₃ are primarily controlled by water and NO₃ fluxes of modern land use.     

Groundwater contamination with arsenic in Sherajdikhan,Bangladesh: geochemical and hydrological implications

An integrated study has been carried out to elucidate the distribution and occurrence of arsenic in selected groundwater samples in the area of Sherajdikhan, Bangladesh. Arsenic and other parameters (T, pH, EC, Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, NO₃ ⁻, SO₄ ²⁻, HCO₃ ⁻, PO₄ ³⁻, Fe, Mn and DOC) have been measured in groundwater samples collected from shallow/deep tube wells at different depths. Hydrogeochemical data suggest that the groundwaters are generally Ca–Mg–HCO₃ and Mg–Ca–HCO₃ types with bicarbonate (HCO₃ ⁻) as the dominant anion, though the other type of water has also been observed. Dissolved arsenic in groundwater ranged from 0.006 to 0.461 mg/l, with 69% groundwater samples exceeded the Bangladesh limit for safe drinking water (0.05 mg/l). Correlation and principal component analysis have been performed to find out possible relationships among the examined parameters in groundwater. Low concentrations of NO₃ ⁻ and SO₄ ²⁻, and high concentrations of DOC, HCO₃ ⁻ and PO₄ ³⁻ indicate the reducing condition of subsurface aquifer where sediments are deposited with abundant organic matter. Distinct relationship of As with Fe and Mn, and strong correlation with DOC suggests that the biodegradation of organic matter along with reductive dissolution of Fe–Mn oxyhydroxides has being considered the dominant process to release As in the aquifers studied herein.     

Benthic biogeochemistry beneath the Mississippi River plume

Biogeochemical processes occurring near the sediment-water interface of shallow (≈20 m) water sediments lying beneath the Mississippi River plume on the Louisiana shelf were studied using benthic chambers and sediment cores. Three sites were chosen with distinctly different characteristics. One was overlain by oxic water where aerobic respiration dominated organic matter remineralization. The second site was overlain by oxic water but organic matter remineralization was dominated by sulfate reduction. The third site was overlain by hypoxic water and aerobic remineralization was of minor significance. Major differences were observed in the fluxes of CO₂(17–56 mmol m⁻² d⁻¹), O₂(2–56 mmol m⁻² d⁻¹) and nutrients (e.g., NH₄ ⁺, 2.6–4.2 mmol m⁻² d⁻¹) across the sediment-water interface, and the relative importance of different electron acceptors, even though the sites were in close proximity and at nearly the same water depth. Large variations in the efficiency of organic-C burial (3%–51%) were also calculated based on a simplified model of the relationships between the fraction of organic matter remineralized by sulfate reduction and the fraction of sulfide produced that is buried as pyrite. These observations demonstrate the high degree of spatial heterogeneity of benthic biogeochemistry in this important near-deltaic environment.     

Importance of submarine groundwater discharge as a source of nutrients for the Neuse River Estuary,North Carolina

Seepage rate and chemical composition of groundwater discharge entering the Neuse River Estuary (NRE) were quantified over an annual cycle from July 2005 through June 2006. Lee type seepage meters were deployed at eight locations within the NRE to quantify the amount of submerged groundwater discharge (SGD) entering the system. Sediment porewater nitrate (NO₃ ⁻), ammonium (NH₄ ⁺), and phosphate (PO₄ ⁻³) were also quantified at each of these locations to determine groundwater chemical composition. Seepage rates for the system ranged from 0.004 to 0.035 m³ m⁻² d⁻¹. Both the average and median value for the system-wide SGD were 0.01 m³ m⁻²d⁻¹. There were no significant differences between upstream and downstream seepage rates or between those at the north and south side of the estuary. Seepage rates varied greatly in time and space. Discharging groundwater was NO₃ ⁻ deplete but highly enriched in NH₄ ⁺. Porewater PO₄ ⁻³ levels varied but were usually present below Redfield values due to NH₄ ⁺ enrichment. SGD nutrient loading represented a small part of watershed nitrogen and phosphorus loading, 0.8% and 1.0%, respectively.     

Geochemistry characterization of groundwater in an agricultural area of Razan,Hamadan, Iran

This study was conducted to evaluate factors regulating groundwater quality in an area with agriculture as main use. Thirty groundwater samples have been collected from Razan area (Hamadan, Iran) for hydrochemical investigations to understand the sources of dissolved ions and assess the chemical quality of the groundwater. The chemical compositions of the groundwater are dominated by Na⁺, Ca²⁺, HCO₃ ⁻, Cl⁻ and SO₄ ²⁻, which have been derived largely from natural chemical weathering of carbonate, gypsum and anthropogenic activities of fertilizer’s source. The production of SO₄ ²⁻ has multiple origins, mainly from dissolution of sulphate minerals, oxidation of sulphide minerals and anthropogenic sources. The major anthropogenic components in the groundwater include Na⁺, Cl⁻, SO₄ ²⁻ and NO₃ ⁻, with Cl⁻ and NO₃ ⁻ being the main contributors to groundwater pollution in Razan area.     

Geologic framework and isotope tracing of the arsenious Quaternary Aquifer of the southwestern North Bengal Plain,West Bengal,India

The aim of the paper is to understand the geological control of groundwater, the recharge sources, the relative age of groundwater and the interaction between surface water and groundwater of the southwestern part of North Bengal Plain in the alluvium filled gap between the Rajmahal hills on the west and the Garo hills on the east. The area is covered by Quaternary alluvia of two different ages, viz. the Older Alluvium and the Newer Alluvium. The Older Alluvium of Pleistocene age is made up of argillaceous bed reddish brown in color and interspread with ‘kankar’ and laterite debris and the Newer Alluvium is dark, loosely compacted and has a high moisture content. A hydrostarigraphic model of the top 120 m geological column has been built by direct field observation, constructing Fence diagram, lithofacies and isotope analyses. The model indicates an oscillating environment of deposition of sediments from bottom to top with oxidizing at the bottom followed by reducing and then oxidizing environment at the top. The hydrogeochemistry of groundwater also suggests a predominantly reducing condition of the aquifer with high HCO₃ ⁻, low SO₄ ²⁻ and NO₃ ⁻ concentrations. The shallow groundwater at places contains heavy metals such as copper, cadmium, manganese, iron, chromium and arsenic. The δ¹⁸O and tritium values of groundwater are within the range of monsoon precipitation composition which indicates that groundwater is probably recharged primarily from precipitation. The plots of δ¹⁸O and δD show slight deviation from the Local Mean Water Lines suggesting that some evaporation of rainfall occurs prior to or during infiltration. Therefore groundwater occurs under unconfined condition. Lithofacies analysis indicates that the sediments below the depth of 40 m are the potential water bearing formation. Depletion or enrichment of δ¹⁸O and δD with depth was not observed and tritium content is also similar at various depths indicating possibility of mixing of groundwater from various depths due to pumping which may lead to contamination of the deeper aquifer by heavy metals and arsenic.     

Biogeochemistry of Major Redox Elements and Mercury in a Tropical Reservoir Lake (Petit Saut,French Guiana)

The hydroelectric reservoir of Petit Saut, French Guiana, was created in 1994–1995 by flooding 350 km² of tropical forest. When sampled in 1999, the lake exhibited a permanent stratification separating the 3–5 m thick, oxygenated epilimnion from the anoxic hypolimnion. The rate of anaerobic organic carbon mineralization below the oxycline was on the order of 1 μmol C m⁻² s⁻¹ and did not show a pronounced difference between wet and dry seasons. Methanogenesis accounted for 76–83% of anaerobic carbon mineralization, with lesser contributions of sulfate reduction and dissimilatory iron reduction. Upward mixing of reduced inorganic solutes explained 90% of the water column O ₂ demand during the dry season, while most O ₂ consumption during the wet season was coupled to aerobic respiration of organic matter synthesized in the surface waters. Inorganic mercury species represented 10–40% of total dissolved mercury in the epilimnion, but were of relatively minor importance (≤10%) in the anoxic portion of the water column. Net production of soluble organic mercury compounds in the flooded soils and anoxic water column did not vary significantly between wet and dry seasons. Methylmercury accounted for about 15% of total dissolved mercury below the oxycline. Its estimated net production rate, 0.04 mg m⁻² yr⁻¹, is of the same order of magnitude as values reported for contaminated lakes and flooded terrestrial ecosystems.     

Hydrogeochemistry of the groundwater flow system in a crystalline terrain: a study from the Kurunegala district,Sri Lanka

Water samples collected from dug wells and tube wells from the Kurunegala District of Sri Lanka have been studied for their major hydrogeochemical parameters to understand the chemical quality of water in the terrain. The region is composed of Precambrian metamorphic rocks where groundwater is only available in the regolith and along weak structural discontinuities. The study of the major chemical constituents of groundwater revealed several relationships with the aquifer lithology. Groundwater from mafic rocks have high dissolved solids, while quartzose metaclastic rocks yield water with low dissolved solids. The study area displays very low SO₄ ²⁻ contents of the groundwater. The chloride content is higher in the dry regions and in terrains underlain by pink granite and marble/calc gneiss while areas with marble, as expected, show high concentrations of Ca and Mg ions. The waters in the region can be classified into non-dominant cations to Na + K dominant and Cl⁻ and HCO₃ ⁻ dominant types. Water from charnockite-bearing areas tends to have non-dominant cations and more CO₃ ²⁻ + HCO₃ ⁻ types. Effects such as soluble salts in the regolith, fracture intensity and climatic variations play a significant role in the behavior of the hydrogeochemistry in the area.     

Transient States in Diagenesis Following the Deposition of a Gravity Layer: Dynamics of O<Subscript>2</Subscript>, Mn,Fe and N-Species in Experimental Units

Biogeochemical processes induced by the deposition of gravity layer in marine sediment were studied in a 295-day experiment. Combining voltammetric microelectrode measurements and conventional analytical techniques, the concentrations of C, O₂, N-species, Mn and Fe have been determined in porewaters and sediments of experimental units. Dynamics of the major diagenetic species following the sudden sediment deposition of few cm-thick layer was explained by alternative diagenetic pathways whose relative importance in marine sediments is still a matter of debate. Time-series results indicated that the diffusion of O₂ from overlying waters to sediments was efficient after the deposition event: anoxic conditions prevailed during the sedimentation. After a few days, a permanent oxic horizon was formed in the top few millimetres. At the same time, the oxidation of Mn²⁺ and then Fe²⁺, which diffused from anoxic sediments, contributed to the surficial enrichment of fresh Mn(III/IV)- and Fe(III)-oxides. Vertical diffusive fluxes and mass balance calculations indicated that a steady-state model described the dynamic of Mn despite the transitory nature of the system. This model was not adequate to describe Fe dynamics because of the multiple sources and phases of Fe²⁺. No significant transfer of Mn and Fe was observed between the underlying sediment and the new deposit: Mn- and Fe-oxides buried at the original interface acted as an oxidative barrier to reduced species that diffused from below. Nitrification processes led to the formation of a NO₃⁻/NO₂⁻ rich horizon at the new oxic horizon. Over the experiment period, NO₃⁻ concentrations were also measured in the anoxic sediment suggesting anaerobic nitrate production.