Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

Hydrogeochemical behavior of arsenic-enriched groundwater in the deltaic environment: comparison between two study sites in West Bengal, India

Groundwaters have been collected from deltaic areas of West Bengal (Chakdaha and Baruipur blocks) to record their hydrogeochemical characteristics, and to verify the mechanism of arsenic (As) release. The data reveals that shallow (<70 m) groundwaters in both areas are of Ca-Mg-HCO(3) type; however deeper (>70 m) groundwaters in Baruipur areas are slightly enriched with Na, Cl and SO(4), indicating possible saline water intrusion. The groundwater is anoxic (mean Eh: -124 and -131 mV) with high levels of As (mean: 116 and 293 mug/L), Fe (mean: 4.74 and 3.83 mg/L), PO(4) (mean: 3.73 and 3.21 mg/L) and Mn (mean: 0.37 and 0.49 mg/L), respectively for Chakdaha and Baruipur areas. The observed values of As and bicarbonate (mean: 409 and 499 mg/L) in the shallow aquifer are indicative of redox processes (e.g., oxidation of organic matter) favouring the release of As. Moreover, the presence of DOC in the shallow aquifer suggests that organic matter is young and reactive, and may actively engage in redox driven processes. Our study further confirms that both Fe- and Mn-reduction processes are the dominant mechanisms for As release in these groundwaters.     

Hydrogeochemical comparison and effects of overlapping redox zones on groundwater arsenic near the Western (Bhagirathi sub-basin, India) and Eastern (Meghna sub-basin, Bangladesh) margins of the Bengal Basin

Although arsenic (As) contamination of groundwater in the Bengal Basin has received wide attention over the past decade, comparative studies of hydrogeochemistry in geologically different sub-basins within the basin have been lacking. Groundwater samples were collected from sub-basins in the western margin (River Bhagirathi sub-basin, Nadia, India; 90 samples) and eastern margin (River Meghna sub-basin; Brahmanbaria, Bangladesh; 35 samples) of the Bengal Basin. Groundwater in the western site (Nadia) has mostly Ca-HCO(3) water while that in the eastern site (Brahmanbaria) is much more variable consisting of at least six different facies. The two sites show differences in major and minor solute trends indicating varying pathways of hydrogeochemical evolution However, both sites have similar reducing, postoxic environments (p(e): +5 to -2) with high concentrations of dissolved organic carbon, indicating dominantly metal-reducing processes and similarity in As mobilization mechanism. The trends of various redox-sensitive solutes (e.g. As, CH(4), Fe, Mn, NO(3)(-), NH(4)(+), SO(4)(2-)) indicate overlapping redox zones, leading to partial redox equilibrium conditions where As, once liberated from source minerals, would tend to remain in solution because of the complex interplay among the electron acceptors.     

龙口市海水入侵动态系统分析与防治对策

海水入侵已成为全球普遍关注的地下水环境问题,它不仅严重地威胁着人类淡水资源,而且破坏生态环境平衡,制约着社会经济可持续发展。以山东省龙口市为靶区,通过分析研究衡量海水入侵重要因子－氯离子浓度时空分布规律及其影响因素,探索海水入侵动态系统规律,提出防治海水入侵的措施和对策。     

Arsenic in groundwater and sediment in the Mekong River delta, Vietnam

A study of groundwater and sediment during 2007-2008 in the Mekong River delta in Vietnam (MDVN) revealed that 26%, 74%, and 50% of groundwater samples were above the US EPA drinking water guidelines for As (10 μg/L), Mn (0.05 mg/L), and Fe (0.3 mg/L). The range of As, Fe, and Mn concentrations in the MDVN were <0.1-1351 μg/L, <0.01-38 mg/L, and <0.01−14 mg/L, respectively. Elevated levels of As were found in groundwater at sampling sites close to the Mekong River and in wells less than 60−70 m deep. An inverse relationship was found between As and Mn concentrations in groundwater. Sediment samples from An Giang and Dong Thap had the highest As concentrations (18 mg/kg and 38 mg/kg, respectively). Arsenic sediment occurred mainly in the poorly crystalline Fe oxide phases. Reductive dissolution of the Fe oxide phase is not necessarily the dominant mechanism of As release to groundwater.     

Dissolution of trace metals from lava ash: influence on the composition of rainwater in the Mount Etna volcanic area

Dissolution of trace metals from lava ash of the Mount Etna volcano in aqueous suspensions is studied as a function of solution pH and aerosol mass loading. The rate of dissolution and the final concentration increase with decreasing pH. Leaching experiments are found to be consistent with the observations of these metals in rainwater of the volcanic area. Elements such as Fe and Mn are important in the aqueous oxidation of SO(2) which increases the acidity of the rainwater. Leaching of Na, Ca, K, Fe and Mg may have a buffering effect in reacting with cloud and aerosol droplets.     

Source and release mechanism of arsenic in aquifers of the Mekong Delta, Vietnam

In order to elucidate the arsenic source and its release mechanism into groundwater in the Mekong Delta, Vietnam, groundwater samples were collected from wells at different depths (20 to 440 m) and core samples (from 20 to 265 m depth) were analyzed. Based on the analytical results for groundwater and core samples, the As source in groundwater is considered to be pyrite (FeS(2)) in acid sulfate soil (ASS) under oxidizing conditions and hydrous ferric oxide (Fe(OH)(3)) under reducing conditions. Geochemical modeling demonstrated that As(III) is the dominant species and the presence of As-bearing sulfides, Fe-bearing sulfides and oxides phases may locally act as potential sinks for As. From variation between Fe and As concentrations in groundwater samples, the release mechanism of As is: dissolution of Fe(OH)(3) containing As under reducing conditions and oxidative decomposition of FeS(2) containing As under oxidizing conditions.     

Geochemical modeling of arsenic release from a deep natural solid matrix under alternated redox conditions

Dissolved arsenic (As) concentrations detected in groundwater bodies of the Emilia-Romagna Region (Italy) exhibit values which are above the regulation limit and could be related to the natural composition of the host porous matrix. To support this hypothesis, we present the results of a geochemical modeling study reproducing the main trends of the dynamics of As, Fe, and Mn concentrations as well as redox potential and pH observed during batch tests performed under alternating redox conditions. The tests were performed on a natural matrix extracted from a deep aquifer located in the Emilia-Romagna Region (Italy). The solid phases implemented in the model were selected from the results of selective sequential extractions performed on the tested matrix. The calibrated model showed that large As concentrations have to be expected in the solution for low crystallinity phases subject to dissolution. The role of Mn oxides on As concentration dynamics appears significant in strongly reducing environments, particularly for large water–solid matrix interaction times. Modeled data evidenced that As is released firstly from the outer surface of Fe oxihydroxides minerals exhibiting large concentrations in water when persistent reducing conditions trigger the dissolution of the crystalline structure of the binding minerals. The presence of organic matter was found to strongly affect pH and redox conditions, thus influencing As mobility.

Effects of Mn(II) and Fe(II) on microbial removal of arsenic (III)

Goal, scope, and background  Arsenic contamination in groundwater creates severe health problems in the world. There are many physiochemical and biological methods available for remediation of arsenic from groundwater. Among them, microbial remediation could be taken as one of the least expensive methods, though it takes longer treatment time. The main objective of this research was to study the improvement on remediation by addition of some essential ion salts such as Mn and Fe. Materials and methods   Staphylococcus aureus, Bacillus subtilis, Klebsiella oxytoca, and Escherichia coli were taken as model microbes from Dhulikhel, 30 km east from Kathmandu, Nepal. Results and discussion  Microbes used in this study showed different abilities in their removal of As(III) with and without addition of Mn and Fe salts. The trend of remediation increased with time. S. aureus was found to be the best among the microbes used. It showed almost 100% removal after 48-h culture, both with and without Fe and Mn salts. Rate of removal of As increased with addition of Fe and Mn for all microbes. Removal efficiency was found to increase by about 32% on average after addition of salts in 24-h cultures of S. aureus.     

The dynamics of arsenic in four paddy fields in the Bengal delta

Irrigation with arsenic contaminated groundwater in the Bengal Delta may lead to As accumulation in the soil and rice grain. The dynamics of As concentration and speciation in paddy fields during dry season (boro) rice cultivation were investigated at 4 sites in Bangladesh and West Bengal, India. Three sites which were irrigated with high As groundwater had elevated As concentrations in the soils, showing a significant gradient from the irrigation inlet across the field. Arsenic concentration and speciation in soil pore water varied temporally and spatially; higher As concentrations were associated with an increasing percentage of arsenite, indicating a reductive mobilization. Concentrations of As in rice grain varied by 2-7 fold within individual fields and were poorly related with the soil As concentration. A field site employing alternating flooded-dry irrigation produced the lowest range of grain As concentration, suggesting a lower soil As availability caused by periodic aerobic conditions.     

Toxic fluoride and arsenic contaminated groundwater in the Lahore and Kasur districts, Punjab, Pakistan and possible contaminant sources

The present study is the first attempt to put forward possible sources of As, F- and SO4(2-) contaminated groundwater in the Kalalanwala area, Punjab, Pakistan. Five rainwater and 24 groundwater samples from three different depths were analyzed. Shallow groundwater from 24 to 27 m depth contained high F- (2.47-21.1mg/L), while the groundwater samples from the deeper depth were free from fluoride contamination. All groundwater samples contained high As (32-1900 microg/L), in excess of WHO drinking water standards. The SO4(2-) ranges from 110 to 1550 mg/L. Delta34S data indicate three sources for SO4(2-) air pollutants (5.5-5.7 per thousand), fertilizers (4.8 per thousand), and household waste (7.0 per thousand). Our important finding is the presence of SO4(2-), As and F- in rainwater, indicating the contribution of these elements from air pollution. We propose that pollutants originate, in part, from coal combusted at brick factories and were mobilized promotionally by the alkaline nature of the local groundwater.     

Enhanced mobilization of arsenic and heavy metals from mine tailings by humic acid

Arsenic and heavy metal mobilization from mine tailings is an issue of concern as it might pose potential groundwater or ecological risks. Increasing attention recently has been focused on the effects of natural organic matter on the mobility behavior of the toxicants in the environment. Column experiments were carried out in this research study to evaluate the feasibility of using humic acid (HA) to mobilize arsenic and heavy metals (i.e., Cu, Pb and Zn) from an oxidized Pb-Zn mine tailings sample collected from Bathurst, New Brunswick, Canada. Capillary electrophoresis analyses indicated that arsenate [As(V)] was the only extractable arsenic species in the mine tailings and the addition of HA at pH 11 did not incur the oxidation-reduction or methylation reactions of arsenic. A 0.1% HA solution with an initial pH adjusted to 11 was selected as the flushing solution, while distilled water (initial pH adjusted to 11) was used as the control to account for the mobilization of arsenic and the heavy metals by physical mixing and the effect of pH. It was found that the HA could significantly enhance the mobilization of arsenic and heavy metals simultaneously from the mine tailings. After a 70-pore-volume-flushing, the mobilization of arsenic, copper, lead and zinc reached 97, 35, 838 and 224 mg kg(-1), respectively. The mobilization of arsenic and the heavy metals was found to be positively correlated with the mobilization of Fe in the presence of the HA. Moreover, the mobilization of arsenic was also correlated well with that of the heavy metals. The mobilization of co-existing metals to some extent might enhance arsenic mobilization in the presence of the HA by helping incorporate it into soluble aqueous organic complexes through metal-bridging mechanisms. Use of HA in arsenic and heavy metal remediation may be developed as an environmentally benign and possible effective remedial option to reduce and avoid further contamination.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): concentrations and solubilities of PM(2.5) trace elements and their implications for source apportionment and health research

The elemental compositions of the water-soluble and acid-digestible fractions of 24-hr integrated fine particulate matter (PM(2.5)) samples collected in Steubenville, OH, from 2000 to 2002 were determined using dynamic reaction cell inductively coupled plasma-mass spectrometry. The water-soluble elemental compositions of PM(2.5) samples collected at four satellite monitoring sites in the surrounding region were also determined. Fe was the most abundant but least water soluble of the elements determined at the Steubenville site, having a mean ambient concentration of 272 ng/m3 and a median fractional solubility of 6%. Fe solubility and its correlations with SO4(2-) and temperature varied significantly by season, consistent with the hypothesis that secondary sulfates may help to mobilize soluble Fe under suitable summertime photochemical conditions. Significantly higher ambient concentrations were observed at Steubenville than at each of the four satellite sites for 10 of the 18 elements (Al, As, Ca, Cd, Fe, Mg, Mn, Na, Pb, and Zn) determined in the water-soluble PM(2.5) fraction. Concentrations of Fe, Mn, and Zn at Steubenville were substantially higher than concentrations reported recently for larger U.S. cities. Receptor modeling identified seven sources affecting the Steubenville site. An (NH4)2SO4-dominated source, likely representing secondary PM(2.5) from coal-fired plants to the west and southwest of Steubenville, accounted for 42% of the PM(2.5) mass, and two sources likely dominated by emissions from motor vehicles and from iron and steel facilities in the immediate Steubenville vicinity accounted for 20% and 10%, respectively. Other sources included an NH4NO3 source (15%), a crustal source (6%), a mixed nonferrous metals and industrial source (3%), and a primary coal combustion source (3%). Results suggest the importance of very different regional and local source mechanisms in contributing to PM(2.5) mass at Steubenville and reinforce the need for further research to elucidate whether metals such as Fe, Mn, and Zn play a role in the PM(2.5) health effects observed previously there.     

Transport and attenuation of metal(loid)s in mine tailings amended with organic carbon: Column experiments

A laboratory-scale column experiment was conducted to evaluate the effect of organic carbon amendments on the mobility of As, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Tl and Zn in mine tailings. Three columns were packed with sulfide- and carbonate-rich tailings, which were amended with a 1:1 (vol.) mixture of peat and spent brewing grain at proportions of 0, 2 and 5vol.%. A simulated input solution characterized by circumneutral pH and elevated concentrations of SO(4) and S(2)O(3) was passed through the columns for 540 days. The input solution contained low concentrations of metal(loid)s during the initial 300 days and elevated concentrations thereafter. Decreases in mass transport of S(2)O(3) were observed in all columns; with increased attenuation observed at 5 vol. % organic carbon content. Removal of Mn, Ni, Cu, Sb and Mo was observed in all columns during the initial 300 days. However, during this time, mobilization of Fe, As, Zn and Pb was observed, with the greatest increases in concentration observed at the higher organic carbon content. During the final 240 days, S(2)O(3) removal was enhanced in columns containing organic carbon, and Fe, Mn, Ni, Tl, As and Sb removal also was observed. This study demonstrates the influence of organic carbon amendments on metal(loid) mobility in mine tailings. Decreases in mass discharge of metal(loid)s may be achieved using this technique; however, site-specific geochemical conditions must be considered before field-scale implementation.     

Contamination by arsenic and other trace elements in tube-well water and its risk assessment to humans in Hanoi, Vietnam

Concentrations of As and other trace elements and their association were examined in groundwater (n = 25) and human hair (n = 59) collected at Gia Lam District and Thanh Tri District, suburban areas of Hanoi, Vietnam, in September 2001. Concentrations of As in the groundwater ranged from <0.10 to 330 microg/l, with about 40% of these exceeding WHO drinking water guideline of 10 microg/l. Also, 76% and 12% of groundwater samples had higher concentrations of Mn and Ba than WHO drinking water guidelines, respectively. Arsenic concentrations in hair of residents in Gia Lam and Thanh Tri Districts (range 0.088-2.77 microg/g dry wt.) were lower than those in other As-contaminated areas of the world, but were higher than those of people in non-contaminated areas. Concentrations of As and Mn in hair of some individuals from the Gia Lam and Thanh Tri Districts exceeded the level associated with their toxicity and, therefore, a potential health risk of As and Mn is a concern for the people consuming the contaminated water in this area. Cumulative As exposure was estimated to be lower than the threshold levels at the present, which might explain the absence of manifestations of chronic As poisoning and arsenicosis in the residents of Gia Lam and Thanh Tri Districts. To our knowledge, this study revealed for the first time that the residents are exposed not only to As but also Mn and Ba from groundwater in the Red River Delta, Vietnam.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

Manganese and trace-metal mobility under reducing conditions following in situ oxidation of TCE by KMnO4: a laboratory column experiment

The stability of Mn oxides, and the potential for mobilization of associated trace metals, were assessed by simulating the onset of microbially-mediated reducing conditions in a continuous-flow column experiment. The column had previously been used for an in situ chemical oxidation (ISCO) experiment in which trichloroethylene was reacted with permanganate in the presence of aqueous trace metals, which produced Mn oxyhydroxides (MnO(x)) that sequestered the trace metals and coated the column sand. The column influent solution represented the incursion of ambient groundwater containing dissolved organic carbon (DOC) into an ISCO treatment zone. The influx of DOC-containing groundwater initiated a series of cation-exchange, surface-complexation and reductive-dissolution reactions that controlled the release of aqueous metals from the system. Peak concentrations in the effluent occurred in the order Na, Mo, Cr, Zn, K, Mn, Fe, Pb, Mg, Ni, Cu and Ca. Manganese release from the column was controlled by a combination of cation exchange, reductive dissolution and precipitation of rhodochrosite. The trend in Fe concentrations was similar to that of Mn, and also resulted from a combination of reductive dissolution and cation exchange. Cation exchange and/or surface-complexation were the primary mechanisms controlling Cu, Ni, Mo and Pb release to solution, while Zn and Cr concentrations did not display coherent trends. Although metal release from the treatment zone was evident in the data, concentrations of trace metals remained below 0.05 mg L(-1) with the exception of Mo which reached concentrations on the order of 1 mg L(-1). The establishment of anaerobic conditions in ISCO-treated aquifers may result in a prolonged flux of aqueous Mn(II), but with the exception of MoO(4)(2-), it is unlikely that trace metals sequestered with MnO(x) during ISCO will be released to the groundwater in elevated concentrations.     

Seawater intrusion vulnerability in the coastal aquifers of southern India—an appraisal of the GALDIT model,parameters’ sensitivity,and hydrochemical indicators

An appraisal of seawater intrusion into the coastal aquifers is one of the major issues for groundwater resource management. The GALDIT model applies to the analysis of multiple parameters using systematic GIS techniques for mapping and assessment of seawater intrusion vulnerability. It demarcates the mapping of potential vulnerability that shows a higher vulnerability to seawater intrusion in various parts of the coast and the estimated vulnerability index value of 7.50 and 9.64. An area of 33.0 km² spread in the low-lying coastal area comprising estuaries, salt marshes, and saltpans shows the high vulnerability condition with an estimated vulnerability value of 6.42–7.50. An area of 73.20 km² spread over coastal and alluvial plains experiences moderate vulnerability (temporal salinity in the groundwater sources) with an estimated vulnerability index value of 5.46–6.42. Aquifers underlying coastal uplands (hard rock formations) and some parts of accretionary beaches (2.05 km²) are relatively protected fresh groundwater sources, wherein the estimated vulnerability index is 4.55–5.46. The vulnerability mapping of the GALDIT model using hydrochemical analysis of primary groundwater parameters such as TDS, Cl^?, HCO₃, and Cl^?/HCO₃ ratio is validated. Higher concentration of TDS (2637–4162 mg/l) and Cl^? (1268–2347 mg/l) is taken for the areas falling under higher vulnerability to seawater intrusion, especially in the placer mining sites and coastal areas facing erosion. Similarly, the groundwater sources of the low-lying areas including estuaries, salt marshes, saltpans, and backwater were noted to have higher values of Cl^?/HCO₃ with a rationality of 9.87–12.18. Hydrological facies shows the highest concentration of NaCl in the groundwater sources within the proximity of eroded beaches, saltwater bodies, and sand mining areas. A hydrochemical facies evolution (HFE) diagram represents the hydrochemical facies of groundwater elements that shows an intrusion of seawater into the coastal aquifers underlying the very high vulnerable zones. Higher bicarbonate concentration (233–318 mg/l) is noticed in the upland areas and some parts of dunes and accreted beaches, sandy coasts, and uplands. Vulnerability analysis reveals that those areas near saltwater bodies and eroding coasts are prone to lateral and vertical diffusion of saltwater. The geodatabase developed through such modeling studies can help in planning and developing activities for sustainable groundwater resource management in coastal areas.

     

Potential for microbially mediated redox transformations and mobilization of arsenic in uncontaminated soils

Surface soil samples, which had no significant As contamination, were examined for As(V) reduction, As(III) oxidation and As mobilization capability. All five soil samples tested exhibited microbial As(V)-reducing activities both in aerobic and anaerobic conditions. Under aerobic conditions when As(V) reduction had almost ceased, oxidation of As(III) to As(V) occurred, whereas only As(V) reduction was observed under anaerobic conditions. In cultures incubated with As(III), As(III) was oxidized by indigenous soil microbes only under aerobic conditions. These results indicate that microbial redox transformations of As are ubiquitous in the natural environment regardless of background As levels. Mobilization through microbially mediated As(V) and Fe(III) reduction occurred both in the presence and absence of oxygen. Significant variation in dissolved As occurred depending on the Fe contents of soils, and re-immobilization of As arose in the presence of oxygen, presumably as a consequence of dissolved As(III) and Fe(II) oxidation. There was no apparent correlation between dissolved Fe(II) and As, suggesting that reductive dissolution of Fe(III) minerals does not necessarily determine the extent of As release from soils.