Evaluation of hydrogeochemical processes in arsenic-contaminated alluvial aquifers in parts of Mid-Ganga Basin,Bihar, Eastern India

The study region covers 1,650 km² of the Mid-Ganga Basin in Bihar, experiencing intensive groundwater draft. The area forms a part of the Gangetic alluvial plain where high incidence of arsenic groundwater contamination (>50 μg/l) has recently been detected. Seventy-seven groundwater samples have been collected and analysed for major ions, iron and arsenic. Arsenic contamination (max 620 μg/l) is confined in hand pump zones (15–35 m) within the newer alluvium deposited during Middle Holocene to Recent age. The older alluvial aquifers are arsenic-safe and recorded maximum concentration as 9 μg/l. Out of 12 hydrochemical facies identified, four have been found arsenic-affected: Ca–HCO₃, Mg–HCO₃, Ca–Mg–HCO₃ and Mg–Ca–HCO₃. The geochemical evolution of groundwater, as investigated by graphical interpretation and statistical techniques (correlation, principal component analysis) revealed that dissolution of detrital calcite, dolomite and infiltration of rainwater are the major processes shaping the groundwater chemistry in the newer alluvium. Arsenic and iron showed strong positive correlation. Rainfall infiltration, carrying organic matter from recently accumulated biomass from this flood-prone belt, plays a critical role in releasing arsenic and iron present in the sediments. Geochemical evolution of groundwater in older alluvium follows a different path, where cation-exchange has been identified as a significant process.     

Origin and mobility of hexavalent chromium in North-Eastern Attica,Greece

An integrated framework that is comprised of field surveys of groundwater, surface water and soils, laboratory process experiments and hydrologic and geochemical modeling is used to identify the origin (anthropogenic versus geogenic sources), fate and transport of hexavalent Cr in Tertiary and Quaternary deposits of Oropos plain in Greece. Groundwater and soils were analyzed in May 2008 and exhibited considerable Cr concentrations. Mineralogical analysis and micro-XRF analysis of the heavy soil fractions (metallic components) showed Cr bearing phases like chromites, Cr-silicate phases with positive correlation between Si, Al, Fe and Cr soil concentrations. Column experiments showed the Cr(VI) desorption ability of soils, e.g. concentration of 20 μg L⁻¹ was detected after the application of 50 mm of rain. The groundwater model simulated the variability of Cr concentrations emanating from both anthropogenic and geogenic sources, successfully using rate constants obtained from the laboratory experiments, e.g. 4.24 nM h⁻¹ for serpentine soil and 0.77 nM h⁻¹ for soil in alluvial deposits. The mineralogical and geochemical results support a geogenic origin for Cr in soils and groundwater of Oropos plain while modeling results suggest that contaminants transported by Asopos River have affected only the upper layers of the subsurface in the vicinity of the river. The framework can be used to establish background concentrations or clean up levels of Cr-contaminated soils and groundwater.     

Evolution of groundwater chemistry in and around Vaniyambadi Industrial Area: Differentiating the natural and anthropogenic sources of contamination

Groundwaters in the crystalline aquifers are the major source of drinking water in Vaniyambadi area of Vellore district. Geochemical methods in collaboration with statistical methods were applied in this industrial area to understand the natural and anthropogenic influences on groundwater quality. To accomplish this objective, groundwater samples were collected and analyzed for physicochemical parameters and the results showed a dominance in the order of Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ and HCO₃⁻ > Cl⁻ > SO₄²⁻ > NO₃⁻ for anions and cations, respectively. In contrast to this anion dominance were changed to Cl⁻ > HCO₃⁻ > SO₄²⁻ > NO₃⁻ in samples collected near the tannery industries. Groundwater quality evaluation using TDS and TH suggested that 57% of the total samples are hard-brackish type, indicating its unsuitability for drinking purpose. Generally the water type is Na⁺Cl⁻ to Ca²⁺Mg²⁺HCO₃⁻ type with an intermediate Ca²⁺Mg²⁺Cl⁻, suggesting the mixing of fresh groundwater with tannery effluent and cation exchange. Factor analysis and bivariate plots of major ions suggests that both natural and anthropogenic inputs are equally influencing the groundwater quality. Further investigations proved that silicate weathering is the dominant geogenic source of groundwater solute content, whereas tannery effluent is the anthropogenic source. Saline water mixing index (SWMI) and Cl⁻ vs NO₃⁻ bivariate plot were employed to differentiate the tannery contamination from the other anthropogenic inputs such as agricultural fertilizers, municipal sewages, etc. This analysis shows that samples 2, 4, 8 and 9 (located within the tannery cluster) have a SWMI value greater than 1, representing the groundwater–tannery effluent mixing. This study infers that groundwater in the Vaniyambadi area is under serious threat from both natural and anthropogenic contamination. However, the controlling discharge of untreated tannery effluents must be regulated to reduce the further deterioration of this vital resource in this part of the country.     

Two types of Archaean supracrustal belts in the Bundelkhand craton,India: Geology,geochemistry, age and implication for craton crustal evolution

Groundwater sampling was carried out in fast growing Vijayawada urban agglomeration in Andhra Pradesh state with a view to generate base line data and to assess groundwater quality, its variations vis-à-vis urbanization and hydrochemical characteristics. The groundwaters are found to be fresh to brackish, hard to very hard, often enriched with nitrate, phosphate,and faecal colliform indicating anthropogenic influence on groundwater on account of urbanization. Manganese and iron of geogenic origin are also found to be in high concentrations in some localities. The quality deterioration is more in shallow aquifers, as also in core urban and red soil covered areas. Spatial variations in groundwater quality are discernible, with high concentrations of SO₄^-4–,NO₃^- in core urban area suggesting the impact of urbanization. A wide range of chemical constituents indicate water rock interactions as influenced by anthropogenic activities controlling the urban aquifers. The order of abundance of cations is Na>Mg>Ca>K, while the order of abundance of anions is Cl>HCO₃>SO₄>NO₃. The baseline study suggests the need to protect the groundwater resource through sound environmental protection measures for the welfare of the inhabitants in the city around which the new capital is proposed to be constructed for newly formed Andhra Pradesh state in India.     

Arsenic enrichment in groundwater in the middle Gangetic Plain of Ghazipur District in Uttar Pradesh,India

Groundwater with high geogenic arsenic (As) is extensively present in the Holocene alluvial aquifers of Ghazipur District in the middle Gangetic Plain, India. A shift in the climatic conditions, weathering of carbonate and silicate minerals, surface water interactions, ion exchange, redox processes, and anthropogenic activities are responsible for high concentrations of cations, anions and As in the groundwater. The spatial and temporal variations for As concentrations were greater in the pre-monsoon (6.4–259.5 μg/L) when compared to the post-monsoon period (5.1–205.5 µg/L). The As enrichment was encountered in the sampling sites that were close to the Ganges River (i.e. south and southeast part of Ghazipur district). The depth profile of As revealed that low concentrations of NO₃⁻ are associated with high concentration of As and that As depleted with increasing depth. The poor relationship between As and Fe indicates the As release into the groundwater, depends on several processes such as mineral weathering, O₂ consumption, and NO₃⁻ reduction and is de-coupled from Fe cycling. Correlation matrix and factor analysis were used to identify various factors influencing the gradual As enrichment in the middle Gangetic Plain. Groundwater is generally supersaturated with respect to calcite and dolomite in post-monsoon period, but not in pre-monsoon period. Saturation in both periods is reached for crystalline Fe phases such as goethite, but not with respect to poorly crystalline Fe phases and any As-bearing phase. The results indicate release of arsenic in redox processes in dry period and dilution of arsenic concentration by recharge during monsoon. Increased concentrations of bicarbonate after monsoon are caused by intense flushing of unsaturated zone, where CO₂ is formed by decomposition of organic matter and reactions with carbonate minerals in solid phase. The present study is vital considering the fact that groundwater is an exclusive source of drinking water in the region which not only makes situation alarming but also calls for the immediate attention.     

Identification of hydrogeochemical processes and pollution sources of groundwater resources in the Marand plain,northwest of Iran

The main aims of the present study are to identify the major factors affecting hydrogeochemistry of groundwater resources in the Marand plain, NW Iran and to evaluate the potential sources of major and trace elements using multivariate statistical analysis such as hierarchical clustering analysis (HCA) and factor analysis (FA). To achieve these goals, groundwater samples were collected in three sampling periods in September 2013, May 2014 and September 2014 and analyzed with regard to ions (e.g., Ca²⁺, Mg²⁺, Na⁺ and K⁺, HCO₃ ^?, SO₄ ^2?, Cl^?, F^? and NO₃ ^?) and trace metals (e.g., Cr, Pb, Cd, Mn, Fe, Al and As). The piper diagrams show that the majority of samples belong to Na–Cl water type and are followed by Ca–HCO₃ and mixed Ca–Na–HCO₃. Cross-plots show that weathering and dissolution of different rocks and minerals, ion exchange, reverse ion exchange and anthropogenic activities, especially agricultural activities, influence the hydrogeochemistry of the study area. The results of the FA demonstrate that 6 factors with 81.7% of total variance are effective in the overall hydrogeochemistry, which are attributed to geogenic and anthropogenic impacts. The HCA categorizes the samples into two clusters. Samples of cluster C1, which appear to have higher values of some trace metals like Pb and As, are spatially located at the eastern and central parts of the plain, while samples of cluster C2, which express the salinization of the groundwater, are situated mainly westward with few local exceptions.     

Hydrogeochemical and isotopic evidences of the groundwater regime in Datong Basin, Northern China

Datong Basin is one of the Cenozoic faulted basins in Northern China’s Shanxi province, where groundwater is the major source of water supply. The results of hydrochemical investigation show that along the groundwater flow path, from the margins to the lower-lying central parts of the basin, groundwater generally shows increases in concentrations of TDS, HCO₃ ^?, SO₄ ^2?, Cl^?, Na⁺ and Mg²⁺ (except for Ca²⁺ content). Along the basin margin, groundwater is dominantly of Ca–HCO₃ type; however, in the central parts of the basin it becomes more saline with Na–HCO₃-dominant or mixed-ion type. The medium-deep groundwater has chemical compositions similar to those of shallow groundwater, except for the local area affected by human activity. From the mountain front to the basin area, shallow groundwater concentrations of major ions increase and are commonly higher than those in medium-deep aquifers, due to intense evapotranspiration and anthropogenic contamination. Hydrolysis of aluminosilicate and silicate minerals, cation exchange and evaporation are prevailing geochemical processes occurring in the aquifers at Datong Basin. The isotopic compositions indicate that meteoric water is the main source of groundwater recharge. Evaporation is the major way of discharge of shallow groundwater. The groundwater in medium-deep aquifers may be related to regional recharges of rainwater by infiltrating along the mountain front faults, and of groundwater permeating laterally from bedrocks of the mountain range. However, in areas of groundwater depression cones, groundwater in the deep confined aquifers may be recharged by groundwater from the upper unconfined aquifer through aquitards.     

Hydrogeochemical genesis of groundwaters with abnormal fluoride concentrations from Zhongxiang City,Hubei Province,central China

The groundwaters from Zhongxiang City, Hubei Province of central China, have high fluoride concentration up to 3.67 mg/L, and cases of dental fluorosis have been found in this region. To delineate the nature and extent of high fluoride groundwaters and to assess the major geochemical factors controlling the fluoride enrichment in groundwater, 14 groundwater samples and 5 Quaternary sediment samples were collected and their chemistry were determined in this study. Some water samples from fissured hard rock aquifers and Quaternary aquifers have high fluoride concentrations, whereas all karst water samples contain fluoride less than 1.5 mg/L due to their high Ca/Na ratios. For the high fluoride groundwaters in the fissured hard rocks, high HCO₃ ⁻ concentration and alkaline condition favor dissolution of fluorite and anion exchange between OH⁻ in groundwater and exchangeable F⁻ in some fluoride-bearing minerals. For fluoride enrichment in groundwaters of Quaternary aquifers, high contents of fluoride in the aquifer sediments and evapotranspiration are important controls.     

Geochemical characteristics and controlling factors of chemical composition of groundwater in a part of Guntur district,Andhra Pradesh,India

A survey on quality of groundwater was carried out for assessing the geochemical characteristics and controlling factors of chemical composition of groundwater in a part of Guntur district, Andhra Pradesh, India, where the area is underlain by Peninsular Gneissic Complex. The results of the groundwater chemistry show a variation in pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, SO₄ ^2?, NO₃ ^? and F^?. The chemical composition of groundwater is mainly characterized by Na⁺?HCO₃ ^? facies. Hydrogeochemical type transits from Na⁺–Cl^?–HCO₃ ^? to Na⁺–HCO₃ ^?–Cl^? along the flow path. Graphical and binary diagrams, correlation coefficients and saturation indices clearly explain that the chemical composition of groundwater is mainly controlled by geogenic processes (rock weathering, mineral dissolution, ion exchange and evaporation) and anthropogenic sources (irrigation return flow, wastewater, agrochemicals and constructional activities). The principal component (PC) analysis transforms the chemical variables into four PCs, which account for 87% of the total variance of the groundwater chemistry. The PC I has high positive loadings of pH, HCO₃ ^?, NO₃ ^?, K⁺, Mg²⁺ and F^?, attributing to mineral weathering and dissolution, and agrochemicals (nitrogen, phosphate and potash fertilizers). The PC II loadings are highly positive for Na⁺, TDS, Cl^? and F^?, representing the rock weathering, mineral dissolution, ion exchange, evaporation, irrigation return flow and phosphate fertilizers. The PC III shows high loading of Ca²⁺, which is caused by mineral weathering and dissolution, and constructional activities. The PC IV has high positive loading of Mg²⁺ and SO₄ ^2?, measuring the mineral weathering and dissolution, and soil amendments. The spatial distribution of PC scores explains that the geogenic processes are the primary contributors and man-made activities are the secondary factors responsible for modifications of groundwater chemistry. Further, geochemical modeling of groundwater also clearly confirms the water–rock interactions with respect to the phases of calcite, dolomite, fluorite, halite, gypsum, K-feldspar, albite and CO₂, which are the prime factors controlling the chemistry of groundwater, while the rate of reaction and intensity are influenced by climate and anthropogenic activities. The study helps as baseline information to assess the sources of factors controlling the chemical composition of groundwater and also in enhancing the groundwater quality management.     

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.     

Hydrogeochemistry and groundwater quality assessment of the multilayered aquifer in Lower Kelantan Basin,Kelantan, Malaysia

Continual expansion of population density, urbanization, agriculture, and industry in most parts of the world has increased the generation of pollution, which contributes to the deterioration of surface water quality. This causes the dependence on groundwater sources for their daily needs to accumulate day by day, which raises concerns about their quality and hydrogeochemistry. This study was carried out to increase understanding of the geological setup and assess the groundwater hydrogeochemical characteristics of the multilayered aquifers in Lower Kelantan Basin. Based on lithological data correlation of exploration wells, the study area can be divided into three main aquifers: shallow, intermediate and deep aquifers. From these three aquifers, 101 groundwater samples were collected and analyzed for various parameters. The results showed that pH values in the shallow, intermediate and deep aquifers were generally acidic to slightly alkaline. The sequences of major cations and anions were Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and HCO₃^? > Cl^? > SO₄^2? > CO₃^2?, respectively. In the intermediate aquifer, the influence of ancient seawater was the primary factor that contributed to the elevated values of electrical conductivity (EC), Cl^? and total dissolved solids (TDS). The main facies in the shallow aquifer were Ca–HCO₃ and Na–HCO₃ water types. The water types were dominated by Na–Cl and Na–HCO₃ in the intermediate aquifer and by Na–HCO₃ in the deep aquifer. The Gibbs diagram reveals that the majority of groundwater samples belonged to the deep aquifer and fell in the rock dominance zone. Shallow aquifer samples mostly fell in the rainfall zone, suggesting that this aquifer is affected by anthropogenic activities. In contrast, the results suggest that the deep aquifer is heavily influenced by natural processes.     

Hydrochemical appraisal of groundwater and its suitability in the intensive agricultural area of Muzaffarnagar district,Uttar Pradesh,India

Muzaffarnagar is an economically rich district situated in the most fertile plains of two great rivers Ganga and Yamuna in the Indo-gangetic plains, with agricultural land irrigated by both surface water as well as groundwater. An investigation has been carried out to understand the hydrochemistry of the groundwater and its suitability for irrigation uses. Groundwater in the study area is neutral to moderately alkaline in nature. Chemistry of groundwater suggests that alkaline earths (Ca + Mg) significantly exceed the alkalis (Na + K) and weak acids exceed the strong acids (Cl + SO₄), suggesting the dominance of carbonate weathering followed by silicate weathering. Majority of the groundwater samples (62%) posses Ca–Mg–HCO₃ type of hydrochemical species, followed by Ca–Na–Mg–HCO₃, Na–Ca–Mg–HCO₃, Ca–Mg–Na–HCO₃–Cl and Na–Ca–HCO₃–SO₄ types. A positive high correlation (r ² = 0.928) between Na and Cl suggests that the salinity of groundwater is due to intermixing of two or more groundwater bodies with different hydrochemical compositions. Barring a few locations, most of the groundwater samples are suitable for irrigation uses. Chemical fertilizers, sugar factories and anthropogenic activities are contributing to the sulphate and chloride concentrations in the groundwater of the study area. Overexploitation of aquifers induced multi componential mixing of groundwater with agricultural return flow waters is responsible for generating groundwater of various compositions in its lateral extent.     

Groundwater arsenic in the Chaco-Pampean Plain,Argentina: case study from Robles county,Santiago del Estero Province

In large parts of rural Argentina people depend on groundwater whose As content exceeds the Argentine drinking water standards (0.05 mg l⁻¹). The most affected areas are located in the Chaco-Pampean Plain, where aquifers comprise Tertiary loess deposits (in the Pampean Plain) and Tertiary and Quaternary fluvial and aeolian sediments (in the Chaco Plain). Robles county is located in the alluvial cone of the Dulce River consisting of loess (aeolian), and gravel, silt, sand and clay (alluvial) deposits. In the shallow aquifers, more than 48% of the 63 studied wells show As at toxic levels (maximum 4.8 mg l⁻¹), while in the deep groundwater the concentration is below 0.05 mg l⁻¹. The pH of the shallow groundwaters range between 6.5 and 9 and generally have high electrical conductivity with mean values of 2072 and 1693 μS/cm⁻¹ in the years 1998 and 1999, respectively. Arsenic concentrations are high in the alkaline Na–HCO₃ type groundwaters, where As correlates positively with Na⁺ and HCO₃⁻. Moreover, As correlates positively with Mo, U, and V, while a negative correlation was observed with Ca²⁺ and Mg²⁺. The potential sources of groundwater As are: (i) layers of volcanic ash with 90% of rhyolitic glass; (ii) volcanic glass dispersed in the sediments; and (iii) clastic sediments of metamorphic and igneous origin. Great lateral variability in the concentration of groundwater As is caused by several hydrogeological and hydrogeochemical factors.     

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle,USA

This study investigated the potential for the uranium mineral carnotite (K₂(UO₂)₂(VO₄)₂·3H₂O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO₂. Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO₄ + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2mCa⁺² > mHCO₃⁻ + 2mCO₃⁻²) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2mCa⁺² < mHCO₃^- + 2mCO₃⁻²) carnotite saturation was not achieved. In systems open to CO_2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO₂ ranging from 10^−3.5 to 10^−2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO₂ equal to 10^−2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO₂.     

Redox zonation and oscillation in the hyporheic zone of the Ganges-Brahmaputra-Meghna Delta: Implications for the fate of groundwater arsenic during discharge

Riverbank sediment cores and pore waters, shallow well waters, seepage waters and river waters were collected along the Meghna Riverbank in Gazaria Upazila, Bangladesh in Jan. 2006 and Oct.–Nov. 2007 to investigate hydrogeochemical processes controlling the fate of groundwater As during discharge. Redox transition zones from suboxic (0–2 m depth) to reducing (2–5 m depth) then suboxic conditions (5–7 m depth) exist at sites with sandy surficial deposits, as evidenced by depth profiles of pore water (n = 7) and sediment (n = 11; diffuse reflectance, Fe(III)/Fe ratios and Fe(III) concentrations). The sediment As enrichment zone (up to ∼700 mg kg⁻¹) is associated with the suboxic zones mostly between 0 and 2 m depth and less frequently between 5 and 7 m depth. The As enriched zones consist of several 5–10 cm-thick dispersed layers and span a length of ∼5–15 m horizontally from the river shore. Depth profiles of riverbank pore water deployed along a 32 m transect perpendicular to the river shore show elevated levels of dissolved Fe (11.6 ± 11.7 mg L⁻¹) and As (118 ± 91 μg L⁻¹, mostly as arsenite) between 2 and 5 m depth, but lower concentrations between 0 and 2 m depth (0.13 ± 0.19 mg L⁻¹ Fe, 1 ± 1 μg L⁻¹ As) and between 5 and 6 m depth (1.14 ± 0.45 mg L⁻¹ Fe, 28 ± 17 μg L⁻¹ As). Because it would take more than a few hundred years of steady groundwater discharge (∼10 m yr⁻¹) to accumulate hundreds of mg kg⁻¹ of As in the riverbank sediment, it is concluded that groundwater As must have been naturally elevated prior to anthropogenic pumping of the aquifer since the 1970s. Not only does this lend unequivocal support to the argument that As occurrence in the Ganges-Brahmaputra-Meghna Delta groundwater is of geogenic origin, it also calls attention to the fate of this As enriched sediment as it may recycle As into the aquifer.     

Evidence for the occurrence of hydrogeochemical processes in the groundwater of Khoy plain,northwestern Iran,using ionic ratios and geochemical modeling

Rapid population growth, industrialization, and agricultural expansion in the Khoy area (northwestern Iran) have led to its dependence on groundwater and degradation of groundwater quality. This study attempts to decipher the major processes and factors that degrade the groundwater quality of the Khoy plain. For this purpose, 54 groundwater samples from unconfined and confined aquifers of the plain were collected in July 2017 and analyzed for major cations and anions (Na, K, Ca, Mg, HCO₃, SO_4, and Cl), minor ions (NO₃ and F), and Al. Magnesium and bicarbonate were identified as the dominant cation and anion, respectively. Several ionic ratios and geochemical modeling using PHREEQC indicated that the most important hydrogeochemical processes to affect groundwater quality in the plain were weathering and dissolution of evaporitic and silicate minerals, mixing, and ion exchange. There were smaller effects from evaporation and anthropogenic factors (e.g., industries). Results showed that the high salinity of the groundwater in the northeast area of the plain was due to the high solubility of the evaporitic minerals, e.g., halite and gypsum. Reverse ion exchange and the contribution of mineral dissolution were more significant than ion exchange in the northeastern part of the plain. Elevated salinity of the groundwater in the southeast was attributed mostly to reverse ion exchange and somewhat to evaporation.     

Arsenic and other drinking water quality issues,Muzaffargarh District,Pakistan

In 49 samples of groundwater, sampled in Muzaffargarh District of south-western Punjab, central Pakistan, concentrations of As exceeded the World Health Organisation provisional guideline value, and United States Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL), of 10 μg L⁻¹ in 58% of samples and reached up to 906 μg L⁻¹. In this semi-arid region canal irrigation has lead to widespread water-logging, and evaporative concentration of salts has the potential to raise As concentrations in shallow groundwater well above 10 μg L⁻¹. In fact, in rural areas, concentrations stay below 25 μg L⁻¹ because As in the oxic shallow groundwater, and in recharging water, is sorbed to aquifer sediments. In some urban areas, however, shallow groundwater is found to contain elevated levels of As. The spatial distribution of As-rich shallow groundwater indicates either direct contamination with industrial or agricultural chemicals, or some other anthropogenic influence. Geochemical evidence suggests that pollutant organics from unconfined sewage and other sources drives reduction of hydrous ferric oxide (HFO) releasing sorbed As to shallow groundwater. The situation is slightly less clear for seven wells sampled which tap deeper groundwater, all of which were found with >50 μg L⁻¹ As. Here As concentrations seem to increase with depth and differing geochemical signatures are seen, suggesting that As concentrations in older groundwater may be governed by different processes. Other data on parameters of potential concern in drinking water are discussed briefly at the end of the paper.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

Identification of He sources and estimation of He ages in groundwater of the North China Plain

Dissolved helium concentrations and ³He/⁴He ratios were measured for 18 groundwater samples collected from the Quaternary confined aquifers in the North China Plain (NCP). The dissolved helium concentrations ranged from 1 × 10⁻⁷ to 1 × 10⁻⁶ cm³STP·g⁻¹ in the 14 samples from the central plain, but was approximately two orders of magnitude higher, between 6 × 10⁻⁶ and 9 × 10⁻⁵ cm³STP·g⁻¹, in 4 samples from the coastal plain. Based on these concentrations and the corresponding ³He/⁴He ratios varying from 0.09 to 0.55 R_a (where R_a is the ³He/⁴He ratio of air), the dissolved helium in groundwater in the central plain was identified to be primarily a mixture of atmospheric helium with radiogenic helium and a representative radiogenic helium ratio was estimated to be 0.035 R_a. Despite the high fraction of terrigenic ⁴He in the samples from the coastal plain, their ³He/⁴He ratios were found to be significantly above this radiogenic value, ranging between 0.20 and 0.37 R_a, indicating the presence of a mantle-derived He component in this area. About 2–4% mantle helium was estimated to be present in the groundwater of the coastal plain, which probably is associated with the regional Cangdong fault and tectonic activities. Based on the radiogenic He component, ⁴He ages of the groundwater in the central plain were calculated by assuming either pure in situ production or an external helium flux J₀ of 4.7 × 10⁻⁸ cm³STPcm⁻²a⁻¹. The estimated ⁴He ages fall between 9.5 and 51.4 ka and are comparable to the ¹⁴C ages, suggesting that the results of ⁴He dating are reasonable and can be an effective tool to estimate groundwater residence times under suitable conditions.