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.     

Reassessing the management of groundwater use from sandy aquifers: acidification and base cation depletion exacerbated by drought and groundwater withdrawal on the Gnangara Mound, Western Australia

The combined effects of low rainfall, groundwater withdrawal in excess of 300 GL/year and reduced recharge in areas covered by pine plantations has caused the water table in a sandy unconfined aquifer on the Gnangara Mound in Western Australia to drop by up to 5 m and aquifer storage to decline by about 500 GL over the last 20 years. Groundwater has become acidic in areas of high drawdown, with pH values typically being less than 5.0 at the water table, and elevated concentrations of SO₄ ^2?, Al, Fe, Zn, Cu, Ni and Pb. Trends of increasing acidity and base cation concentrations in deep water supply wells in the Mirrabooka wellfield indicate that about 0.7 keq/ha/year of base cations are being leached from soil within cones of depression of pumping wells. These results indicate that the assessment of the sustainable yields of aquifers under conditions of low rainfall needs to consider geochemical interactions between groundwater, aquifer sediments, soils and vegetation, and not be just based on aquifer hydraulics and water-balance changes.     

Natural organic matter in sedimentary basins and its relation to arsenic in anoxic ground water: the example of West Bengal and its worldwide implications

In order to investigate the mechanism of As release to anoxic ground water in alluvial aquifers, the authors sampled ground waters from 3 piezometer nests, 79 shallow (<45 m) wells, and 6 deep (>80 m) wells, in an area 750 m by 450 m, just north of Barasat, near Kolkata (Calcutta), in southern West Bengal. High concentrations of As (200–1180 μg L⁻¹) are accompanied by high concentrations of Fe (3–13.7 mg L⁻¹) and PO₄ (1–6.5 mg L⁻¹). Ground water that is rich in Mn (1–5.3 mg L⁻¹) contains <50 μg L⁻¹ of As. The composition of shallow ground water varies at the 100-m scale laterally and the metre-scale vertically, with vertical gradients in As concentration reaching 200 μg L⁻¹ m⁻¹. The As is supplied by reductive dissolution of FeOOH and release of the sorbed As to solution. The process is driven by natural organic matter in peaty strata both within the aquifer sands and in the overlying confining unit. In well waters, thermo-tolerant coliforms, a proxy for faecal contamination, are not present in high numbers (<10 cfu/100 ml in 85% of wells) showing that faecally-derived organic matter does not enter the aquifer, does not drive reduction of FeOOH, and so does not release As to ground water.Arsenic concentrations are high (≫50 μg L⁻¹) where reduction of FeOOH is complete and its entire load of sorbed As is released to solution, at which point the aquifer sediments become grey in colour as FeOOH vanishes. Where reduction is incomplete, the sediments are brown in colour and resorption of As to residual FeOOH keeps As concentrations below 10 μg L⁻¹ in the presence of dissolved Fe. Sorbed As released by reduction of Mn oxides does not increase As in ground water because the As resorbs to FeOOH. High concentrations of As are common in alluvial aquifers of the Bengal Basin arise because Himalayan erosion supplies immature sediments, with low surface-loadings of FeOOH on mineral grains, to a depositional environment that is rich in organic mater so that complete reduction of FeOOH is common.     

Arsenic concentration variability in public water system wells in Minnesota,USA

There is significant random and systematic variability in As concentrations in numerous public water system wells in Minnesota. Arsenic concentrations fluctuate above and below the USA’s As drinking water Maximum Contaminant Level (MCL) of 10 μg/L. The average As concentration is commonly within one standard deviation of the MCL. Results of intensive sampling conducted over the course of approximately 1 year at 3 public water system wells is consistent with the analysis of historic As measurements. In some cases, significant As concentration variability was noted over a short period of time. In these wells, the As concentration was less than 10 μg/L shortly after pumping started, but the As concentration increased over time to a level exceeding 10 μg/L. In these wells, the As concentration decreased to below 10 μg/L again when pumping was briefly restarted after being stopped for 4 h. The As concentration variability is likely due to As adsorption reactions between Fe oxides in the well borehole and in the aquifer near the well borehole during periods when the pump is not in operation. When it is crucial to accurately determine true average As concentrations – for example, at one of the many wells that fluctuate above and below the regulatory As limit of 10 μg/L – it is worthwhile collecting samples frequently during pumping to more accurately determine the average As concentration. Determining a reliable average depends on the standard deviation (SD) of the measurements, with more measurements required if the SD is larger.     

Arsenic enrichment in unconfined sections of the southern Gulf Coast aquifer system, Texas

Groundwater arsenic concentrations exceeding the federal drinking water standard are common in the southern Gulf Coast aquifer system in Texas, including in aerobic, unconfined groundwater which provides much of the municipal and domestic water supplies for the region. The objective of this study was to determine geochemical factors affecting the occurrence and distribution of groundwater As in unconfined portions of the southern Gulf Coast aquifer system through a comparative transect study of groundwater across three major hydrostratigraphic units (the Catahoula Formation, Jasper aquifer and Evangeline aquifer) and analysis of regional water quality data. Results show that As concentrations decrease with increasing distance from the Catahoula Formation, which is consistent with Miocene volcanic ash as the main source of As to groundwater in the region. Arsenic concentrations correlate with V, SiO₂ and K, all of which were released during weathering of volcanic sediments and their degradation products. In all three units, carbonate weathering and active recharge in the unconfined zones result in circum-neutral pH and oxidizing groundwater, which are typically amenable to As immobilization by adsorption of arsenate onto mineral oxides and clays. However, As concentrations exceed 10 μg/L in approximately 30% of wells. Silica that was co-released with As may compete for sorption sites and reduce the capacity for arsenate adsorption.     

Quality assessment of groundwater at south Al Madinah Al Munawarah area, Saudi Arabia

Groundwater is the main source of irrigation within south Al Madinah Al Munawarah region. It is also an important source of drinking water in many areas including Madinah city. The wells installed in the aquifer of the study area (south Madinah city) are not currently regulated by the local authorities although they are a key component of water supply. The aquifers in the study area range from unconfined to semi-confined and confined. The main aim of this study is to assess the groundwater in the region for drinking and agricultural uses. For this purpose, hydrochemical analyses of major, minor and trace constituents and nutrients were performed on 29 groundwater samples from the aquifer located about 20 km south of Madinah. The recharge rate of the aquifer of the study area was estimated to be 6.58 % of the annual precipitation using the chloride mass-balance method. Chloride was positively correlated with major ions, which suggests that agricultural activities have some effect on groundwater chemistry through leaching of readily soluble salts from the soil zone. Groundwater of the study area is characterized by dominance of Na over Ca. Chloride was found to be the most dominant anion and replaced by HCO₃, thus reflecting geochemical evolution in the study area. The groundwater of the study area is not safe for drinking but can be safely used for salt-tolerant crops.     

Influences of groundwater extraction on flow dynamics and arsenic levels in the western Hetao Basin,Inner Mongolia,China

Data on spatiotemporal variations in groundwater levels are crucial for understanding arsenic (As) behavior and dynamics in groundwater systems. Little is known about the influences of groundwater extraction on the transport and mobilization of As in the Hetao Basin, Inner Mongolia (China), so groundwater levels were recorded in five monitoring wells from 2011 to 2016 and in 57 irrigation wells and two multilevel wells in 2016. Results showed that groundwater level in the groundwater irrigation area had two troughs each year, induced by extensive groundwater extraction, while groundwater levels in the river-diverted (Yellow River) water irrigation area had two peaks each year, resulting from surface-water irrigation. From 2011 to 2016, groundwater levels in the groundwater irrigation area presented a decreasing trend due to the overextraction. Groundwater samples were taken for geochemical analysis each year in July from 2011 to 2016. Increasing trends were observed in groundwater total dissolved solids (TDS) and As. Owing to the reverse groundwater flow direction, the Shahai Lake acts as a new groundwater recharge source. Lake water had flushed the near-surface sediments, which contain abundant soluble components, and increased groundwater salinity. In addition, groundwater extraction induced strong downward hydraulic gradients, which led to leakage recharge from shallow high-TDS groundwater to the deep semiconfined aquifer. The most plausible explanation for similar variations among As, Fe(II) and total organic carbon (TOC) concentrations is the expected dissimilatory reduction of Fe(III) oxyhydroxides.     

The hydraulic conductivity field and groundwater flow in the unconfined aquifer system of the Keta Strip,Ghana

This study investigates the hydraulic conductivity field and the groundwater flow pattern as predicted by a calibrated steady state groundwater flow model for the Keta Strip, southeastern Ghana. The hydraulic conductivity field is an important parameter in evaluating aquifer properties in space, and in general basin-wide groundwater resources evaluation and management. This study finds that the general hydraulic conductivity of the unconsolidated unconfined aquifer system of the Keta Strip ranges between 2 m/d and 20 m/d, with an average of 15 m/d. The spatial variation in horizontal hydraulic conductivity appears to take the trend in the variations in the nature of the material in space. Calibrated groundwater recharge suggests that 6.9–34% of annual precipitation recharges the shallow aquifer system. This amount of recharge is significant and suggests high fortunes in terms of groundwater resources development for agriculture and industrial activities in the area. A spatial distribution of groundwater recharge from precipitation is presented in this study. The spatial pattern appears to take the form of the distribution in horizontal hydraulic conductivity, and suggests that the vertical hydraulic conductivity takes the same pattern of spatial variation as the horizontal hydraulic conductivity. This is consistent with observations in other areas. The resulting groundwater flow is dominated by local flow systems as the unconfined system is quite shallow. A general northeast – southwest flow pattern has been observed in the study area.     

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.     

Is 222Rn a suitable tracer of stream–groundwater interactions? A case study in central Italy

River water infiltration into an unconfined porous aquifer (∼73% gravels, ∼12% sands, ∼15% silts and clays) in the Petrignano d’Assisi plain, central Italy, was traced combining isotopic techniques (²²²Rn) with hydrochemical and hydrogeologic techniques in order to characterize the system under study. The ²²²Rn gave information about the river water residence times within the aquifer and hydrochemical data, in a two-component mixing model, which allowed estimating the extent of mixing between surface waters and groundwater in wells at increasing distances from the river. The mixing measured in the well closer to the riverbank indicated a higher contribution of river water (up to 99%) during the groundwater recession phase and a moderate contribution (up to 64%) during the recharge phase. A model describing ²²²Rn concentrations in groundwater as the result of both parent/daughter nuclide equilibrium and mixing process (²²²Rn mixing/saturation model) was used to describe observed Rn concentrations and mixing index trends with the aim of evaluating water mean infiltration velocities along the transect. The stream bank infiltration velocities obtained by the model ranged from 1 m day⁻¹ during groundwater recharge periods, when river water infiltration is lower, to 39 m day⁻¹ during recession phases, when river water infiltration is larger.     

Effects of human-induced alteration of groundwater flow on concentrations of naturally-occurring trace elements at water-supply wells

The effects of human-induced alteration of groundwater flow patterns on concentrations of naturally-occurring trace elements were examined in five hydrologically distinct aquifer systems in the USA. Although naturally occurring, these trace elements can exceed concentrations that are considered harmful to human health. The results show that pumping-induced hydraulic gradient changes and artificial connection of aquifers by well screens can mix chemically distinct groundwater. Chemical reactions between these mixed groundwaters and solid aquifer materials can result in the mobilization of trace elements such as U, As and Ra, with subsequent transport to water-supply wells. For example, in the High Plains aquifer near York, Nebraska, mixing of shallow, oxygenated, lower-pH water from an unconfined aquifer with deeper, confined, anoxic, higher-pH water is facilitated by wells screened across both aquifers. The resulting higher-O₂, lower-pH mixed groundwater facilitated the mobilization of U from solid aquifer materials, and dissolved U concentrations were observed to increase significantly in nearby supply wells. Similar instances of trace element mobilization due to human-induced mixing of groundwaters were documented in: (1) the Floridan aquifer system near Tampa, Florida (As and U), (2) Paleozoic sedimentary aquifers in eastern Wisconsin (As), (3) the basin-fill aquifer underlying the California Central Valley near Modesto (U), and (4) Coastal Plain aquifers of New Jersey (Ra). Adverse water-quality impacts attributed to human activities are commonly assumed to be related solely to the release of the various anthropogenic contaminants to the environment. The results show that human activities including various land uses, well drilling, and pumping rates and volumes can adversely impact the quality of water in supply wells, when associated with naturally-occurring trace elements in aquifer materials. This occurs by causing subtle but significant changes in geochemistry and associated trace element mobilization as well as enhancing advective transport processes.     

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.     

Influence of hydrostratigraphy and structural setting on the arsenic occurrence in groundwater of the Cimino-Vico volcanic area (central Italy)

Arsenic occurrence in groundwater near the Cimino-Vico volcanoes (central Italy) was analysed considering the hydrostratigraphy and structural setting and the shallow and deep flows interacting within the Quaternary volcanics. Groundwater is the local source of drinking water. As documented in the past, arsenic in the groundwater has become a problem, and the European maximum allowable contaminant level was recently lowered to 10 μg/L. Chemical analyses of groundwater were conducted, sampled over an area of about 900 km², from 65 wells and springs representative of the volcanic aquifer and thermal waters. Considering the type of aquifer, the nature of the aquifer formation and its substratum, the hydrochemical data highlight that the arsenic content of the groundwater is mainly connected with the hydrothermal processes in the volcanic area. Thermal waters (54–60°C) fed from deep-rising fluids show higher arsenic concentrations (176–371 μg/L). Cold waters sampled from the volcanic aquifer are characterized by a wide variability in their arsenic concentration (1.6–195 μg/L), and about 62% exceed the limit of 10 μg/L. Where the shallow volcanic aquifer is open to deep-rising thermal fluids, relatively high arsenic concentrations (20–100 μg/L) are found. This occurs close to areas of the more recent volcano-tectonic structures.     

Source and distribution of naturally occurring arsenic in groundwater from Alberta’s Southern Oil Sands Regions

Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrations in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(−I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.     

Characterization of accumulated precipitates during subsurface iron removal

The principle of subsurface iron removal for drinking water supply is that aerated water is periodically injected into the aquifer through a tube well. On its way into the aquifer, the injected O₂-rich water oxidizes adsorbed Fe²⁺, creating a subsurface oxidation zone. When groundwater abstraction is resumed, the soluble Fe²⁺ is adsorbed and water with reduced Fe concentrations is abstracted for multiple volumes of the injection water. In this article, Fe accumulation deposits in the aquifer near subsurface treatment wells were identified and characterized to assess the sustainability of subsurface iron removal regarding clogging of the aquifer and the potential co-accumulation of other groundwater constituents, such as As. Chemical extraction of soil samples, with Acid-Oxalate and HNO₃, showed that Fe had accumulated at specific depths near subsurface iron removal wells after 12 years of operation. Whether it was due to preferred flow paths or geochemical mineralogy conditions; subsurface iron removal clearly favoured certain soil layers. The total Fe content increased between 11.5 and 390.8 mmol/kg ds in the affected soil layers, and the accumulated Fe was found to be 56-100% crystalline. These results suggest that precipitated amorphous Fe hydroxides have transformed to Fe hydroxides of higher crystallinity. These crystalline, compact Fe hydroxides have not noticeably clogged the investigated well and/or aquifer between 1996 and 2008. The subsurface iron removal wells even need less frequent rehabilitation, as drawdown increases more slowly than in normal production wells. Other groundwater constituents, such as Mn, As and Sr were found to co-accumulate with Fe. Acid extraction and ESEM-EDX showed that Ca occurred together with Fe and by X-ray Powder Diffraction it was identified as calcite.     

Identification and regional quantification of hydrochemical processes at the contact zone between anoxic groundwater and surface water in poldered floodplains (Oderbruch polder,Germany)

The hydrochemistry in the largest polder of the Oder River, named Oderbruch, is affected by long-term infiltration of water from the Oder into the aquifer below an alluvial loamy top layer of the polder. These exceptional hydraulic conditions are a result of dyke constructions which were built more than 250 a ago. The objective of this investigation is a better understanding and a characterisation of the contact zone between the anaerobic groundwater and the surface water of a vast drainage system. Induced by changing water levels, different hydraulic conditions occur, which strongly influence the hydrochemistry of the shallow aquifer and therefore the natural sink function of the polder area.Field investigations with a hydrochemical and hydraulic characterisation of selected drainage ditch locations show considerable chemical interactions between groundwater and surface water. Depending on the drainage ditch type, which is defined by the hydraulic situation, the redox processes create a chemical gradient combined with a distinct enrichment of Fe and Mn. The source of the high amounts of Fe and Mn in the groundwater are reduced Fe- and Mn-hydroxides from the aquifer sediments.Under exfiltrating conditions interrupted by dry phases, more than 50 g kg⁻¹ Fe and 0.25 g kg⁻¹ Mn have accumulated in the drainage ditch floor sediments since the construction of the drainage ditches 35 a ago. The results show a very effective fixation of trace metals in the drainage ditch sediments under these conditions. Under permanent exfiltration conditions, the enrichment of Fe and Mn is relatively low. The maximum Fe content was 4 g kg⁻¹ sediment and the Mn content reached only 0.4 g kg⁻¹. This is less than 10% of the mobile Fe²⁺ and less than 1% of the Mn²⁺ which migrates from the aquifer into the surface water.     

Hydrology of part of the Oramiriukwa River basin,southeast of Owerri,Imo State,Nigeria

The Oramiriukwa River is within the sandy coastal plain strata of the Benin formation (Miocene–Recent). The base flow is very high ranging from 79.13–98.56%, which is caused by the excellent hydraulic interconnection between the river and the adjacent unconfined aquifer. Recharge rates are high, estimated to range from 1.8×10¹²–2.5×10¹² m³/year. Coastal sands are medium-to-coarse grained, moderately-to-poorly sorted, angular to subangular, with lenses of clay and clayey fine-grained sands. The coastal sands and clay lenses form aquifer and aquitard systems, which are unconfined to semi-confined. Groundwater recharge potential is high. Runoff from precipitation is low. Groundwater and surface water are fairly acidic; pH ranges from 5.5–6.1 (groundwater) and 5.8–6.5 (surface water), and hardness is generally low. Chemical analysis and percentage sodium show that groundwater and surface water are somewhat potable after some pH modification of the surface water. The waters are good for agricultural use, especially for irrigation and poultry water supply. However, pollution from landfill leachate is serious. Electronic Publication     

Groundwater chemistry and redox processes: Depth dependent arsenic release mechanism

Patchy occurrences of elevated As are often encountered in groundwater from the shallow aquifers (<50 m) of the Bengal Delta Plain (BDP). A clear understanding of various biogeochemical processes, responsible for As mobilization, is very important to explain this patchy occurrence and thus to mitigate the problem. The present study deals with the periodical monitoring of groundwater quality of five nested piezometeric wells between December 2008 and July 2009 to investigate the temporal changes in groundwater chemistry vis-a-vis the prevalent redox processes in the aquifer. Geochemical modeling has been carried out to identify key phases present in groundwater. A correlation study among different aqueous redox parameters has also been performed to evaluate prevailing redox processes in the aquifer. The long term monitoring of hydrochemical parameters in the multilevel wells together with hydrogeochemical equilibrium modeling has shown more subtle differences in the geochemical environment of the aquifer, which control the occurrence of high dissolved As in BDP groundwater. The groundwater is generally of Ca-HCO₃ type. The dissolved As concentration in groundwater exceeded both WHO and National drinking water standard (Bureau of Indian Standards; BIS, 10 μg L⁻¹) throughout the sampling period. The speciation of As and Fe indicate persistent reducing conditions within the aquifer [As(III): 87-97% of As_T and Fe(II): 76-96% of Fe_T]. The concentration of major aqueous solutes is relatively high in the shallow aquifer (wells A and B) and gradually decreases with increasing depth in most cases. The calculation of SI indicates that groundwater in the shallow aquifer is also relatively more saturated with carbonate minerals. This suggests that carbonate mineral dissolution is possibly influencing the groundwater chemistry and thereby controlling the mobilization of As in the monitored shallow aquifer. Hydrogeochemical investigation further suggests that Fe and/or Mn oxyhydroxide reduction is the principal process of As release in groundwater from deeper screened piezometric wells. The positive correlations of U and V with As, Fe and Mn indicate redox processes responsible for mobilization of As in the deeper screened piezometric wells are possibly microbially mediated. Thus, the study advocates that mobilization of As is depth dependent and concentrations of As in groundwater depends on single/combined release mechanisms.     

Hydrogeochemical evolution of confined groundwater in northeastern Osaka Basin,Japan: estimation of confined groundwater flux based on a cation exchange mass balance method

A confined aquifer system has developed in argillaceous marine and freshwater sediments of Pliocene–Holocene age in the northeastern Osaka Basin (NEOB) in central Japan. The shallow groundwater (<100 m) in the system is recharged in a northern hilly to mountainous area with dominantly Ca-HCO₃ type water, which changes as it flows toward the SW to Mg-HCO₃ type and then to Na-HCO₃ type water. Comparison of the chemical and Sr isotopic compositions of the groundwater with those of the bulk and exchangeable components of the underground sediments indicates that elements leached from the sediments contribute negligibly to the NEOB aquifer system. Moreover, model calculations show that contributions of paleo-seawater in the deep horizon and of river water at the surface are not major factors of chemical change of the groundwater. Instead, the zonal pattern of the HCO₃-dominant groundwater is caused by the loss of Ca²⁺ from the water as it is exchanged for Mg²⁺ in clays, followed by loss of Mg + Ca as they are exchanged for Na + K in clays between the Ca-HCO₃ type recharge water and the exchangeable cations in the clay layers, which were initially enriched in Na⁺. Part of this process was reproduced in a chromatographic experiment in which Na type water with high ⁸⁷Sr/⁸⁶Sr was obtained from Mg type water with low ⁸⁷Sr/⁸⁶Sr by passing it through marine clay packed in a column. The flux of recharge water into the confined aquifer system according to this chromatographic model is estimated to be 0.99 mm/day, which is compatible with the average recharge flux to unconfined groundwater in Japan (1 mm/day).