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.     

Holocene estuarine sediments as a source of arsenic in Pleistocene groundwater in suburbs of Hanoi,Vietnam

Groundwater pollution by arsenic is a major health threat in suburban areas of Hanoi, Vietnam. The present study evaluates the effect of the sedimentary environments of the Pleistocene and Holocene deposits, and the recharge systems, on the groundwater arsenic pollution in Hanoi suburbs distant from the Red River. At two study sites (Linh Dam and Tai Mo communes), undisturbed soil cores identified a Pleistocene confined aquifer (PCA) and Holocene unconfined aquifer (HUA) as major aquifers, and Holocene estuarine and deltaic sediments as an aquitard layer between the two aquifers. The Holocene estuarine sediments (approximately 25–40 m depth, 9.6–4.8 cal ka BP) contained notably high concentrations of arsenic and organic matter, both likely to have been accumulated by mangroves during the Holocene sea-level highstand. The pore waters in these particular sediments exhibited elevated levels of arsenic and dissolved organic carbon. Arsenic in groundwater was higher in the PCA (25–94 μg/L) than in the HUA (5.2–42 μg/L), in both the monitoring wells and neighboring household tubewells. Elevated arsenic concentration in the PCA groundwater was likely due to vertical infiltration through the arsenic-rich and organic-matter-rich overlying Holocene estuarine sediments, caused by massive groundwater abstraction from the PCA. Countermeasures to prevent arsenic pollution of the PCA groundwater may include seeking alternative water resources, reducing water consumption, and/or appropriate choice of aquifers for groundwater supply.     

Geochemical and palaeohydrological controls on the composition of shallow groundwater in the Netherlands

With the exception of the south of the country, the Netherlands has a strong bipartite hydrogeology: the Holocene part with a coastal dune belt and confining top layer of clay and peat further inland, and the Pleistocene, where thick phreatic aquifers dominate. This research aimed to ascertain the geochemical and palaeohydrological controls on the composition of shallow groundwater in 27 regions. Close to 6000 groundwater analyses were grouped and interpreted in terms of 1. salinity, 2. redox status, 3. acid/base and carbonate status and 4. natural nutrients NH₄ and PO₄. The a priori classification into geographical regions and geological formations revealed many statistically significant differences in medians, even for geologically or geographically related data groups. The compound-specific interpretation indicates that there are geogenically controlled, systematic differences in groundwater composition at the regional scale. The imprint of the geological sediments on the groundwater composition decreases in the order marine/estuarine via limnological, fluvial to aeolian. The imprints with respect to pH and carbonate status, natural nutrients and redox status are not necessarily interrelated. The vertical stratification in groundwater composition turns out to be often limited at the regional scale due to mutual occurrence of infiltrating and exfiltrating groundwater in regions and either the presence of a highly reactive Holocene, confining top layer or temporal changes in contamination. In the Holocene part, the salinity is controlled by the palaeoenvironmental conditions during the Holocene and by the recharge origin: the average Cl concentration decreases from estuarine via lagoonal to the former Zuider Sea (which was a bay). The most reduced states and also the highest nutrient concentrations and highest CO₂ pressure are related to the presence of Holocene marine sediments in the confining top layer. Degradation of marine-derived organic matter as a nutrient source, is likely more intense in the Holocene deposits than that of peat and sedimentary remnants of terrestrial plants. A broad range in pH, carbonate status and redox status is encountered in the Pleistocene part. Here, the palaeohydrological evolution in terms of carbonate leaching together with the geological controls on the calcareous nature of the shallow sedimentary deposits cause regional differences in pH, calcite saturation and silicate weathering. One region with Late Pleistocene limnological deposits has deviating groundwater characteristics and appears more similar to the Holocene part of the Netherlands. Furthermore, reactive Fe is not abundant in all Pleistocene fluvial sediments nor is it maximally mobilised, as not all anoxic groundwater in these sediments is siderite-saturated. This leads to considerable intra- and inter-region variability.     

Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

Redox control of arsenic mobilization in Bangladesh groundwater

Detailed hydrochemical measurements, δ³⁴S_SO4 and ³H analyses were performed on 37 groundwater samples collected during February 1999, January and March 2000 from 6 locations in eastern and southeastern Bangladesh to examine redox processes that lead to As mobilization in groundwater. The study sites were chosen based on available nation-wide As surveys to span the entire spectrum of As concentrations in Bangladesh groundwater, and to represent 3 of 5 major geological units of the Ganges-Brahmaputra Delta: uplifted Pleistocene terrace, fluvial flood plain and delta plain. Arsenic was found to be mobilized under Fe-reducing conditions in shallow aquifers (<35 m depth), presumably of Holocene age. It remained mobile under SO₄-reducing conditions, suggesting that authigenic sulfide precipitation does not constitute a significant sink for As in these groundwaters. The redox state of the water was characterized by a variety of parameters including dissolved O₂, NO₃⁻, Mn²⁺, Fe²⁺ concentrations, and SO₄²⁻/Cl⁻ ratios. High dissolved [As] (> 50 μg/l; or > 0.7 μM ) were always accompanied by high dissolved [HCO₃⁻] (> 4 mM), and were close to saturation with respect to calcite. Groundwater enriched in As (200–800 μg/l; or 2.7–10.7 μM) and phosphate (30–100 μM) but relatively low in dissolved Fe (5–40 μM) probably resulted from re-oxidation of reducing, As and Fe enriched water. This history was deduced from isotopic signatures of δ³⁴S_SO4 and ³H₂O (³H) to delineate the nature of redox changes for some of the reducing groundwaters. In contrast, As is not mobilized in presumed Pleistocene aquifers, both shallow (30–60 m) and deep (150–270 m), because conditions were not reducing enough due to lack of sufficient O₂ demand.     

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

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

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 and hydrogeological contrasts between shallow and deeper aquifers in two villages of Araihazar, Bangladesh: Implications for deeper aquifers as drinking water sources

Sediment and groundwater profiles were compared in two villages of Bangladesh to understand the geochemical and hydrogeological factors that regulate dissolved As concentrations in groundwater. In both villages, fine-grained sediment layers separate shallow aquifers (< 28 m) high in As from deeper aquifers (40-90 m) containing < 10 μg/L As. In one village (Dari), radiocarbon dating indicates deposition of the deeper aquifer sediments > 50 ka ago and a groundwater age of thousands of years. In the other village (Bay), the sediment is < 20 ka old down to 90 m and the deeper aquifer groundwater is younger, on the order of hundreds of years. The shallow aquifers in both villages that are high in As contain bomb-³H and bomb-¹⁴C, indicating recent recharge. The major and minor ion compositions of the shallow and deeper aquifers also differ significantly. Deeper aquifer water is of the Na⁺-HCO₃^- type, with relatively little dissolved NH₄⁺ (76 ± 192 μmol/L), Fe (27 ± 43 μmol/L) and Mn (3 ± 2 μmol/L). In contrast, shallow aquifer water is of the Ca²⁺-Mg²⁺-HCO₃^- type, with elevated concentrations of dissolved NH₄⁺ (306 ± 355 μmol/L), Fe (191 ± 73 μmol/L), and Mn (27 ± 43 μmol/L). In both villages, the quantity of As extractable from deeper aquifer sands with a 1 mol/L phosphate solution (0.2 ± 0.3 mg/kg, n = 12; 0.1 ± 0.1 mg/kg, n = 5) is 1 order of magnitude lower than P-extractable As from shallow deposits (1.7 ± 1.2 mg/kg, n = 9; 1.4 ± 2.0 mg/kg, n = 11). The differences suggest that the concentration of P-extractable As in the sediment is a factor controlling the concentration of As in groundwater. Low P-extractable As levels are observed in both deeper aquifers that are low in As, even though there is a large difference in the time of deposition of these aquifers in the two villages. The geochemical data and hydrographs presented in this study suggest that both Holocene and Pleistocene deeper aquifers that are low in As should be a viable source of drinking water as long as withdrawals do not exceed recharge rates of ∼1 cm/yr.     

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.     

Hopane,sterane and n-alkane distributions in shallow sediments hosting high arsenic groundwaters in Cambodia

The presence of elevated As in ground waters exploited for drinking water and irrigation in South-East Asia is causing serious impacts on human health. A key mechanism that causes the mobilization of As in these waters is microbially mediated reductive transformation of As-bearing Fe(III) hydrated oxides and the role of degradable organic matter (OM) in this process is widely recognized. A number of different types of OM that drive As release in these aquifers have been suggested, including petroleum derived hydrocarbons naturally seeping into shallow sediments from deeper thermally mature source rocks. However, the amount of information on the characteristics of the OM in South-East Asian aquifers is limited. Here the organic geochemical analyses of the saturated hydrocarbon fractions and radiocarbon analysis, of two additional sites in SE Asia are reported. The results show that the OM in a given sedimentary horizon likely derives from multiple sources including naturally occurring petroleum. The importance of naturally occurring petroleum as one of the sources was clearly indicated by the n-alkane CPI of approximately 1, the presence of an unresolved complex mixture, and hopane (dominated by 17α(H),21β(H) hopanes) and sterane distribution patterns. The results also indicate that the OM in these aquifers varies tremendously in content, character and potential bioavailability. Furthermore, the presence of petroleum derived OM in sediments at both sites doubles the number of locations where their presence has been observed in association with As-rich, shallow aquifers, suggesting that the role of petroleum derived OM in microbially mediated As release might occur over a wider range of geographical locations than previously thought.     

Palaeo-hydrogeological control on groundwater As levels in Red River delta,Vietnam

To study the geological control on groundwater As concentrations in Red River delta, depth-specific groundwater sampling and geophysical logging in 11 monitoring wells was conducted along a 45 km transect across the southern and central part of the delta, and the literature on the Red River delta’s Quaternary geological development was reviewed. The water samples (n = 30) were analyzed for As, major ions, Fe²⁺, H₂S, NH₄, CH₄, δ¹⁸O and δD, and the geophysical log suite included natural gamma-ray, formation and fluid electrical conductivity. The SW part of the transect intersects deposits of grey estuarine clays and deltaic sands in a 15–20 km wide and 50–60 m deep Holocene incised valley. The NE part of the transect consists of 60–120 m of Pleistocene yellowish alluvial deposits underneath 10–30 m of estuarine clay overlain by a 10–20 m veneer of Holocene sediments. The distribution of δ¹⁸O-values (range −12.2‰ to −6.3‰) and hydraulic head in the sample wells indicate that the estuarine clay units divide the flow system into an upper Holocene aquifer and a lower Pleistocene aquifer. The groundwater samples were all anoxic, and contained Fe²⁺ (0.03–2.0 mM), Mn (0.7–320 μM), SO₄ (<2.1 μM–0.75 mM), H₂S (<0.1–7.0 μM), NH₄ (0.03–4.4 mM), and CH₄ (0.08–14.5 mM). Generally, higher concentrations of NH₄ and CH₄ and low concentrations of SO₄ were found in the SW part of the transect, dominated by Holocene deposits, while the opposite was the case for the NE part of the transect. The distribution of the groundwater As concentration (<0.013–11.7 μM; median 0.12 μM (9 μg/L)) is related to the distribution of NH₄, CH₄ and SO₄. Low concentrations of As (?0.32 μM) were found in the Pleistocene aquifer, while the highest As concentrations were found in the Holocene aquifer. PHREEQC-2 speciation calculations indicated that Fe²⁺ and H₂S concentrations are controlled by equilibrium for disordered mackinawite and precipitation of siderite. An elevated groundwater salinity (Cl range 0.19–65.1 mM) was observed in both aquifers, and dominated in the deep aquifer. A negative correlation between aqueous As and an estimate of reduced SO₄ was observed, indicating that Fe sulphide precipitation poses a secondary control on the groundwater As concentration.     

Role of Quaternary stratigraphy on arsenic-contaminated groundwater from parts of Middle Ganga Plain,UP–Bihar,India

Late Quaternary stratigraphy and sedimentation in the Middle Ganga Plain (MGP) (Uttar Pradesh–Bihar) have influenced groundwater arsenic contamination. Arsenic contaminated aquifers are pervasive within narrow entrenched channels and flood plains (T₀-Surface) of fine-grained grey to black coloured argillaceous organic rich Holocene sediments (Newer Alluvium). Contaminated aquifers are often located close to distribution of abandoned or existing channels and swamps. The Pleistocene Older Alluvium upland terraces (T₂-Surface) made up of oxidized yellowish brown sediments with calcareous and ferruginous concretions and the aquifers within it are free of arsenic contamination. MGP sediments are mainly derived from the Himalaya with minor inputs from the Peninsular India. The potential source of arsenic in MGP is mainly from the Himalaya. The contaminated aquifers in the Terai belt of Nepal are closely comparable in nature and age to those of the MGP. Arsenic was transported from disseminated sources as adsorbed on dispersed phases of hydrated-iron-oxidea and later on released to groundwater mainly by reductive dissolution of hydrated-iron-oxide and corresponding oxidation of organic matter in aquifer. Strong reducing nature of groundwater is indicated by high concentration of dissolved iron (11.06 mg/l). Even within the arsenic-affected areas, dugwells are found to be arsenic safe due to oxyginated nature.     

Origin and extent of fresh groundwater, salty paleowaters and recent saltwater intrusions in Red River flood plain aquifers, Vietnam

A model has been established on the origin and extent of fresh groundwater, salty paleowaters and saltwater from recent seawater intrusions in the Red River flood plain in Vietnam. This was done with geological observations, geophysical borehole logging and transient electromagnetic methods. Salt paleowater is present up to 50–75?km from the coastline, with occurrence controlled by the Holocene transgression. A density-driven leaching of salty porewater has occurred from high-permeability Holocene sediments into underlying Pleistocene deposits, whereas diffusion has dominated in low-permeability layers. In the Pleistocene aquifer, the highest content of dissolved solids is found below two intrinsic valleys with Holocene marine sediments and along the coastline. Recent intrusion of saltwater from the South China Sea is observed in shallow groundwater 35?km inland, probably a result of transport of salty water inland in rivers or leaching of paleowaters from very young near-coast marine sediments. The observed inverted salinity profile, with high saline water overlying fresher groundwater, has been formed due to the global eustatic sea-level changes during the last 8,000–9,000?years. The proposed model may therefore be applicable to other coastal aquifers, with a proper incorporation of the local geological environments.     

Accidents due to oxygen deficiency and methane gas blow-off in Tokyo area,Japan

The groundwater leve in the Tokyo area had declined to about 60 m below the surface because of excess withdrawal of groundwater from various aquifers. Many construction workers died due to oxygen deficiency at construction sites from 1960 to 1980, the period of decreasing groundwater level. The compressed air in pneumatic foundation construction sites passed easily through the aquifer, and the oxygen in it was consumed by ferrous ions oxidizing to ferric ions. During periods of high barometric pressure, atmospheric air penetrates into the strata and it is deoxygenated there. Suffocation occurred not only at construction sites in underground excavations, but also in residences in Tokyo. Such acidents have become less frequent with recovery of the pore-water pressure in aquifers, which has accompanied the recovery of the groundwater level since 1972.With the recovery of the pore-water pressure and the groundwater level in the aquifer, fires and explosions resulting from gushes of methane have occurred in Tokyo lowlands since 1973. These blow-off gases are classified into two types: Kameido and Asakusa.The gas of the Kameido type originates from the Kazusa Group and migrates into upper alluvial deposits or Pleistocene sediments because of the recovery of pore-water pressure in the Kazusa Group. The gas of the Asakusa type formed from the air that penetrated the aquifers during the period of low groundwater level. Methane was produced by the depletion of oxygen accumulated in alluvial deposits and Pleistocene sediments. This gas blows off through wells in alluvial deposits and Pleistocene sediments at times of low barometric pressure. Accidents of the Asakusa type will not happen when the groundwater level and pore-water pressure in alluvial and Pleistocene sediments is restored to previous levels.     

Arsenic in groundwater,Quaternary sediments,and suspended river sediments from the Middle Gangetic Plain,India: distribution,field relations,and geomorphological setting

A groundwater arsenic (As) survey in Mirzapur, Varanasi, Ghazipur, Ballia, Buxar, Ara, Patna, and Vaishali districts of UP and Bihar shows that people from these districts are drinking As-contaminated groundwater (max. 1,300 μg/l). About 66 % of tubewells from Buxar to Mirzapur areas and 89 % of tubewells from Patna to Ballia areas have As?>?10 μg/l (WHO guideline). Moreover, 36 % of tubewells from Buxar to Mirzapur areas and 50 % of tubewells from Patna to Ballia areas have As above 50 μg/l. Most of the As-affected villages are located close to abandoned or present meander channels of the Ganga River. In contrast, tubewells located in Mirzapur, Chunar, Varanasi, Saidpur, Ghazipur, Muhammadabad, Ballia, Buxar, Ara, Chhapra, Patna, and Hazipur towns are As-safe in groundwater because of their positions on the Pleistocene Older Alluvium upland surfaces. The iron (Fe) content in tubewell water samples varies from 0.1 to 12.93 mg/l. About 77 % As-contaminated tubewells are located within the depth of 21 to 40 m in the Holocene Newer Alluvium aquifers. The potential source of As in sediments carried through the rivers from the Himalayas. Maximum As concentrations in the Older and Newer Alluvium sediments are 13.73 and 30.91 mg/kg, respectively. The Himalayas rivers, i.e. Yamuna, Ganga, Gomati, Ghaghara, Gondak, Buri Gandak, and Kosi rivers carrying suspended sediments have high content of As (max. 10.59 mg/kg).     

Occurrence and geochemistry of arsenic in the groundwater of Eastern Croatia

In order to examine the extent of the As enrichment and the factors influencing this enrichment in the groundwater of Eastern Croatia, groundwater samples were collected from 56 production wells in two counties, Osijek-Baranja and Vukovar-Srijem, suspected to be more affected. Hydrochemical analyses were performed at all locations including in situ As speciation at 32 locations. Arsenic was detected in 46 out of 56 groundwater samples with total As concentrations up to 491 μg/L. Thirty-six of the studied wells yielded groundwater with total As concentrations that exceeded the WHO Maximum Contaminant Level for arsenic in drinking water of 10 μg/L. Only inorganic As species were detected with arsenite As(III) as the predominant form. The spatial distribution of As in the groundwater was significantly linked with geological, geomorphological and hydrogeological development of the alluvial basin of the Drava and Sava rivers. The most probable groundwater As sources are deeper sediments from the Middle and Upper Pleistocene. The results obtained suggest that biogeochemical processes controlling As concentration in the groundwater are complex and location-specific. Reductive dissolution of Fe oxides, desorption of As from Fe oxides and/or clay minerals as well as competition for the sorption sites with organic matter and phosphate could be the principal mechanisms that control As mobilization. The extent of those processes vary in the different parts of the Drava and Sava depressions and could be linked to different site related parameters, such as lithology, mineralogy, local hydrology and hydrogeology; thus different processes of As mobilization have been proposed for the different types of water in relation to groundwater evolution.     

Groundwater recharge in suburban areas of Hanoi,Vietnam: effect of decreasing surface-water bodies and land-use change

Over-exploited groundwater is expected to remain the predominant source of domestic water in suburban areas of Hanoi, Vietnam. In order to evaluate the effect on groundwater recharge, of decreasing surface-water bodies and land-use change caused by urbanization, the relevant groundwater systems and recharge pathways must be characterized in detail. To this end, water levels and water quality were monitored for 3 years regarding groundwater and adjacent surface-water bodies, at two typical suburban sites in Hanoi. Stable isotope (δ¹⁸O, δD of water) analysis and hydrochemical analysis showed that the water from both aquifers and aquitards, including the groundwater obtained from both the monitoring wells and the neighboring household tubewells, was largely derived from evaporation-affected surface-water bodies (e.g., ponds, irrigated farmlands) rather than from rivers. The water-level monitoring results suggested distinct local-scale flow systems for both a Holocene unconfined aquifer (HUA) and Pleistocene confined aquifer (PCA). That is, in the case of the HUA, lateral recharge through the aquifer from neighboring ponds and/or irrigated farmlands appeared to be dominant, rather than recharge by vertical rainwater infiltration. In the case of the PCA, recharge by the above-lying HUA, through areas where the aquitard separating the two aquifers was relatively thin or nonexistent, was suggested. As the decrease in the local surface-water bodies will likely reduce the groundwater recharge, maintaining and enhancing this recharge (through preservation of the surface-water bodies) is considered as essential for the sustainable use of groundwater in the area.

     

Recharge and sustainability of a coastal aquifer in northern Albania

The River Mati in Albania has formed a coastal plain with Holocene and Pleistocene sediments. The outer portion of the plain is clay, with three underlying aquifers that are connected to an alluvial fan at the entry of the river into the plain. The aquifers supply water for 240,000 people. Close to the sea the aquifers are brackish. The brackish water is often artesian and found to be thousands of years old. Furthermore, the salinity, supported by δ¹⁸O results, does not seem to be due to mixing with old seawater but due to diffusion from intercalated clay layers. Heavy metals from mines in the upstream section of River Mati are not an immediate threat, as the pH buffering of the river water is good. Moreover, the heavy metals are predominantly found in suspended and colloidal phases. Two sulphur isotope signatures, one mirroring seawater sulphate in the brackish groundwater (δ³⁴S >21 ‰) and one showing the influence of sulphide in the river and the fresh groundwater (δ³⁴S <10 ‰), indicate that the groundwater in the largest well field is recharged from the river. The most serious threat is gravel extraction in the alluvial fan, decreasing the hydraulic head necessary for recharge and causing clogging of sediments.     

Organic carbon mobilization in a Bangladesh aquifer explained by seasonal monsoon-driven storativity changes

Currently, the most widely accepted hypothesis to explain high As concentrations in Bangladesh groundwaters is that dissolved organic C (DOC) reduces solid Fe (hydr)oxides and mobilizes sorbed arsenate. The nature of the DOC and its release mechanism are still controversial. Based on weekly to biweekly sampling over the course of one monsoon cycle at six monitoring wells of different depths, it is proposed that storativity changes drive natural DOC release from clay–peat layers to the adjacent aquifers. With a decrease in hydraulic heads during the dry season, total mineralization and DOC concentrations increased. With the onset of the rainy season and an increase in hydraulic heads, release of clay–peat derived components stopped and vertical water displacement due to groundwater recharge from rainwater occurred, causing aquifer flushing and a decrease in total mineralization and DOC concentrations. Total As and DOC concentrations correlated over depth. However, at the depth of maximum concentrations, the As peak was observed during the rainy season. At present, the reason for this inverse seasonal trend between As and DOC is unclear. Higher mineralization or DOC concentrations could lead to increased As sorption or the increased arsenite release is a time-lag abiotic or microbial response to the DOC peak. The vulnerability of the Pleistocene aquifer towards increased As concentrations was found to be much higher than previously assumed. Though sorption capacities were determined to be higher than in the Holocene aquifer, probably due to intact Fe (hydr)oxides, long-term continuous As input from overlying clay and peat layers by the proposed seasonal storativity changes has led to increased aqueous As concentrations of 85 μg/L, considerably higher than drinking water standards. Until now, aquifer and especially aquitard and aquiclude hydraulics have not been considered sufficiently when attempting to explain As mobilization in Bangladesh.