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Iron minerals are the most important arsenic host in As-contaminated deltaic sediments. Arsenic release from Fe minerals to groundwater exposes millions of people worldwide to a severe health threat. To understand the coupling of Fe mineralogy with As (im)mobilization dynamics, we analyzed the geochemistry and mineralogy of a 46 m long sediment core drilled into the redox transition zone where a high As Holocene aquifer is juxtaposed to a low As Pleistocene aquifer in the Red River delta, Vietnam. We specifically concentrated on mm- to cm-scale redox interfaces within the sandy aquifer. Various Fe phases, such as Fe- and Mn- bearing carbonates, pyrite, magnetite, hematite and Fe-hydroxides (goethite, lepidocrocite) with distinct As concentrations were identified by a combination of high-resolution microscopic, magnetic and spectroscopic methods. The concentration of As and its redox species in the different Fe-minerals were quantified by microprobe analysis and synchrotron X-ray absorption. We developed a conceptual model integrating Fe-mineral transformations and related As (im)mobilization across the redox interfaces. Accordingly, As is first mobilized via the methanogenic dissolution of Fe(III) (oxyhydr)oxide mineral coatings on sand grains when reducing groundwater from the Holocene aquifer intruded into the Pleistocene sands. This stage is followed by the formation of secondary Fe(II)-containing precipitates (mainly Fe- and Mn-bearing carbonates with relatively low As

Iron oxides control the mobility of a host of contaminants in aquifer systems, and the microbial reduction of iron oxides in the subsurface is linked to high levels of arsenic in groundwater that affects greater than 150 million people globally. Paired observations of groundwater and solid-phase aquifer composition are critical to understand spatial and temporal trends in contamination and effectively manage changing water resources, yet field-representative mineralogical data are sparse across redox gradients relevant to arsenic contamination. We characterize iron mineralogy using X-ray absorption spectroscopy across a natural gradient of groundwater arsenic contamination in Vietnam. Hierarchical cluster analysis classifies sediments into meaningful groups delineating weathering and redox changes, diagnostic of depositional history, in this first direct characterization of redox transformations in the field. Notably, these groupings reveal a signature of iron minerals undergoing active reduction before the onset of arsenic contamination in groundwater. Pleistocene sediments undergoing postdepositional reduction may be more extensive than previously recognized due to previous misclassification. By upscaling to similar environments in South and Southeast Asia via multinomial logistic regression modeling, we show that active iron reduction, and therefore susceptibility to future arsenic contamination, is more widely distributed in presumably pristine aquifers than anticipated.

Widespread contamination of groundwater with geogenic arsenic is attributed to microbial dissolution of arsenic-bearing iron (oxyhydr)oxides minerals coupled to the oxidation of organic carbon. The recharge sources to an aquifer can influence groundwater arsenic concentrations by transport of dissolved arsenic or reactive constituents that affect arsenic mobilization. To understand how different recharge sources affect arsenic contamination—in particular through their influence on organic carbon and sulfate cycling—we delineated and quantified recharge sources in the arsenic affected region around Hanoi, Vietnam. We constrained potential end-member compositions and employed a novel end-member mixing model using an ensemble approach to apportion recharge sources. Groundwater arsenic and dissolved organic carbon concentrations are controlled by the dominant source of recharge. High arsenic concentrations are prevalent regardless of high dissolved organic carbon or ammonium levels, indicative of organic matter decomposition, where the dominant recharge source is riverine. In contrast, high dissolved organic carbon and significant organic matter decomposition are required to generate elevated groundwater arsenic where recharge is largely nonriverine. These findings suggest that in areas of riverine recharge, arsenic may be efficiently mobilized from reactive surficial environments and carried from river-aquifer interfaces into groundwater. In groundwaters derived from nonriverine recharge areas, significantly more organic carbon mineralization is required to obtain equivalent levels of arsenic mobilization within inland sediments. This method can be broadly applied to examine the connection between hydrology, geochemistry and groundwater quality.

Although phosphate (PO43-) may play a decisive role in enriching toxic arsenic (As) in the groundwater of many Asian deltas, knowledge gaps exist regarding its interactions with As. This study investigates the simultaneous immobilisation of PO43- and As in aquifer sediments at a redox transition zone in the Red River Delta of Vietnam. The majority of PO43- and As was found to be structurally bound in layers of Fe(III)-(oxyhydr)oxide precipitates, indicating that their formation represents a dominant immobilisation mechanism. This immobilisation was also closely linked to sorption. In the surface sorbed sediment pools, the molar ratios of total P to As were one order of magnitude higher than found in groundwater, reflecting a preferential sorption of PO43- over As. However, this competitive sorption was largely dependent on the presence of Fe(III)-(oxyhydr)oxides. Ongoing contact of the aquifer sediments with iron-reducing groundwater resulted in the reductive dissolution of weakly crystalline Fe(III)-(oxyhydr)oxides, which was accompanied by decreased competition for sorption sites between PO43- and As. Our results emphasise that, to be successful in the medium and long term, remediation approaches and management strategies need to consider competitive sorption between PO43- and As and dynamics of the biogeochemical Fe-cycle.

The fate of arsenic (As) in groundwater is determined by multiple interrelated microbial and abiotic processes that contribute to As (im)mobilization. Most studies to date have investigated individual processes related to As (im)mobilization rather than the complex networks present in situ. In this study, we used RNA-based microbial community analysis in combination with groundwater hydrogeochemical measurements to elucidate the behavior of As along a 2 km transect near Hanoi, Vietnam. The transect stretches from the riverbank across a strongly reducing and As-contaminated Holocene aquifer, followed by a redox transition zone (RTZ) and a Pleistocene aquifer, at which As concentrations are low. Our analyses revealed fermentation and methanogenesis as important processes providing electron donors, fueling the microbially mediated reductive dissolution of As-bearing Fe(III) minerals and ultimately promoting As mobilization. As a consequence of high CH4 concentrations, methanotrophs thrive across the Holocene aquifer and the redox transition zone. Finally, our results underline the role of SO42−-reducing and putative Fe(II)-/As(III)-oxidizing bacteria as a sink for As, particularly at the RTZ. Overall, our results suggest that a complex network of microbial and biogeochemical processes has to be considered to better understand the biogeochemical behavior of As in groundwater.

Lead poisoning is considered a public health threat, particularly in developing countries. Health problems from Pb exposure occur in many parts of the world, especially near Pb mines, Pb smelters, and used lead-acid battery (ULAB) recycling plants. In this study, we analyzed the urine metabolome of residents in a village located near a ULAB recycling facility to investigate the biological effects of Pb exposure (ULAB: n = 44, Reference: n = 51). Lasso linear regression models were moderately predictive of blood Pb levels, as evaluated by a training set (R2 = 0.813) and against an external test set (R2EXT = 0.647). In lasso logistic regression models, areas under receiver operating characteristic curves, as measured by 5-fold cross-validation (AUCCV = 0.871) and against an external test set (AUCEXT = 0.917), indicated accurate classification of urine samples from the affected village and from a reference site. Ten candidate biomarkers identified at false discovery rates of

The migration of arsenic (As) enriched groundwater into Pleistocene aquifers as a consequence of extensive groundwater abstraction represents an increasing threat to the precious water resources in Asian delta regions. Pleistocene aquifer sediments are typically rich in FeIII-(hydr)oxides and are capable to adsorb high amounts of As. This results in a pronounced accumulation of As in Pleistocene aquifers, where high As groundwater infiltrates from adjacent Holocene aquifers. However, As retention by Pleistocene aquifers over long-term time scales remains largely unknown. We studied As sorption in situ by placing natural Pleistocene sediments and pure mineral phases directly inside groundwater monitoring wells at a study site near Hanoi (Vietnam). This in situ exposure allows for constant flushing of the samples with unaltered groundwater and the establishment of undisturbed sorption equilibria similar to those in local aquifer sediments, which is not readily attainable in traditional laboratory sorption experiments. The groundwaters in our experimental wells were characterized by different As concentrations (0.01–6.63 μmol/L) and redox states, reaching from suboxic to anoxic conditions (Eh of +159 to −4 mV). Results show that adsorption is the dominant As retention mechanism, independent from the respective groundwater chemistry (i.e. concentrations of dissolved P, HCO3− and Si). Whilst most of the As sorbed within the first week, sorption further increased slowly but consistently by 6–189%, respectively, within six months. Hence, the As sorption behavior of Pleistocene aquifer sediments should be determined over longer periods to avoid an underestimation of the As sorption capacity. Accompanying desorption experiments revealed that about 51% of the sorbed As was remobilized within six months when exposed to low As groundwater. We therefore conclude that a considerable proportion of the As accumulated in the aquifer sediments is prone to remobilization once the As concentrations in migrating groundwater decline. Remobilization of As should be considered in local water management plans to avoid contamination of precious groundwater resources with this As legacy.

Geogenic arsenic (As) contamination of groundwater poses a major threat to global health, particularly in Asia. To mitigate this exposure, groundwater is increasingly extracted from low-As Pleistocene aquifers. This, however, disturbs groundwater flow and potentially draws high-As groundwater into low-As aquifers. Here we report a detailed characterisation of the Van Phuc aquifer in the Red River Delta region, Vietnam, where high-As groundwater from a Holocene aquifer is being drawn into a low-As Pleistocene aquifer. This study includes data from eight years (2010–2017) of groundwater observations to develop an understanding of the spatial and temporal evolution of the redox status and groundwater hydrochemistry. Arsenic concentrations were highly variable (0.5–510 μg/L) over spatial scales of, Science of The Total Environment, 717, ISSN:0048-9697, ISSN:1879-1026

Many aquifers that are highly contaminated by arsenic in South and Southeast Asia are in the floodplains of large river networks. Under natural conditions, these aquifers would discharge into nearby rivers; however, large-scale groundwater pumping has reversed the flow in some areas so that rivers now recharge aquifers. At a field site near Hanoi Vietnam, we find river water recharging the aquifer becomes high in arsenic, reaching concentrations above 1000 µg/L, within the upper meter of recently ( 50 µg/L) aqueous arsenic concentrations are found in aquifer regions adjacent to zones where the river has recently deposited sediment and low arsenic concentrations are found in aquifer regions adjacent to erosional zones. High arsenic concentrations are even found adjacent to a depositional river reach in a Pleistocene aquifer, a type of aquifer sediment which generally hosts low arsenic water. Using geochemical and isotopic data, we estimate the in situ rate of arsenic release from riverbed sediments to be up to 1000 times the rates calculated on inland aquifer sediments in Vietnam. Geochemical data for riverbed porewater conditions indicate that the reduction of reactive, poorly crystalline iron oxides controls arsenic release. We suggest that aquifers in these regions may be susceptible to further arsenic contamination where riverine recharge drawn into aquifers by extensive groundwater pumping flows through recently deposited river sediments before entering the aquifer.

The arsenic content in groundwater of the Red River floodplain decreases with the burial age of the aquifer sediment over a 6000 year period. This decrease is caused by diminishing reactivities of both sedimentary organic carbon, Fe-oxides as well as CaCO3. Here we present a 1-D reactive transport model developed in PHREEQC-3 that quantifies the resulting changes in groundwater bulk chemistry as well as arsenic content over the last six millennia.

Recharge of Red River water into arsenic-contaminated aquifers below Hanoi was investigated. The groundwater age at 40 m depth in the aquifer underlying the river was 1.3 ± 0.8 years, determined by tritium–helium dating. This corresponds to a vertical flow rate into the aquifer of 19 m/year. Electrical conductivity and partial pressure of CO2 (PCO2) indicate that water recharged from the river is present in both the sandy Holocene and gravelly Pleistocene aquifers and is also abstracted by the pumping station. Infiltrating river water becomes anoxic in the uppermost aquifer due to the oxidation of dissolved organic carbon. Further downward, sedimentary carbon oxidation causes the reduction of As-containing Fe-oxides. Because the release of arsenic by reduction of Fe-oxides is controlled by the reaction rate, arsenic entering the solution becomes highly diluted in the high water flux and contributes little to the groundwater arsenic concentration. Instead, the As concentration in the groundwater of up to 1 μM is due to equilibrium-controlled desorption of arsenic, adsorbed to the sediment before river water started to infiltrate due to municipal pumping. Calculations indicate that it will take several decades of river water infiltration to leach arsenic from the Holocene aquifer to below the World Health Organization limit of 10 μg/L.

Groundwater drawn daily from shallow alluvial sands by millions of wells over large areas of south and southeast Asia exposes an estimated population of over a hundred million people to toxic levels of arsenic. Holocene aquifers are the source of widespread arsenic poisoning across the region. In contrast, Pleistocene sands deposited in this region more than 12,000 years ago mostly do not host groundwater with high levels of arsenic. Pleistocene aquifers are increasingly used as a safe source of drinking water and it is therefore important to understand under what conditions low levels of arsenic can be maintained. Here we reconstruct the initial phase of contamination of a Pleistocene aquifer near Hanoi, Vietnam. We demonstrate that changes in groundwater flow conditions and the redox state of the aquifer sands induced by groundwater pumping caused the lateral intrusion of arsenic contamination more than 120 metres from a Holocene aquifer into a previously uncontaminated Pleistocene aquifer. We also find that arsenic adsorbs onto the aquifer sands and that there is a 16-20-fold retardation in the extent of the contamination relative to the reconstructed lateral movement of groundwater over the same period. Our findings suggest that arsenic contamination of Pleistocene aquifers in south and southeast Asia as a consequence of increasing levels of groundwater pumping may have been delayed by the retardation of arsenic transport.

Human exposure to lead (Pb) due to uncontrolled Pb-acid battery recycling has been an environmental health issue in newly developed industrial regions. We conducted a human monitoring survey in Dong Mai, a battery recycling village in Vietnam, to assess exposure status to Pb. Lead level was measured in hair, blood and urine samples of residents in Dong Mai and two reference sites during 4 years spanning 2007–2011. In Dong Mai, Pb levels in three matrixes were significantly higher than those in reference sites. Blood Pb levels of all adults and children exceeded 10 μg/dL, the Centers for Disease Control and Prevention definition of an elevated blood Pb level. Clear increase of urinary δ-aminolevulinic acid (ALA) level with increasing blood Pb level indicated disruption of heme synthesis. One adult exceeded 100 μg/dL of blood Pb, where encephalopathy is of concern. The blood Pb levels achieved various toxic effect threshold values, and elevated blood Pb was not limited to recycling workers, but was also in children and women of reproductive age. Serious pollution status of Dong Mai village suggests an importance of further monitoring surveys in various developing Asian countries.

Three surface complexation models (SCMs) developed for, respectively, ferrihydrite, goethite and sorption data for a Pleistocene oxidized aquifer sediment from Bangladesh were used to explore the effect of multicomponent adsorption processes on As mobility in a reduced Holocene floodplain aquifer along the Red River, Vietnam. The SCMs for ferrihydrite and goethite yielded very different results. The ferrihydrite SCM favors As(III) over As(V) and has carbonate and silica species as the main competitors for surface sites. In contrast, the goethite SCM has a greater affinity for As(V) over As(III) while PO43− and Fe(II) form the predominant surface species. The SCM for Pleistocene aquifer sediment resembles most the goethite SCM but shows more Si sorption. Compiled As(III) adsorption data for Holocene sediment was also well described by the SCM determined for Pleistocene aquifer sediment, suggesting a comparable As(III) affinity of Holocene and Pleistocene aquifer sediments. A forced gradient field experiment was conducted in a bank aquifer adjacent to a tributary channel to the Red River, and the passage in the aquifer of mixed groundwater containing up to 74% channel water was observed. The concentrations of As (

The adsorption of arsenic onto aquifer sediment from the Red River floodplain, Vietnam, was determined in a series of batch experiments. Due to water supply pumping, river water infiltrates into the aquifer at the field site and has leached the uppermost aquifer sediments. The leached sediments remain anoxic but contain little reactive arsenic and iron, and are used in our experiments. The adsorption and desorption experiments were carried out by addition or removal of arsenic from the aqueous phase in sediment suspensions under strictly anoxic conditions. Also the effects of HCO3, Fe(II), PO4 and Si on arsenic adsorption were explored. The results show much stronger adsorption of As(V) as compared to As(III), full reversibility for As(III) adsorption and less so for As(V). The presence or absence of HCO3 did not influence arsenic adsorption. Fe(II) enhanced As(V) sorption but did not influence the adsorption of As(III) in any way. During simultaneous adsorption of As(III) and Fe(II), As(III) was found to be fully desorbable while Fe(II) was completely irreversibly adsorbed and clearly the two sorption processes are uncoupled. Phosphate was the only solute that significantly could displace As(III) from the sediment surface. Compiling literature data on arsenic adsorption to aquifer sediment in Vietnam and Bangladesh revealed As(III) isotherms to be almost identical regardless of the nature of the sediment or the site of sampling. In contrast, there was a large variation in As(V) adsorption isotherms between studies. A tentative conclusion is that As(III) and As(V) are not adsorbing onto the same sediment surface sites. The adsorption behavior of arsenic onto aquifer sediments and synthetic Fe-oxides is compared. Particularly, the much stronger adsorption of As(V) than of As(III) onto Red River as well as on most Bangladesh aquifer sediments, indicates that the perception that arsenic, phosphate and other species compete for the same surface sites of iron oxides in sediments with properties similar to those of, for example a synthetic goethite, probably is not correct. A simple two-component Langmuir adsorption model was constructed to quantitatively describe the reactive transport of As(III) and PO4 in the aquifer.

Arsenic contamination of groundwater continues to threaten the health of millions of people in southeast Asia. The oxidation of organic carbon, coupled to the reductive dissolution of arsenic-bearing iron oxides, is thought to control the release of sediment-bound arsenic into groundwater. However, the cause of the high spatial variability in groundwater arsenic concentrations—which can range from 5 to 500 μg l−1 within distances of a few kilometres—has been uncertain. Here, we combine measurements of sediment age, organic-matter reactivity and water chemistry at four locations along a cross-section of the arsenic-contaminated Red River floodplain in Vietnam to determine the origin of variations in groundwater arsenic concentrations. The burial age of the aquifer sediments, determined using optical stimulated luminescence, ranged from 460 years near the course of the present-day river to 5,900 years at the margin of the floodplain. The groundwater arsenic content and the reactivity of sedimentary organic carbon, determined using radiotracer measurements of the rate of methanogenesis, declined with sediment age. The sedimentary pools of both iron and arsenic also declined with the burial age of the sediments. We suggest that the age of aquifer sediments is a key determinant of groundwater arsenic concentrations. Arsenic contamination of groundwater threatens the health of millions of people in southeast Asia. Measurements in an arsenic-contaminated aquifer in Vietnam point to sediment age as a key determinant of groundwater arsenic concentrations.

Few studies have investigated the human exposure to the ensemble of dioxin-related compounds (DRCs) released from uncontrolled e-waste recycling, especially from a toxic effect standpoint. This study evaluated the TCDD toxic equivalents (TEQs) in persistent extracts of settled house dust from two Vietnamese e-waste recycling sites (EWRSs) using the Dioxin-Responsive Chemically Activated LUciferase gene eXpression assay (DR-CALUX), combined with chemical analysis of PCDD/Fs, DL-PCBs, PBDD/Fs, and monobromo PCDD/Fs to determine their TEQ contribution. The CALUX-TEQ levels in house dust ranged from 370 to 1000 pg g(-1) in the EWRSs, approximately 3.5-fold higher than in the urban control site. In EWRS house dust, the concentrations of the unregulated PBDFs were 7.7-63 ng g(-1), an order of magnitude higher than those of regulated DRCs (PCDD/Fs and DL-PCBs), and PBDFs were also principal CALUX-TEQ contributors (4.2-22%), comparable to PCDD/Fs (8.1-29%). The CALUX-TEQ contribution of DRCs varied, possibly depending on thermal processing activities (higher PCDD/F-TEQs) and PBDE content in the waste (higher PBDF-TEQs). However, the percentage of unknown dioxin-like activities was high in all dust samples, indicating large contribution from unidentified DRCs and/or synergy among contaminants. Estimates of TEQ intake from dust ingestion suggest that children in the EWRSs may be adversely affected by DRCs from dust.

To elucidate the role of genetic factors in arsenic (As) metabolism, we studied associations of single nucleotide polymorphisms (SNPs) in As (+3 oxidation state) methyltransferase (AS3MT) with the As concentrations in hair and urine, and urinary As profile in residents in the Red River Delta, Vietnam. Concentrations of total As in groundwater were 0.7-502 mug/l. Total As levels in groundwater drastically decreased by using sand filter, indicating that the filter could be effective to remove As from raw groundwater. Concentrations of inorganic As (IAs) in urine and total As in hair of males were higher than those of females. A significant positive correlation between monomethylarsonic acid (MMA)/IAs and age in females indicates that older females have higher methylation capacity from IAs to MMA. Body mass index negatively correlated with urinary As concentrations in males. Homozygote for SNPs 4602AA, 35991GG, and 37853GG, which showed strong linkage disequilibrium (LD), had higher percentage (%) of dimethylarsinic acid (DMA) in urine. SNPs 4740 and 12590 had strong LD and associated with urinary %DMA. Although SNPs 6144, 12390, 14215, and 35587 comprised LD cluster, homozygotes in SNPs 12390GG and 35587CC had lower DMA/MMA in urine, suggesting low methylation capacity from MMA to DMA in homo types for these SNPs. SNPs 5913 and 8973 correlated with %MMA and %DMA, respectively. Heterozygote for SNP 14458TC had higher MMA/IAs in urine than TT homozygote, indicating that the heterozygote may have stronger methylation ability of IAs. To our knowledge, this is the first study on the association of genetic factors with As metabolism in Vietnamese.

Groundwater contamination by arsenic is a serious environmental problem in the world. Yet there have been few studies conducted in Southeast Asian countries. This article surveys arsenic contamination in groundwater and residents from Vietnam, and is based on our previous studies. Samples of groundwater (n = 118), human hair (n = 59), and urine (n = 100) were collected in the Red River and Mekong River Deltas during 2001–2004. Arsenic was detected in most of the groundwater samples, and its level ranged from

The spatial variability of As concentrations in aquifers of the Red River Delta, Vietnam, was studied in the vicinity of Hanoi. Two sites, only 700 m apart but with very different As concentrations in groundwater (site L: NH 4 + (∼10 mg/L), HCO 3 - (500 mg/L) and dissolved P (600 mg/L), in addition to elevated As at site H are consistent with a release coupled to microbially induced reductive dissolution of Fe oxyhydroxides. Other processes such as precipitation of siderite and vivianite, which are strongly supersaturated at site H, or the formation of amorphous Fe(II)/As(III) phases and Fe sulfides, may also influence the partitioning of As between groundwater and aquifer sands. The origin of the redox contrast between the two sites is presently unclear. Peat was observed at site L, but it was embedded within a thick clayey silt layer. At site H, instead, organic rich layers were only separated from the underlying aquifer by thin silt layers. Leaching of organic matter from this source could cause reducing conditions and therefore potentially be related to particularly high concentrations of dissolved NH 4 + , HCO 3 - , P and DOC in the portion of the aquifer where groundwater As concentrations are also elevated.

Groundwater contamination by arsenic in Vietnam poses a serious health threat to millions of people. In the larger Hanoi area, elevated arsenic levels are present in both, the Holocene and Pleistocene aquifers. Family-based tubewells predominantly tap the Holocene aquifer, while the Hanoi water works extract more than 600,000 m3/day of groundwater from the Pleistocene aquifer. Detailed groundwater and sediment investigations were conducted at three locations exhibiting distinct geochemical conditions, i.e., i) high levels of dissolved arsenic (av. 121 µg/L) at the river bank, ii) low levels of dissolved arsenic (av. 21 µg/L) at the river bank and, iii) medium levels of dissolved arsenic (60 µg/L) in an area of buried peat and excessive groundwater abstraction. Seasonal fluctuations in water chemistry were studied over a time span of 14 months. Sediment-bound arsenic (1.3–22 µg/g) is in a natural range. Arsenic correlates with iron (r2 > 0.8) with variation related to grain size. Sediment leaching experiments showed that arsenic can readily be mobilized at each of the three locations. Low levels of arsenic in groundwater (< 10 µg/L) generally exhibit manganese reducing conditions, whereas elevated levels are caused by reductive dissolution under iron- and sulphate reducing conditions. Average arsenic concentrations in groundwater are twofold higher at the river bank than in the peat area. The lower levels of arsenic contamination in the peat area are likely controlled by the high abundance of iron present in both the aqueous and sediment phases. With median molar Fe/As ratios of 350 in water and 8700 in the sediments of the peat area, reduced iron possibly forms new mineral phases that resorb (or sequester) previously released arsenic to the sediment. Despite similar redox conditions, resorption is much less significant at the river bank (Fe/As(aq) = 68, Fe/As(s) = 4700), and hence, arsenic concentrations in groundwater reach considerably higher levels. Drawdown of Holocene water to the Pleistocene aquifer in the peat area, caused by the pumping for the Hanoi water works, clearly promotes reducing conditions in Pleistocene groundwater. This demonstrates that excessive abstraction of water from deep wells, i.e., wells tapping water below the arsenic burdened depth, can cause a downward shift of iron-reducing conditions and concurrently mobilize arsenic along the way. Vertical migration of reduced groundwater may also impact aquifers under natural hydrological conditions. Seepage of DOC-enriched groundwater derived from degradation of organic matter in the clayey sediments at the river bank was observed to enhance (and maintain) iron-reducing conditions in the aquifer where organic matter is scarce. Once the aquifer becomes reduced, arsenic is released from the aquifer solid-hosts but additionally derives from the arsenic-enriched groundwater seeping from the clay into the aquifer. This behaviour is an important mechanism for arsenic contamination in aquifers that might not necessarily contain enough organic matter in their sediments to induce reducing conditions independently.

Large alluvial deltas of the Mekong River in southern Vietnam and Cambodia and the Red River in northern Vietnam have groundwaters that are exploited for drinking water by private tube-wells, which are of increasing demand since the mid-1990s. This paper presents an overview of groundwater arsenic pollution in the Mekong delta: arsenic concentrations ranged from 1-1610 microg/L in Cambodia (average 217 microg/L) and 1-845 microg/L in southern Vietnam (average 39 microg/L), respectively. It also evaluates the situation in Red River delta where groundwater arsenic concentrations vary from 1-3050 microg/L (average 159 microg/L). In addition to rural areas, the drinking water supply of the city of Hanoi has elevated arsenic concentrations. The sediments of 12-40 m deep cores from the Red River delta contain arsenic levels of 2-33 microg/g (average 7 microg/g, dry weight) and show a remarkable correlation with sediment-bound iron. In all three areas, the groundwater arsenic pollution seem to be of natural origin and caused by reductive dissolution of arsenic-bearing iron phases buried in aquifers. The population at risk of chronic arsenic poisoning is estimated to be 10 million in the Red River delta and 0.5-1 million in the Mekong delta. A subset of hair samples collected in Vietnam and Cambodia from residents drinking groundwater with arsenic levels50 microg/L have a significantly higher arsenic content than control groups (50 microg/L). Few cases of arsenic related health problems are recognized in the study areas compared to Bangladesh and West Bengal. This difference probably relates to arsenic contaminated tube-well water only being used substantially over the past 7 to 10 years in Vietnam and Cambodia. Because symptoms of chronic arsenic poisoning usually take more than 10 years to develop, the number of future arsenic related ailments in Cambodia and Vietnam is likely to increase. Early mitigation measures should be a high priority.

Arsenic metabolism affects the susceptibility of humans to arsenic toxicity; therefore, clarification of the factors associated with individual variations in arsenic metabolism is an important task. Genetic polymorphisms such as single nucleotide polymorphisms (SNPs) in arsenic (+3 oxidation state) methyltransferase (AS3MT), which can methylate arsenic compounds using S-adenosyl-l-methionine (AdoMet), have been reported to modify arsenic methylation. In this review, we summarize studies conducted by us in Vietnam and by others on the association of AS3MT genetic polymorphisms with arsenic metabolism as well as human health effects. Most of the SNPs in AS3MT showed inconsistent results in terms of genotype-dependent differences in arsenic metabolism among the studies. However, AS3MT 12390 (rs3740393) and 14458 (rs11191439) were consistently related to arsenic methylation regardless of the study population: AS3MT 12390 (rs3740393) affected the second step of methylation of arsenic, whereas 14458 (rs11191439) affected the first methylation step.

The haptoglobin (HP) gene deletion allele (HP(del)) is responsible for anhaptoglobinemia and a genetic risk factor for anaphylaxis reaction after transfusion due to production of the anti-HP antibody. The distribution of this allele has been explored by several groups including ours. Here, we studied the frequency of HP(del) in addition to the distribution of common HP genotypes in 293 Vietnamese. The HP(del) was encountered with the frequency of 0.020. The present result suggested that this deletion allele is restricted to East and Southeast Asians. Thus, this allele seems to be a potential ancestry informative marker for these populations.

This study demonstrated the contamination levels of polychlorinated biphenyls (PCBs), hydroxylated PCBs (OH-PCBs), polybrominated diphenyl ethers (PBDEs), methoxylated PBDEs (MeO-PBDEs), hydroxylated PBDEs (OH-PBDEs), and bromophenols (BPhs), and their relationships with thyroid hormones (THs), in the serum of human donors from an e-waste recycling site and a rural site in Hung Yen province, Vietnam. Occupationally related exposure was indicated by significantly higher residue levels of PCBs, OH-PCBs, PBDEs, and BPhs in the serum of donors from the e-waste recycling site (median: 420, 160, 290, and 300pgg(-1) wet wt, respectively) than those in the serum of donors from the rural site (median: 290, 82, 230, and 200pgg(-)(1) wet wt, respectively). On the other hand, levels of OH-/MeO-PBDEs were significantly higher in serum of donors from the reference site (median: 160 and 20pgg(-1) wet wt, respectively) than in those from the e-waste recycling site (median: 43 and 0.52pgg(-1) wet wt, respectively). In addition, we implemented stepwise generalized linear models to assess the association between the levels of TH and PCBs, PBDEs, and their related compounds. In females, we found positive associations of PCBs and OH-PCB concentrations with total thyroxine, free thyroxine, total triiodothyronine, and free triiodothyronine, and a negative association with thyroid-stimulating hormone concentrations.

Household sand filters are applied to treat arsenic- and iron-containing anoxic groundwater that is used as drinking water in rural areas of North Vietnam. These filters immobilize poisonous arsenic (As) via co-oxidation with Fe(II) and sorption to or co-precipitation with the formed Fe(III) (oxyhydr)oxides. However, information is lacking regarding the effect of the frequency and duration of filter use as well as of filter sand replacement on the residual As concentrations in the filtered water and on the presence of potentially pathogenic bacteria in the filtered and stored water. We therefore scrutinized a household sand filter with respect to As removal efficiency and the presence of fecal indicator bacteria in treated water as a function of filter operation before and after sand replacement. Quantification of As in the filtered water showed that periods of intense daily use followed by periods of non-use and even sand replacement did not significantly (p

Perchlorate (ClO4 −) and thiocyanate (SCN−) interfere with iodide (I−) uptake by the sodium/iodide symporter, and thereby these anions may affect the production of thyroid hormones (THs) in the thyroid gland. Although human exposure to perchlorate and thiocyanate has been studied in the United States and Europe, few investigations have been performed in Asian countries. In this study, we determined concentrations of perchlorate, thiocyanate, and iodide in 131 serum samples collected from 2 locations in Northern Vietnam, Bui Dau (BD; electrical and electronic waste [e−waste] recycling site) and Doung Quang (DQ; rural site) and examined the association between serum levels of these anions with levels of THs. The median concentrations of perchlorate, thiocyanate, and iodide detected in the serum of Vietnamese subjects were 0.104, 2020, and 3.11 ng mL−1, respectively. Perchlorate levels were significantly greater in serum of the BD population (median 0.116 ng mL−1) than those in the DQ population (median 0.086 ng mL−1), which indicated greater exposure from e-waste recycling operations by the former. Serum concentrations of thiocyanate were not significantly different between the BD and DQ populations, but increased levels of this anion were observed among smokers. Iodide was a significant positive predictor of serum levels of FT3 and TT3 and a significant negative predictor of thyroid-stimulating hormone in males. When the association between serum levels of perchlorate or thiocyanate and THs was assessed using a stepwise multiple linear regression model, no significant correlations were found. In addition to greater concentrations of perchlorate detected in the e-waste recycling population, however, given that lower concentrations of iodide were observed in the serum of Vietnamese females, detailed risk assessments on TH homeostasis for females inhabiting e-waste recycling sites, especially for pregnant women and their neonates, are required.

Vietnam is an agricultural country with a population of about 88 million, with some 18 million inhabitants living in the Red River Delta in Northern Vietnam. The present study reports the chemical analyses of 68 water and 213 biological (human hair and urine) samples conducted to investigate arsenic contamination in tube well water and human arsenic exposure in four districts (Tu Liem, Dan Phuong, Ly Nhan, and Hoai Duc) in the Red River Delta. Arsenic concentrations in groundwater in these areas were in the range of

The human FUT2 gene encodes a secretor-type α(1,2)fucosyltransferase, and many population-specific polymorphisms have been reported in the coding region.Direct sequencing, real-time polymerase chain reaction, and high-resolution melt (HRM) analysis were done to detect single-nucleotide polymorphism (SNPs) and copy number variations (CNVs) in a Vietnamese population. The impacts of two novel mutations on the encoded enzyme were examined by a transient expression study.The major nonfunctional allele in the 294 Vietnamese was se(357,385), whereas no CNV was detected. Two novel SNPs, 818CA (Thr273Asn) and 853GA (Ala285Thr), distributed at low frequency, were shown to remarkably affect the enzyme activity.The allelic polymorphism of FUT2 in Vietnamese is similar to that of other East and Southeast Asian populations. This result may reflect the history and gene flow of this population. In addition, HRM analysis seems to be a simple and effective method for screening rare SNPs of FUT2 in a large number of samples. [Correction statement added after online publication 21-Dec-2011: Thr273Ala has been updated to Thr273Asn throughout.]

We investigated the association of As exposure and genetic polymorphism in glutathione S-transferase π1 (GSTP1) with As metabolism in 190 local residents from the As contaminated groundwater areas in the Red River Delta, Vietnam. Total As concentrations in groundwater ranged from0.1 to 502 μg l(-1). Concentrations of dimethylarsinic acid (DMA(V)), monomethylarsonic acid (MMA(V)), and arsenite (As(III)) in human urine were positively correlated with total As levels in the groundwater, suggesting that people in these areas may be exposed to As through the groundwater. The concentration ratios of urinary As(III)/arsenate (As(V)) and MMA(V)/inorganic As (IA; As(III) + As(V))(M/I), which are indicators of As metabolism, increased with the urinary As level. Concentration and proportion of As(III) were high in the wild type of GSTP1 Ile105Val compared with the hetero type, and these trends were more pronounced in the higher As exposure group (56 μg l(-1) creatinine in urine), but not in the lower exposure group. In the high As exposure group, As(III)/As(V) ratios in the urine of wild type of GSTP1 Ile105Val were significantly higher than those of the hetero type, while the opposite trend was observed for M/I. These results suggest that the excretion and metabolism of IA may depend on both the As exposure level and the GSTP1 Ile105Val genotype.

In this review, we summarize the current knowledge on exposure, metabolism, and health effects of arsenic (As) in residents from As-contaminated groundwater areas of Vietnam and Cambodia based on our findings from 2000 and other studies. The health effects of As in humans include severe gastrointestinal disorders, hepatic and renal failure, cardiovascular disturbances, skin pigmentation, hyperkeratosis, and cancers in the lung, bladder, liver, kidney, and skin. Arsenic contamination in groundwater is widely present at Vietnam and Cambodia and the highest As levels are frequently found in groundwater from Cambodia. Sand filter system can reduce As concentration in raw groundwater. The results of hair and urine analyses indicate that residents from these As-contaminated areas are exposed to As. In general, sex, age, body mass index, and As exposure level are significantly associated with As metabolism. Genetic polymorphisms in arsenic (+III) methyltransferase and glutathione-S-transferase isoforms may be influenced As metabolism and accumulation in a Vietnamese population. It is suggested oxidative DNA damage is caused by exposure to As in groundwater from residents in Cambodia. An epidemiologic study on an association of As exposure with human health effects is required in these areas.

To elucidate the role of genetic factors in arsenic metabolism, we investigated associations of genetic polymorphisms in the members of glutathione S-transferase (GST) superfamily with the arsenic concentrations in hair and urine, and urinary arsenic profile in residents in the Red River Delta, Vietnam. Genotyping was conducted for GST omega1 (GSTO1) Ala140Asp, Glu155del, Glu208Lys, Thr217Asn, and Ala236Val, GST omega2 (GSTO2) Asn142Asp, GST pi1 (GSTP1) Ile105Val, GST mu1 (GSTM1) wild/null, and GST theta1 (GSTT1) wild/null. There were no mutation alleles for GSTO1 Glu208Lys, Thr217Asn, and Ala236Val in this population. GSTO1 Glu155del hetero type showed higher urinary concentration of As{sup V} than the wild homo type. Higher percentage of DMA{sup V} in urine of GSTM1 wild type was observed compared with that of the null type. Strong correlations between GSTP1 Ile105Val and arsenic exposure level and profile were observed in this study. Especially, heterozygote of GSTP1 Ile105Val had a higher metabolic capacity from inorganic arsenic to monomethyl arsenic, while the opposite trend was observed for ability of metabolism from As{sup V} to As{sup III}. Furthermore, other factors including sex, age, body mass index, arsenic level in drinking water, and genotypes of As (+ 3 oxidation state) methyltransferase (AS3MT) were also significantly co-associatedmore » with arsenic level and profile in the Vietnamese. To our knowledge, this is the first study indicating the associations of genetic factors of GST superfamily with arsenic metabolism in a Vietnamese population.« less

This study presents a transnational groundwater survey of the 62,000 km2 Mekong delta floodplain (Southern Vietnam and bordering Cambodia) and assesses human health risks associated with elevated concentrations of dissolved toxic elements. The lower Mekong delta generally features saline groundwater. However, where groundwater salinity is

Arsenic removal efficiencies of 43 household sand filters were studied in rural areas of the Red River Delta in Vietnam. Simultaneously, raw groundwater from the same households and additional 31 tubewells was sampled to investigate arsenic coprecipitation with hydrous ferric iron from solution, i.e., without contact to sand surfaces. From the groundwaters containing 10-382 microg/L As,0.1-48 mg/L Fe,0.01-3.7 mg/L P, and 0.05-3.3 mg/L Mn, similar average removal rates of 80% and 76% were found for the sand filter and coprecipitation experiments, respectively. The filtering process requires only a few minutes. Removal efficiencies of Fe, phosphate, and Mn were99%, 90%, and 71%, respectively. The concentration of dissolved iron in groundwater was the decisive factor for the removal of arsenic. Residual arsenic levels below 50 microg/L were achieved by 90% of the studied sand filters, and 40% were even below 10 microg/L. Fe/As ratios ofor = 50 oror = 250 were required to ensure arsenic removal to levels below 50 or 10 microg/L, respectively. Phosphate concentrations2.5 mg P/L slightly hampered the sand filter and coprecipitation efficiencies. Interestingly, the overall arsenic elimination was higher than predicted from model calculations based on sorption constants determined from coprecipitation experiments with artificial groundwater. This observation is assumed to result from As(lll) oxidation involving Mn, microorganisms, and possibly dissolved organic matter present in the natural groundwaters. Clear evidence of lowered arsenic burden for people consuming sand-filtered water is demonstrated from hair analyses. The investigated sand filters proved to operate fast and robust for a broad range of groundwater composition and are thus also a viable option for mitigation in other arsenic affected regions. An estimation conducted for Bangladesh indicates that a median residual level of 25 microg/L arsenic could be reached in 84% of the polluted groundwater. The easily observable removal of iron from the pumped water makes the effect of a sand filter immediately recognizable even to people who are not aware of the arsenic problem.

In this study, we report the first ever large-scale environmental validation of a microbial reporter-based test to measure arsenic concentrations in natural water resources. A bioluminescence-producing arsenic-inducible bacterium based on Escherichia coli was used as the reporter organism. Specific protocols were developed with the goal to avoid the negative influence of iron in groundwater on arsenic availability to the bioreporter cells. A total of 194 groundwater samples were collected in the Red River and Mekong River Delta regions of Vietnam and were analyzed both by atomic absorption spectroscopy (AAS) and by the arsenic bioreporter protocol. The bacterial cells performed well at and above arsenic concentrations in groundwater of 7 microg/L, with an almost linearly proportional increase of the bioluminescence signal between 10 and 100 microg As/L (r2 = 0.997). Comparisons between AAS and arsenic bioreporter determinations gave an overall average of 8.0% false negative and 2.4% false positive identifications for the bioreporter prediction at the WHO recommended acceptable arsenic concentration of 10 microg/L, which is far betterthan the performance of chemical field test kits. Because of the ease of the measurement protocol and the low application cost, the microbiological arsenic test has a great potential in large screening campaigns in Asia and in other areas suffering from arsenic pollution in groundwater resources.

Concentrations of As and other trace elements and their association were examined in groundwater (n = 25) and human hair (n = 59) collected at Gia Lam District and Thanh Tri District, suburban areas of Hanoi, Vietnam, in September 2001. Concentrations of As in the groundwater ranged from

Environmental context Household sand filters are widely used in Vietnam to remove As, Fe and Mn from groundwater used as drinking water. From the solid-phase characterisation of a sand filter that has been used for 8 years, we conclude that As and Fe are retained by a combination of fast sorption reactions, surface-catalysed Fe oxidation and mediated As co-oxidation and that microbial processes are probably involved in effective Mn retention. This study contributes to a better mechanistic understanding of filter functioning as a basis for further improvements in filter design and operation. Abstract Household sand filters are widely used in Vietnam to remove As, Fe and Mn from anoxic groundwater used as a drinking water resource. To expand the mechanistic knowledge of the filter functioning, we investigated the bulk and micrometre-scale distribution of Fe, As, P and Mn and the speciation of Fe, Mn and As in a sand filter after 8 years of operation using bulk and micro-focussed X-ray fluorescence spectrometry (XRF) and X-ray absorption spectroscopy (XAS) and scanning electron microscopy coupled with energy dispersive X-ray detection (SEM-EDX). Effective oxygenation of the anoxic groundwater enables the oxidative removal of Fe, As and Mn in the filter sand. Our results show that Fe is retained in the filter as a 2-line ferrihydrite-like FeIII-precipitate that coats sand grains, and that As accumulates dominantly as pentavalent arsenate. The very close spatial correlation of accumulated As and P with Fe throughout the filter sand and down to the micrometre-scale and the effective Fe, P and As retention at an estimated average water residence time of only 30min suggest that their uptake is governed by a combination of fast sorption reactions, surface-catalysed FeII oxidation and mediated AsIII co-oxidation. In contrast, Mn is retained in separate MnIV/III-(oxyhydr)oxide coatings and concretions, probably as a result of coupled surface-catalysed and microbial MnII oxidation. Silicate sorbed to the ferrihydrite-like FeIII-coatings inhibits their crystallisation and associated remobilisation of P and As. The periodic drainage and aeration of the filter favours the oxidation of any residual FeII and AsIII and the formation of dense Fe precipitates and may thereby contribute to effective filter operation over several years.

Groundwater drawn daily from shallow alluvial sands by millions of wells over large areas of south and southeast Asia exposes an estimated population of over a hundred million people to toxic levels of arsenic. Holocene aquifers are the source of widespread arsenic poisoning across the region. In contrast, Pleistocene sands deposited in this region more than 12,000 years ago mostly do not host groundwater with high levels of arsenic. Pleistocene aquifers are increasingly used as a safe source of drinking water and it is therefore important to understand under what conditions low levels of arsenic can be maintained. Here we reconstruct the initial phase of contamination of a Pleistocene aquifer near Hanoi, Vietnam. We demonstrate that changes in groundwater flow conditions and the redox state of the aquifer sands induced by groundwater pumping caused the lateral intrusion of arsenic contamination more than 120 metres from a Holocene aquifer into a previously uncontaminated Pleistocene aquifer. We also find that arsenic adsorbs onto the aquifer sands and that there is a 16–20-fold retardation in the extent of the contamination relative to the reconstructed lateral movement of groundwater over the same period. Our findings suggest that arsenic contamination of Pleistocene aquifers in south and southeast Asia as a consequence of increasing levels of groundwater pumping may have been delayed by the retardation of arsenic transport.