Aquifers on the Red River flood plain with burial ages ranging from 500 to 6000 years show, with increasing age, the following changes in solute concentrations; a decrease in arsenic, increase in Fe(II) and decreases in both pH, Ca and bicarbonate. These changes were interpreted in terms of a reaction network comprising the kinetics of organic carbon degradation, the reduction kinetics of As containing Fe-oxides, the sorption of arsenic, the kinetics of siderite precipitation and dissolution, as well as of the dissolution of CaCO 3 . The arsenic released from the Fe-oxide is preferentially partitioned into the water phase, and partially sorbed, while the released Fe(II) is precipitated as siderite. The reaction network involved in arsenic mobilization was analyzed by 1-D reactive transport modeling. The results reveal complex interactions between the kinetics of organic matter degradation and the kinetics and thermodynamic energy released by Fe-oxide reduction. The energy released by Fe-oxide reduction is strongly pH dependent and both methanogenesis and carbonate precipitation and dissolution have important influences on the pH. Overall it is the rate of organic carbon degradation that determines the total electron flow. However, the kinetics of Fe-oxide reduction determines the distribution of this flow of electrons between methanogenesis, which is by far the main pathway, and Fe-oxide reduction. Modeling the groundwater arsenic content over a 6000 year period in a 20 m thick aquifer shows an increase in As during the first 1200 years where it reaches a maximum of about 600 μg/L. During this initial period the release of arsenic from Fe-oxides actually decreases but the adsorption of arsenic onto the sediment delays the build-up in the groundwater arsenic concentration. After 1200 years the groundwater arsenic content slowly decreases controlled both by desorption and continued further, but diminishing, release from Fe-oxide being reduced. After 6000 years the arsenic content has decreased to 33 μg/L. The modeling enables a quantitative description of how the aquifer properties, the reactivity of organic carbon and Fe-oxides, the number of sorption sites and the Correspondence to: Dieke Postma. Europe PMC Funders Group Europe PMC Funders Author ManuscriptsEurope PMC Funders Author Manuscripts buffering mechanisms change over a 6000 year period and how the combined effect of these interacting processes controls the groundwater arsenic content.

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Groundwater arsenic (As) concentrations in the Red River Delta (Vietnam) are often patchy and related to the microbially induced reduction of Fe oxy-hydroxides. In this study, we explored the influence of the origin, composition and availability of natural organic matter on the hydrochemical variability in the aquifers of Van Phuc. Carbon isotope signatures (δ 13 C org ) and C/N ratios were assessed in combination with lithology, geochemistry, hydrochemistry, hydrology and the distribution of specific biomarkers.The elationship of C/N ratios and δ 13 C org distinguished four groups of sediment types that differ in their organic carbon sources. This includes organic carbon originating predominantly from vascular C 3 plants (C/N: 15.4-21.0, δ 13 C org : -28.6 to -26.7 ‰), C 4 plants (C/N: 10.6; δ 13 C org : -14.8 ‰), freshwater derived particulate organic carbon (C/N: ≤8; δ 13 C org :≤-24 ‰) as well as mixtures incorporating both sources. At the high As sites, we found particulate organic carbon (POC) being 1 to 2 ‰ less depleted in δ 13 C org than at low As sites. More importantly, however, our assessment shows that, the availability of organic matter has to be considered decisive with regard to groundwater As contamination. Fine-grained clayey sediments overlaying sands generally protect organic matter from substantial degradation and its leaching into an adjacent aquifer. However, at the sites that are high in dissolved As n Van Phuc, sediment layers rich in organic matter are hydraulically connected to the underlying aquifer. Here, soluble organic matter seeping into the aquifer can induce and/or

Arsenic contamination in groundwater and its effect on human health has been a growing concern over recent decades. Some of the most severe incidents occurred in South and Southeast Asia, including the Red river delta, Vietnam. The highest concentration of arsenic found in the Red river delta was 810 μg/L, 16 times higher than the standard guidelines given by WHO for levels of arsenic concentration in groundwater (50 μg/L). However, the contamination levels were not uniform in the whole area. The arsenic levels might be affected by natural factors such as the characteristics of the aquifer, the chemical composition of groundwater and by human activities such as the exploitation of groundwater in the urban and industrial areas or irrigation in rural areas. Due to the complex mobilisation of arsenic in sediment and groundwater, questions remain about arsenic distribution, which are yet to be answered and are in need of further study.

In this study, the author report detailed results of the variation of arsenic in groundwater along a transect in an area near the Hanoi city centre. The results showed that 64% of collected samples exceeded the WHO guideline value for arsenic concentration in drinking water. The arsenic concentration varied in a wide range, strongly depending on the sediment characteristics of each zone along the transect. Aside from As, groundwater in this area also was contaminated by elevated concentrations of Fe, Mn, and ammonium. The study also pointed out a positive correlation between As and reductive chemical species, namely DOC, NH4+, and CH4 in groundwater. Although there is no clear trend in the correlation between As and Fe, Mn, it can be concluded that the formation of arsenic in groundwater in the study area was due to the reductive dissolution of As-bearing iron minerals under the presence of organic matter.