Groundwater arsenic content in quaternary aquifers of the Red River delta, Vietnam, controlled by the hydrogeological processes.

The relation between arsenic groundwater concentrations and hydrogeological processes was investigated in the proximal part of the Red River delta, Vietnam, west of the depression cone formed by the exploitation of groundwater in Hanoi. Flow paths in the Quaternary aquifers were modeled based on previously interpreted geological structure and hydrogeological data gathered during field work in 2014-2017. Sedimentary structures and simulated flow patterns were compared with the spatial distribution of the groundwater arsenic concentration. The regression of the sea in the area started 4 ka BP in the Holocene. The low tectonic subsidence rate of the Red River delta led to intensive erosion and replacement of fine grained sediments of the sea level high stand by sandy channel belts, resulting in hydraulic connections between the Pleistocene and Holocene aquifers. The Pleistocene aquifer is recharged by both regional flow paths and naturally occurring vertical recharge through Holocene sand and clay layers. Young groundwater (<40 a) in the shallow Holocene aquifer generally discharges to surface water bodies. The shallow flow system is also seasonally recharged with surface water, as indicated by δ18O enrichment of groundwater and oscillating groundwater ages in wells in the vicinity of water channels. The deeper flow system discharges into the Red River and Day River or flows parallel to the rivers, toward the sea. The overall pattern of arsenic groundwater concentrations (decreasing with increasing sediment age) is modified by groundwater flow. The arsenic contamination of the Pleistocene aquifer of the Red River delta is not only caused by the intensive groundwater abstraction in Hanoi, as reported previously, but also by the natural flow of high arsenic groundwater from Holocene to Pleistocene aquifers in areas located outside of the depression cone. Groundwater with < 50 µg L-1 arsenic is found in the Pleistocene aquifer close to the recharge zone in the mountains bordering the Red River delta and in the Holocene and Pleistocene aquifers where clay deposits were eroded. Close to the recent Red River channel, recharge of older Holocene and Pleistocene sediments occurs partially by arsenic-contaminated groundwater from the youngest Holocene aquifers, and here arsenic concentrations exceed 50 µg L-1. A high arsenic concentration is also present in the early Holocene-Pleistocene aquifer, beneath thick clay layers, indicating a limited extent of flushing and the inflow of fresh organic matter.

Spatial Variability of Groundwater Arsenic Concentration as Controlled by Hydrogeology: Conceptual Analysis Using 2-D Reactive Transport Modeling.

Combined geological, hydrogeological, and geochemical controls on the arsenic concentration of contaminated aquifers in SE Asia were explored by two-dimensional (2-D) reactive transport modeling of data sets from Bangladesh, Cambodia, and Vietnam. For each site, the field data are summarized and used to create a conceptual 2-D reactive transport model that elucidates characteristic features influencing the groundwater arsenic concentration. Comparison of models for Bangladesh and Vietnam indicates that fine-grained layers overlying young sandy aquifers generate shallow high arsenic groundwater because low vertical groundwater velocities allow sufficient time for kinetic As release from the sediment. The low vertical groundwater velocity below major river channels, predicted by the model, also creates long groundwater residence times, leading to high arsenic groundwater. Young aquifer sediments release more arsenic than older sediments, and alternating young and older sediments create complex patterns of high and low arsenic groundwater. Over time, floodplain basins will subside, and river channels migrate, causing sedimentation and erosion on the floodplain while creating local environments with evolving hydrogeology and groundwater geochemistry. We have developed a three-step model for the evolution of the Red River floodplain with sedimentation and shifting channels over the last 6000 years. The results show comparable timescales between the dynamics of arsenic release and of river migration, causing complex groundwater As distributions, comprising geochemical palinopsia of long vanished rivers.

Fate of Arsenic during Red River Water Infiltration into Aquifers beneath Hanoi, Vietnam.

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.

A model for the evolution in water chemistry of an arsenic contaminated aquifer over the last 6000 years, Red River floodplain, Vietnam.

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 CaCO3. 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 buffering mechanisms change over a 6000 year period and how the combined effect of these interacting processes controls the groundwater arsenic content.