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Procedia Earth and Planetary Science 17 (2017) 85 – 87

15th Water-Rock Interaction International Symposium, WRI-15

Reactive transport modeling of arsenic mobilization in

groundwater of the Red River floodplain, Vietnam
Dieke Postma1,a, Pham Thi Kim Trangb, Helle Ugilt Søa, Vi Mai Lanb, Rasmus Jakobsena
a
GEUS, Østervoldgade 10, 1350 Copenhagen Denmark
b
Research Centre for Environmental Technology and Sustainable Development (CETASD), Hanoi University of Science (VNU), Hanoi, Vietnam.

Abstract

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.
© 2017
© 2017Published
The Authors. Published
by Elsevier by Elsevier
B.V. This B.V.
is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of WRI-15.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of WRI-15
Keywords: geochemistry, groundwater, arsenic, Red River, Vietnam, reactive transport, modeling

1. Introduction

Geogenic arsenic in groundwater probably constitutes the largest global drinking water contamination problem.
Alone in southern and southeast Asia it has been estimated that more than 100 million people are exposed to
drinking water with a arsenic content exceeding the WHO recommended maximum value of 10 µg/L As 1,2. Chronic
intake of too much arsenic enhances risks for developing various forms of cancers and heart diseases.
On the big delta complexes of S and SE Asia, arsenic enters the system in association with Fe-oxides which
together with clays and sands have been deposited on the floodplain. Once the sediment the sediment becomes part
of the saturated groundwater zone anoxic conditions develop because of organic matter degradation. Organic matter
degradation leads to the reduction of As-containing Fe-oxide, resulting in the release of Fe(II) and As(III) to the
groundwater3,4,5. Secondary processes that may affect the groundwater arsenic concentration, comprise the
adsorption and desorption of arsenic to the sediment6.

*
Corresponding author. Tel.:+45 30273702; fax:+45 4538142050.
E-mail address: diekepostma@gmail.com

1878-5220 © 2017 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of WRI-15
doi:10.1016/j.proeps.2016.12.003
86 Dieke Postma et al. / Procedia Earth and Planetary Science 17 (2017) 85 – 87

We have studied the geochemical processes related to arsenic mobilization in the floodplain of the Red River,
Vietnam, at a field site located 30 km NW of Hanoi5,7,8,9. Here local aquifers are found were the sediment has burial
ages ranging from 600 to 6000 years. We have shown previously that the arsenic content of the groundwater is
related to the sediment burial age8. In young sediments the groundwater concentration is up to 500 µg/L As, while in
5900 year old sediments the maximum arsenic concentration only reaches 20 µg/L. In addition we have shown that
the rates of organic matter degradation strongly decreases with increasing burial age. Clearly, the geochemical
properties of the sediments change significantly during the 6000 year period, leading to a diminishing mobilization
of arsenic over time. In this contribution we present a reactive transport model that quantifies the geochemical
processes related to arsenic mobilization to the groundwater over the last 6000 years. The model has been
constructed as a one-dimensional flow tube in PHREEQC-310 considering only the vertical component of
groundwater flow. This simplification is based on groundwater dating showing a rather homogeneous infiltration
rate of 0.5 m/yr at the various sites and the assumption that the infiltration rate has been the same over the last 6000
years. The objective is to obtain a quantitative understanding of the geochemical processes controlling the bulk
groundwater chemistry as well as the arsenic concentration on a 6000 year time scale.

2. Geochemical Processes and Model Developments

The measured content of arsenic in the iron oxides of the aquifer sediment corresponds to a As/Fe ratio of about
1.2 mmol/mol M corresponding to a stoichiometric composition of Fe(OH)2.9964(AsO4)0.0012. Both Fe and As(V) can
be mobilized during reductive dissolution with organic carbon functioning as the electron donor:

CH2O + 4FeOOH + 7H+ → 4Fe2+ + HCO3- + 6H2O (1)

In this reaction arsenic has been omitted for simplicity but in the course of the reaction the As(V) in the Fe-oxide
will become reduced to As(III) and enter the groundwater. No other electron acceptors, such as sulfate, are
important in the aquifer but methanogenesis constitutes the second pathway for organic carbon degradation
following the overall reaction:

2CH2O → CH4 + CO2 (2)

The measured methane concentration of up to 1.5 mM CH 4 indicates methanogenesis to be of importance. The

overall rate of both reactions (1) and (2) is controlled by the kinetics of organic matter degradation which again
depends on the reactivity of the organic carbon present in the aquifer. It must be expected that the organic carbon
reactivity will diminish over time as the most reactive material is consumed first. To describe this process we have
developed the following rate equation:

-dCC/dt = mo ∙9.3∙10-12∙(mt/mo)2.5 (mol/sec) (3)

Here mo = 1.36 mol/L is the initial mass of organic matter based on the measured concentration of 0.27 % C in
the youngest sediment recalculated to the concentration per liter of contacting groundwater, mt, the mass of organic
carbon at time t and 9.3∙10-12 sec-1 the rate constant. The exponent to (mt/mo) reflects the heterogeneity of the
organic carbon reactivity, the difference between the most and least reactive organic carbon. The parameters in this
rate equation were found by trial and error fitting to the groundwater chemistry data.
The distribution of the electron flow coming from organic matter to either the reduction of Fe-oxides (reaction (1))
or to methanogenesis (reaction (2)) is controlled by the kinetics of reductive dissolution of Fe-oxide. The kinetics of
Fe-oxide reduction will depend on factors like surface area, crystallinity and microbial catalysis, but is also
dependent on the thermodynamic energy release of the Fe-oxide reduction reaction which is a function of the
mineralogy of the Fe-oxide as well as the solution composition. In the presence of an unstable and poorly crystalline
ferrihydrite, iron reduction would be the predominant process while in the presence of well crystalline goethite or
hematite, methanogenesis may become most important. The rate equation for Fe-oxide reduction is constructed as:

-dCFeOOH/dt = mo ∙ 2.54∙10-11∙(mt/mo)1.5 ∙ (1 – SRFeOOH) (mol/s) (4)

 Dieke Postma et al. / Procedia Earth and Planetary Science 17 (2017) 85 – 87 87

Here mo is 0.394 mol/L corresponding to 65 µmol FeOOH/g obtained by extrapolation from the field data. SR FeOOH
is the Saturation Ratio (IAP/K) representing the thermodynamic contribution. In the model, the solubility of Fe-
oxide (K) is much closer to goethite than to ferrihydrite.
There is a very strong effect of the pH on the reduction of iron by organic carbon (Reaction (1)). This pH effect
on the energy release of iron reduction (1) may result in both positive and negative feed-back mechanisms. Iron
oxide reduction by itself increases the pH (reaction (1)) and disfavors the process. The CO2 produced by
methanogenesis (reaction (2)) will dissolve as carbonic acid and lower the pH, thereby stimulating Fe-oxide
reduction. Additional processes like the dissolution or precipitation of siderite or calcite and the CO 2 pressure of
infiltrating water from the soil zone will also affect the pH. Together, all these reactions form an interacting reaction
network where the relative importance of the different reactions changes over time.

3. Model results

The results of the PHREEQC model are able to satisfactorily describe the water chemistry in the aquifers with
different burial ages, including the decreases in arsenic, alkalinity, Ca and pH over time as well as the increase in
dissolved Fe(II). The model results indicate methanogenesis to be the more important pathway for organic carbon
degradation as compared to iron reduction. Both the rates of organic carbon degradation (3) and the rate of iron
oxide reduction (4) decrease over time but the latter decreases faster than the first and as the result the reaction
stoichiometry changes over time. The rate of arsenic release is directly related to the rate of iron oxide reduction and
therefore decreases over time. If this was the only process to occur, the groundwater arsenic concentration should
initially be highest and thereafter diminish. However, the model predicts that the groundwater arsenic content will
increase over the first 1200 years because adsorption of As(III) onto the sediment removes much of the arsenic and
delays the build-up in the groundwater. After the first 1200 years, the decreasing arsenic release rates will, in
combination with desorption of arsenic from the sediment, slowly decrease the groundwater arsenic content. After
6000 years the arsenic concentration will have decreased to 20 µg/L corresponding to twice the WHO recommended
maximum level. Almost all of the Fe(II) that is released by Fe-oxide reduction in the model is precipitated in the
sediment as siderite. Over time the CaCO 3 in the soil and aquifer sediment is leached out, which causes the pH and
alkalinity to decrease while enabling more Fe(II) to stay in solution and finally also results in the dissolution of
siderite.

Acknowledgements

This research has been funded by the European Research Council under the ERC Advanced Grant ERG-2013-
ADG. Grant Agreement Number 338972.

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