Department Water Resources and Drinking Water

Natural organic matter (NOM) can contribute to arsenic (As) mobilization as an electron donor for microbially-mediated reductive dissolution of As-bearing Fe(III) (oxyhydr)oxides. However, to investigate this process, instead of using NOM, most laboratory studies used simple fatty acids or sugars, often at relatively high concentrations. To investigate the role of relevant C sources, we therefore extracted in situ NOM from the upper aquitard (clayey silt) and lower sandy aquifer sediments in Van Phuc (Hanoi area, Vietnam), characterized its composition, and used 100-day microcosm experiments to determine the effect of in situ OM on Fe(III) mineral reduction, As mobilization, and microbial community composition. We found that OM extracted from the clayey silt (OMC) aquitard resembles young, not fully degraded plant-related material, while OM from the sandy sediments (OMS) is more bioavailable and related to microbial biomass. Although all microcosms were amended with the same amount of C (12 mg C/L), the extent of Fe(III) reduction after 100 days was the highest with acetate/lactate (43 ± 3.5% of total Fe present in the sediments) followed by OMS (28 ± 0.3%) and OMC (19 ± 0.8%). Initial Fe(III) reduction rates were also higher with acetate/lactate (0.53 mg Fe(II) in 6 days) than with OMS and OMC (0.18 and 0.08 mg Fe(II) in 6 days, respectively). Although initially more dissolved As was detected in the acetate/lactate setups, after 100 days, higher concentrations of As (8.3 ± 0.3 and 8.8 ± 0.8 μg As/L) were reached in OMC and OMS, respectively, compared to acetate/lactate-amended setups (6.3 ± 0.7 μg As/L). 16S rRNA amplicon sequence analyses revealed that acetate/lactate mainly enriched Geobacter, while in situ OM supported growth and activity of a more diverse microbial community. Our results suggest that although the in situ NOM is less efficient in stimulating microbial Fe(III) reduction than highly bioavailable acetate/lactate, it ultimately has the potential to mobilize the same amount or even more As.

The generation of hydroxyl radicals (^•OH) during the chlorination of air saturated solutions of different hydroxyphenols (hydroquinone, resorcinol, catechol, gallic and tannic acids) at pH 7 has been determined by the formation of phenol (in presence of benzene in excess) or 2-hydroxyterephthalic acid (in presence of terephthalic acid). Formation of ^•OH was only detected during the chlorination of o- or p-hydroxyphenols, compounds that react with chlorine by electron transfer forming the corresponding semiquinones/quinones. In aerated solutions, oxygen is reduced by the semiquinone to the superoxide radical, O₂^•-, which reacts with HOCl to ^•OH. Compared to the studied o-hydroxyphenols, the lower reactivity of hydroquinone towards chlorine favours the reaction between chlorine and O₂^•-, and its ^•OH formation potential is ∼50 times higher. The extent of ^•OH generated increased with the concentration of the hydroxyphenol and chlorine, but the ^•OH yield (moles formed per mole of hydroxyphenol eliminated), decreased due to the formation of the quinone, that acts as O₂^•- scavenger. The yield was almost not affected by the pH (6 ≤ pH ≤ 7.5), whereas a strong impact of dissolved O₂ was observed. The ^•OH production was null in absence of O₂ and 2.5-3 times higher at oxygen saturated conditions compared to air-saturated. Contrary to chlorination, during bromination of hydroquinone ^•OH was not formed, which can be attributable to a much faster consumption of the oxidant, with no chance for O₂^•- to react with bromine.
Formation of ^•OH during the chlorination of different NOM extracts (SRHA, SRFA, PLFA and Nordic Lake NOM) and water from Lake Greifensee (Switzerland) was also studied using terephthalic acid as ^•OH scavenger. For SRHA, SRFA and Nordic Lake NOM (all of allochthonous origin and presenting high electron-donating capacity, EDC), ^•OH yields expressed as moles formed per mole of DOC₀ (%), were between 1.1 and 2.0, similar to that of hydroquinone (∼1.5). For PLFA and Lake Greifensee water (autochthonous, lower EDC) much lower ^•OH yields were observed (0.1-0.3). Both chlorination rate and EDC, the later favouring the formation/stabilization of O₂^•-, seem to be key factors involved in ^•OH generation during the chlorination of NOM. A mechanism for these findings is proposed based on kinetic simulations of hydroquinone chlorination at pH 7.

Multiphase flow is ubiquitous in subsurface energy applications and natural processes, such as oil recovery, CO₂ sequestration, and water flow in soils. Despite its importance, we still lack a thorough understanding of the coupling of multiphase flow and reaction of transported fluids with the confining media, including rock dissolution and mineral precipitation. Through the use of geomaterial microfluidic flow experiments and high-performance computer simulations, we identify key pore-scale mechanisms that control this coupling. We compare the reactivity of fractured limestone with CO₂-saturated brine (single phase) and a mixture of supercritical (sc) CO₂ and CO₂-saturated brine (multiphase). We find that the presence of scCO₂ bubbles significantly changes both the flow dynamics and the resulting reaction patterns from a single-phase system, spatially homogenizing the rock dissolution. In addition, bubbles redirect oversaturated fluid into low-velocity regions, thereby enhancing carbonate precipitation occurs.