Removal of carcinogenic arsenic (As) from groundwater is essential for providing safe drinking water. Arsenate (As(V)) is more effectively removed in groundwater filters than arsenite (As(III)), making the oxidation of As(III) to As(V) a key step in the treatment process. This study distinguishes between surface-catalytic and biological As(III) oxidation on natural manganese oxide (MnO_x) coated filter sand, since it is unknown which pathway dominates in filters. The MnO_xcoated sand was collected from a full-scale groundwater filter and consisted of a mixture of different abiotically and biologically formed Mn oxides, such as Birnessite and Todorokite. A lab-scale filter setup was operated with As(III)-containing water. Within 3 weeks, a shift from surface-catalytic to biological As(III) oxidation was observed. Initially, surface-catalytic As(III) oxidation (k_CHEM= 0.318 min^–1) was coupled to Mn(II) release at a ratio of 0.96, approximating the stoichiometric ratio of 1. This coupling disappeared over time, indicating the biological nature of the reaction, as confirmed by microbial inhibition. An increase in relative abundance of the known As-oxidizing families Comamonadaceae, with Polaromonas as the dominant genus, and Microscillaceae were found post experiments. Except for these changes, the microbial community on the sand grains stayed relatively similar prior to and post experiments. No significant changes in the physical-chemical properties of the MnO_xcoating were found post experiments. A first-order biological As(III) oxidation rate constant k_BIOof 4.64 min^–1was found, yielding a half-life of 9 s. This represents a 14-fold acceleration compared with surface-catalytic oxidation, revealing that kinetic limitations rather than surface passivation can be attributed to the loss of surface-catalytic oxidation. Our study demonstrates that biological oxidation of As(III) can outpace the acknowledged oxidizing power of MnO_x, offering a potential new pathway for the development of effective As removal systems.

To meet the increasing drinking water demand, membrane technologies are used to treat previously unavailable water sources. A byproduct of membrane technologies is the concentrate stream, containing valuable resources in higher concentrations. We studied the recovery of iron from different groundwater matrices and anaerobic reverse osmosis (RO) concentrates via precipitation of vivianite and the co-removal of other common groundwater divalent cations Mn²⁺, Mg²⁺ and Ca²⁺ during vivianite precipitation. The formed precipitates were characterized using X-Ray Diffraction and Scanning Electron Microscopy. Vivianite precipitation removed a maximum of 89 % of Fe²⁺ in raw groundwater and 52 % Fe²⁺ from RO concentrate. Substantial co-removal of Mn²⁺ (max 91 %) and limited co-removal of Mg²⁺ (max 7 %) were found, without hindering Fe removal efficiencies or altering morphological changes of the vivianite crystal. In contrast, co-removal of Ca²⁺ occurred at the expense of iron removal, forming amorphous calcium phosphate precipitates. This study shows the potential of vivianite precipitation for iron recovery across a wide range of groundwater matrices and highlights the need for further research to optimize this novel method to treat concentrate streams that are challenging to dispose of.

Iron-based adsorbents are commonly used to remove arsenic (As) from water for drinking water purposes. Here, we study the role of biological As(III) oxidation on iron-based adsorbents in filters and its effect on overall As uptake. A lab-scale filter with iron oxide coated sand (IOCS), a commonly used adsorbent, was operated with water containing As(III) and As(V), while water samples were taken periodically over its height. As(III) oxidation initiated after approximately 10 days and increased to a first order rate constant of 0.09 s⁻¹ after 57 days resulting in full oxidation of As(III) in <50 s. Consequently, the filter shifted from an As(III) to an As(V) adsorbing filter. Oxidation was not observed after inhibiting the microbial activity using sodium azide confirming its biogenic nature. This implies that As(III) oxidizing biomass can grow on iron-based adsorbents in water filters without requiring inoculation. As the experimental conditions were similar to full-scale As treatment plants, we believe that biological As(III) oxidation is widely overlooked in these systems. Occurrence of biological oxidation is, however, beneficial for removal, as at pH <8 the adsorption capacity for As(V) can be up to 10-fold higher than for As(III). With these new insights, arsenic treatment using iron-based adsorbents can be further optimized. We suggest a more robust new design with a biological active As(III) oxidizing top layer and an As(V) adsorbing bottom layer.

Iron in anaerobic groundwater is commonly removed by oxidation followed by sand filtration. This produces large volumes of iron(III)(hydr)oxide sludge with little value. Our research investigates the novel concept of anaerobic iron(II) recovery from groundwater as the valuable mineral vivianite (Fe₃(PO₄)₂ • 8 H₂O) by the addition of phosphate to the water. We found that vivianite precipitated both in synthetic and natural groundwater when the saturation index (SI) was higher than 4. The SI can be increased by elevating the pH, which allows for iron removal at lower concentrations. Anaerobic iron removal reached 93.7% in natural groundwater, which increased further to 99.9% after a subsequent aeration step. Vivianite precipitation followed second order kinetics with a rate constant of 2.3 M⁻¹s⁻¹ and the sludge volume decreased by two third compared to iron oxidation. We therefore conclude that anaerobic iron removal is a promising new approach towards sustainable groundwater treatment.