The abiotic removal of organic micropollutants with iron and manganese oxides in rapid sand filters for groundwater treatment.

Rapid sand filters (RSFs) have shown potential for removing organic micropollutants (OMPs) from groundwater. However, the abiotic removal mechanisms are not well understood. In this study, we collect sand from two field RSFs that are operated in series. The sand from the primary filter abiotically removes 87.5% of salicylic acid, 81.4% of paracetamol, and 80.2% of benzotriazole, while the sand from the secondary filter only removes paracetamol (84.6%). The field collected sand is coated by a blend of iron oxides (FeOx) and manganese oxides (MnOx) combined with organic matter, phosphate, and calcium. FeOx adsorbs salicylic acid via bonding of carboxyl group with FeOx. The desorption of salicylic acid from field sand indicates that salicylic acid is not oxidized by FeOx. MnOx adsorbs paracetamol through electrostatic interactions, and further transforms it into p-benzoquinone imine through hydrolysis-oxidation. FeOx significantly adsorbs organic matter, calcium, and phosphate, which in turn influences OMP removal. Organic matter on field sand surfaces limits OMP removal by blocking sorption sites on the oxides. However, calcium and phosphate on field sand support benzotriazole removal via surface complexation and hydrogen bonding. This paper provides further insight into the abiotic removal mechanisms of OMPs in field RSFs.

Exploring organic micropollutant biodegradation under dynamic substrate loading in rapid sand filters.

Microbial removal of trace organic micropollutants (OMPs) from drinking water sources remains challenging. Nitrifying and heterotrophic bacteria in rapid sand filters (RSFs) are capable of biodegrading OMPs while growing on ammonia and dissolved organic matter (DOM). The loading patterns of ammonia and DOM may therefore affect microbial activities as well as OMP biodegradation. So far, there is very limited information on the effect of substrate loading on OMP biodegradation at environmentally relevant concentrations (∼ 1 µg/L) in RSFs. We investigated the biodegradation rates of 16 OMPs at various substrate loading rates and/or empty bed contact times (EBCT). The presence of DOM improved the biodegradation of paracetamol (41.8%) by functioning as supplementary carbon source for the heterotrophic degrader, while hindering the biodegradation of 2,4-D, mecoprop and benzotriazole due to substrate competition. Lower loading ratios of DOM/benzotriazole benefited benzotriazole biodegradation by reducing substrate competition. Higher ammonia loading rates enhanced benzotriazole removal by stimulating nitrification-based co-metabolism. However, stimulating nitrification inhibited heterotrophic activity, which in turn inhibited the biodegradation of paracetamol, 2,4-D and mecoprop. A longer EBCT promoted metformin biodegradation as it is a slowly biodegradable compound, but suppressed the biodegradation of paracetamol and benzotriazole due to limited substrate supply. Therefore, the optimal substrate loading pattern is contingent on the type of OMP, which can be chosen based on the priority compounds in practice. The overall results contribute to understanding OMP biodegradation mechanisms at trace concentrations and offer a step towards enhancing microbial removal of OMPs from drinking water by optimally using RSFs.

Unravelling the contribution of nitrifying and methanotrophic bacteria to micropollutant co-metabolism in rapid sand filters.

The presence of organic micropollutant (OMP) in groundwater threatens drinking water quality and public health. Rapid sand filter (RSF) rely on biofilms with nitrifying and methanotrophic bacteria to remove ammonia and methane during drinking water production. Previous research observed the partial removal of OMPs with active nitrification and methane oxidation due to co-metabolic conversion of OMPs. However, the contribution of indigenous nitrifying and methanotrophic communities from RSF has yet to be fully explored. Accordingly, experiments were carried out with biofilm-covered sand collected from field-scale RSF, to assess the removal of nine OMPs by nitrifying and methanotrophic bacteria. Results indicated that stimulating nitrification resulted in significantly more removal of caffeine, 2,4-dichlorophenoxyacetic acid and bentazone. Stimulating methanotrophic conditions enhanced the removal of caffeine, benzotriazole, 2,4-dichlorophenoxyacetic acid and bentazone. Microbial community analysis based on 16 S rRNA gene sequencing revealed Nitrosomonas and Nitrospira are the dominant genus in the community under nitrifying conditions. The three genera Methylobacter, Methylomonas and Methylotenera were enriched under methanotrophic conditions. This study highlights that nitrifying and methanotrophic bacteria play important roles during OMP removal in field RSF. Furthermore, results suggest that bioaugmentation with an enriched nitrifying and methanotrophic culture is a promising approach to improve OMP removal in RSF.

Prolonged lifetime of biological activated carbon filters through enhanced biodegradation of melamine.

Micropollutants can be removed in Biological Activated Carbon (BAC) filters through biodegradation, besides adsorption, when the conditions are favorable. In the present study, we build upon previous work on melamine biodegradation and activated carbon regeneration in batch experiments and assess the efficiency of this process in continuous flow lab-scale BAC filters. Melamine is frequently detected at low concentrations in surface water and is used here as a model micropollutant. BAC filters were inoculated with melamine degrading biomass and the contribution of biodegradation to melamine removal was assessed. Furthermore, we tested the effect of an additional carbon source (methanol) and the effect of contact time on melamine removal efficiency. We demonstrate that inoculation of activated carbon filters with melamine degrading biomass increases melamine removal efficiency by at least 25%. When an additional carbon source (methanol) is supplied, melamine removal is almost complete (up to 99%). Finally, through a nitrogen mass balance, we demonstrate that around 60% of the previously adsorbed melamine desorbs from the BAC surface when biodegradation rates in the liquid phase increase. Melamine desorption resulted in a partial recovery of the adsorption capacity.

Unravelling pH Changes in Electrochemical Desalination with Capacitive Deionization.

Membrane capacitive deionization (MCDI) is a water desalination technology employing porous electrodes and ion-exchange membranes. The electrodes are cyclically charged to adsorb ions and discharged to desorb ions. During MCDI operation, a difference in pH between feed and effluent water is observed, changing over time, which can cause the precipitation of hardness ions and consequently affect the long-term stability of electrodes and membranes. These changes can be attributed to different phenomena, which can be divided into two distinct categories: Faradaic and non-Faradaic. In the present work, we show that during long-term operation, as the electrodes age over time, the magnitude and direction of pH changes shift. We studied these changes for two different feed water solutions: a NaCl solution and a tap water solution. Whereas we observe a pH decrease during the regeneration with a NaCl solution, we observe an increase during regeneration with tap water, potentially resulting in the precipitation of hardness ions. We compare our experimental findings with theory and conclude that with aged electrodes, non-Faradaic processes are the prominent cause of pH changes. Furthermore, we find that for desalination with tap water, the adsorption and desorption of HCO3-and CO32- ions affect the pH changes.

Melamine degradation to bioregenerate granular activated carbon.

The industrial chemical melamine is often detected in surface water used for drinking water production, due to its wide application and insufficient removal in conventional wastewater treatment plants. Melamine can be removed from water by adsorption onto granular activated carbon (GAC), nevertheless, GAC needs periodic reactivation in costly and energy intense processes. As an alternative method, GAC can also be regenerated using biomass capable of degrading melamine in a process called bioregeneration. We assessed melamine biodegradation in batch experiments in fully oxic and anoxic, as well as in alternating oxic and anoxic conditions. Additionally, we studied the effect of an additional carbon source on the biodegradation. The most favourable conditions for melamine biodegradation were applied to bioregenerate GAC loaded with melamine. We demonstrate that melamine can be biodegraded in either oxic or anoxic conditions and that melamine degrading biomass can restore at least 28% of the original GAC adsorption capacity. Furthermore, our results indicate that bioregeneration occurs mainly in the largest pore fraction of GAC, impacting adsorption kinetics. Overall, we show that bioregeneration has a large potential for restoring GAC adsorption capacity in industrial wastewater.

Mobility and redox transformation of arsenic during treatment of artificially recharged groundwater for drinking water production.

In this study we investigate opportunities for reducing arsenic (As) to low levels, below 1 µg/L in produced drinking water from artificially infiltrated groundwater. We observe that rapid sand filtration is the most important treatment step for the oxidation and removal of As at water treatment plants which use artificially recharged groundwater as source. Removal of As is mainly due to As co-precipitation with Fe(III)(oxyhydr)oxides, which shows higher efficiency in rapid sand filter beds compared to aeration and supernatant storage. This is due to an accelerated oxidation of As(III) to As(V) in the filter bed which may be caused by the manganese oxides and/or As(III) oxidizing bacteria, as both are found in the coating of rapid sand filter media grains by chemical analysis and taxonomic profiling of the bacterial communities. Arsenic removal does not take place in treatment steps such as granular activated carbon filtration, ultrafiltration or slow sand filtration, due to a lack of hydrolyzing iron in their influent and a lack of adsorption affinity between As and the filtration surfaces. Further, we found that As reduction to below 1 µg/L can be effectively achieved at water treatment plants either by treating the influent of rapid sand filters by dosing potassium permanganate in combination with ferric chloride or by treating the effluent of rapid sand filters with ferric chloride dosing only. Finally, we observe that reducing the pH is an effective measure for increasing As co-precipitation with Fe(III)(oxyhydr)oxides, but only when the oxidized arsenic, As(V), is the predominant species in water.

Biodegradation and adsorption of micropollutants by biological activated carbon from a drinking water production plant.

The presence of micropollutants in surface water is a potential threat for the production of high quality and safe drinking water. Adsorption of micropollutants onto granular activated carbon (GAC) in fixed-bed filters is often applied as a polishing step in the production of drinking water. Activated carbon can act as a carrier material for biofilm, hence biodegradation can be an additional removal mechanism for micropollutants in GAC filters. To assess the potential of biofilm to biodegrade micropollutants, it is necessary to distinguish adsorption from biodegradation as a removal mechanism. We performed experiments at 5 °C and 20 °C with biologically active and autoclaved GAC to assess the biodegradation of micropollutants by the biofilm grown on the GAC surface. Ten micropollutants were selected as model compounds. Three of them, iopromide, iopamidol and metformin, were biodegraded by the GAC biofilm. Additionally, we observed that temperature can increase or decrease adsorption, depending on the micropollutant studied. Finally, we compared the adsorption capacity of GAC used for more than 100,000 bed volumes and fresh GAC. We demonstrated that used GAC shows a higher adsorption capacity for guanylurea, metformin and hexamethylenetetramine and only a limited reduction in adsorption capacity for diclofenac and benzotriazole compared to fresh GAC.

Diffusion of hydrophilic organic micropollutants in granular activated carbon with different pore sizes.

Hydrophilic organic micropollutants are commonly detected in source water used for drinking water production. Effective technologies to remove these micropollutants from water include adsorption onto granular activated carbon in fixed-bed filters. The rate-determining step in adsorption using activated carbon is usually the adsorbate diffusion inside the porous adsorbent. The presence of mesopores can facilitate diffusion, resulting in higher adsorption rates. We used two different types of granular activated carbon, with and without mesopores, to study the adsorption rate of hydrophilic micropollutants. Furthermore, equilibrium studies were performed to determine the affinity of the selected micropollutants for the activated carbons. A pore diffusion model was applied to the kinetic data to obtain pore diffusion coefficients. We observed that the adsorption rate is influenced by the molecular size of the micropollutant as well as the granular activated carbon pore size.

Characteristics of Fe and Mn bearing precipitates generated by Fe(II) and Mn(II) co-oxidation with O2, MnO4 and HOCl in the presence of groundwater ions.

In this work, we combined macroscopic measurements of precipitate aggregation and chemical composition (Mn/Fe solids ratio) with Fe and Mn K-edge X-ray absorption spectroscopy to investigate the solids formed by co-oxidation of Fe(II) and Mn(II) with O2, MnO4, and HOCl in the presence of groundwater ions. In the absence of the strongly sorbing oxyanions, phosphate (P) and silicate (Si), and calcium (Ca), O2 and HOCl produced suspensions that aggregated rapidly, whereas co-oxidation of Fe(II) and Mn(II) by MnO4 generated colloidally stable suspensions. The aggregation of all suspensions decreased in P and Si solutions, but Ca counteracted these oxyanion effects. The speciation of oxidized Fe and Mn in the absence of P and Si also depended on the oxidant, with O2 producing Mn(III)-incorporated lepidocrocite (Mn/Fe = 0.01-0.02 mol/mol), HOCl producing Mn(III)-incorporated hydrous ferric oxide (HFO) (Mn/Fe = 0.08 mol/mol), and MnO4 producing poorly-ordered MnO2 and HFO (Mn/Fe > 0.5 mol/mol). In general, the presence of P and Si decreased the crystallinity of the Fe(III) phase and increased the Mn/Fe solids ratio, which was found by Mn K-edge XAS analysis to be due to an increase in surface-bound Mn(II). By contrast, Ca decreased the Mn/Fe solids ratio and decreased the fraction of Mn(II) associated with the solids, suggesting that Ca and Mn(II) compete for sorption sites. Based on these results, we discuss strategies to optimize the design (i.e. filter bed operation and chemical dosing) of water treatment plants that aim to remove Fe(II) and Mn(II) by co-oxidation.

Exceptional Water Desalination Performance with Anion-Selective Electrodes.

Capacitive deionization (CDI) typically uses one porous carbon electrode that is cation adsorbing and one that is anion adsorbing. In 2016, Smith and Dmello proposed an innovative CDI cell design based on two cation-selective electrodes and a single anion-selective membrane, and thereafter this design was experimentally validated by various authors. In this design, anions pass through the membrane once, and desalinated water is continuously produced. In the present work, this idea is extended, and it is experimentally shown that also a choice for anion-selective electrodes, in combination with a cation-selective membrane, leads to a functional cell design that continuously desalinates water. Anion-selective electrodes are obtained by chemical modification of the carbon electrode with (3-aminopropyl)triethoxysilane. After chemical modification, the activated carbon electrode shows a substantial reduction of the total pore volume and Brunauer-Emmett-Teller (BET) surface area, but nevertheless maintains excellent CDI performance, which is for the first time that a low-porosity carbon electrode is demonstrated as a promising material for CDI.

Energy recovery in membrane capacitive deionization.

Membrane capacitive deionization (MCDI) is a water desalination technology based on applying a cell voltage between two oppositely placed porous carbon electrodes. In front of each electrode, an ion-exchange membrane is positioned, and between them, a spacer is situated, which transports the water to be desalinated. In this work, we demonstrate for the first time that up to 83% of the energy used for charging the electrodes during desalination can be recovered in the regeneration step. This can be achieved by charging and discharging the electrodes in a controlled manner by using constant current conditions. By implementing energy recovery as an integral part of the MCDI operation, the overall energy consumption can be as low as 0.26 (kW·h)/m(3) of produced water to reduce the salinity by 10 mM, which means that MCDI is more energy efficient for treatment of brackish water than reverse osmosis. Nevertheless, the measured energy consumption is much higher than the thermodynamically calculated values for desalinating the water, and therefore, a further improvement in thermodynamic efficiency will be needed in the future.

Soluble complexes in aqueous mixtures of low charge density comb polyelectrolyte and oppositely charged surfactant probed by scattering and NMR.

A low charge density polyelectrolyte with a high graft density of 45 units long poly(ethylene oxide) side-chains has been synthesized. In this comb polymer, denoted PEO(45)MEMA:METAC-2, 2 mol% of the repeating methacrylate units in the polymer backbone carry a permanent positive charge and the remaining 98 mol% a 45 unit long PEO side-chain. Here we describe the solution conformation of this polymer and its association with an anionic surfactant, sodium dodecylsulfate, SDS. It will be shown that the polymer can be viewed as a stiff rod with a cross-section radius of gyration of 29 A. The cross section of the rod contracts with increasing temperature due to decreased solvency of the PEO side-chains. The anionic surfactant associates to a significant degree with PEO(45)MEMA:METAC-2 to form soluble complexes at all stoichiometries. A cooperative association is observed as the free SDS concentration approaches 7 mM. At saturation the number of SDS molecules associated with the polymer amounts to 10 for each PEO side-chain. Two distinct populations of associated surfactants are observed, one is suggested to be molecularly distributed over the comb polymer and the other constitutes small micellar-like structures at the periphery of the aggregate. These conclusions are reached based on results from small-angle neutron scattering, static light scattering, NMR, and surface tension measurements.