Spatiotemporal Mineral Phase Evolution and Arsenic Retention in Microfluidic Models of Zerovalent Iron-Based Water Treatment.

Arsenic (As) is a toxic element, and elevated levels of geogenic As in drinking water pose a threat to the health of several hundred million people worldwide. In this study, we used microfluidics in combination with optical microscopy and X-ray spectroscopy to investigate zerovalent iron (ZVI) corrosion, secondary iron (Fe) phase formation, and As retention processes at the pore scale in ZVI-based water treatment filters. Two 250 µm thick microchannels filled with single ZVI and quartz grain layers were operated intermittently (12 h flow/12 h no-flow) with synthetic groundwater (pH 7.5; 570 µg/L As(III)) over 13 and 49 days. Initially, lepidocrocite (Lp) and carbonate green rust (GRC) were the dominant secondary Fe-phases and underwent cyclic transformation. During no-flow, lepidocrocite partially transformed into GRC and small fractions of magnetite, kinetically limited by Fe(II) diffusion or by decreasing corrosion rates. When flow resumed, GRC rapidly and nearly completely transformed back into lepidocrocite. Longer filter operation combined with a prolonged no-flow period accelerated magnetite formation. Phosphate adsorption onto Fe-phases allowed for downstream calcium carbonate precipitation and, consequently, accelerated anoxic ZVI corrosion. Arsenic was retained on Fe-coated quartz grains and in zones of cyclic Lp-GRC transformation. Our results suggest that intermittent filter operation leads to denser secondary Fe-solids and thereby ensures prolonged filter performance.

Microbial communities contribute to the elimination of As, Fe, Mn, and NH4+ from groundwater in household sand filters.

Household sand filters (SFs) are widely applied to remove iron (Fe), manganese (Mn), arsenic (As), and ammonium (NH4+) from groundwater in the Red River delta, Vietnam. Processes in the filters probably include a combination of biotic and abiotic reactions. However, there is limited information on the microbial communities treating varied groundwater compositions and on whether biological oxidation of Fe(II), Mn(II), As(III), and NH4+ contributes to the overall performance of SFs. We therefore analyzed the removal efficiencies, as well as the microbial communities and their potential activities, of SFs fed by groundwater with varying compositions from low (3.3 µg L-1) to high (600 µg L-1) As concentrations. The results revealed that Fe(II)-, Mn(II)-, NH4+-, and NO2--oxidizing microorganisms were prevalent and contributed to the performance of SFs. Additionally, groundwater composition was responsible for the differences among the present microbial communities. We found i) microaerophilic Fe(II) oxidation by Sideroxydans in all SFs, with the highest abundance in SFs fed by low-As and high-Fe groundwater, ii) Hyphomicropbiaceae as the main Mn(II)-oxidizers in all SFs, iii) As sequestration on formed Fe and Mn (oxyhydr)oxide minerals, iv) nitrification by ammonium-oxidizing archaea (AOA) followed by nitrite-oxidizing bacteria (NOB), and v) unexpectedly, the presence of a substantial amount of methane monooxygenase genes (pmoA), suggesting microbial methane oxidation taking place in SFs. Overall, our study revealed diverse microbial communities in SFs used for purifying arsenic-contaminated groundwater, and our data indicate an important contribution of microbial activities to the key functional processes in SFs.

Quantification of individual Rare Earth Elements from industrial sources in sewage sludge.

Rare Earth Elements (REEs) are used in increasing amounts in technical applications and consumer products. However, to date, the contribution of industrial sources to the loads of individual REEs in wastewater streams have not been quantified. Here, we determine the REE contents in sludge collected from 63 wastewater treatment plants (WWTPs) across Switzerland. To quantify the industrial fraction of individual REEs in the sewage sludge, we develop two complementary approaches, based on REE ratios and REE pattern fitting. Unspecific (background) inputs, with REE patterns similar to the averaged REE pattern of soils collected across Switzerland, dominate the REE budget of most WWTPs. A few WWTPs receive significant REE inputs from specific industrial sources. Based on population equivalents of Switzerland, we estimate a total annual load of 4200 kg Cerium (Ce, 0.5 g Ce year-1 capita-1), with an industrial contribution of 2000 kg year-1. The latter agrees with estimates of probabilistic mass flow models for engineered nanoscale CeO2 particles discharged to the sewer network. About 7 kg year-1 of Samarium (Sm,total for Switzerland: 184 kg year-1 or 0.02 g Sm year-1 capita-1) and 3 kg year-1 of Europium (Eu,total for Switzerland: 44 kg year-1 or 0.005 g Eu year-1 capita-1) are assigned to industrial inputs from single WWTPs. Gadolinium (Gd) is used in the form of a stable complex as contrast agent in magnetic resonance imaging. Assuming 10% removal of Gd during wastewater treatment, we calculate an annual discharge of 90 kg of Gd from one individual WWTP to surface waters. WWTPs with exceptionally high industrial inputs of specific REEs warrant detailed investigations to identify the respective sources and to assess whether REE concentrations in effluents are elevated to the same degree.

Catalytic effects of photogenerated Fe(II) on the ligand-controlled dissolution of Iron(hydr)oxides by EDTA and DFOB.

Low bioavailability of iron due to poor solubility of iron(hydr)oxides limits the growth of microorganisms and plants in soils and aquatic environments. Previous studies described accelerated dissolution of iron(hydr)oxides under continuous illumination, but did not distinguish between photoreductive dissolution and non-reductive processes in which photogenerated Fe(II) catalyzes ligand-controlled dissolution. Here we show that short illuminations (5-15 min) accelerate the dissolution of iron(hydr)oxides by ligands during subsequent dark periods under anoxic conditions. Suspensions of lepidocrocite (Lp) and goethite (Gt) (1.13 mM) with 50 µM EDTA or DFOB were illuminated with UV-A light of comparable intensity to sunlight (pH 7.0, bicarbonate-CO2 buffered solutions). During illumination, the rate of Fe(II) production was highest with Gt-EDTA; followed by Lp-EDTA > Lp-DFOB > Lp > Gt-DFOB > Gt. Under anoxic conditions, photochemically produced Fe(II) increased dissolution rates during subsequent dark periods by factors of 10-40 and dissolved Fe(III) reached 50 µM with DFOB and EDTA. Under oxic conditions, dissolution rates increased by factors of 3-5 only during illumination. With DFOB dissolved Fe(III) reached 35 µM after 10 h of illumination, while with EDTA it peaked at 15 µM and then decreased to below 2 µM. The observations are explained and discussed based on a kinetic model. The results suggest that in anoxic bottom water of ponds and lakes, or in microenvironments of algal blooms, short illuminations can dramatically increase the bioavailability of iron by Fe(II)-catalyzed ligand-controlled dissolution. In oxic environments, photostable ligands such as DFOB can maintain Fe(III) in solution during extended illumination.

Kanchan arsenic filters in the lowlands of Nepal: mode of operation, arsenic removal, and future improvements.

In the lowlands of Nepal (Terai), the WHO drinking water guideline concentration of 10 µg/L for arsenic (As) is frequently exceeded. Since their introduction in 2006, iron-assisted bio-sand filters (Kanchan filters) are widely used to treat well water in Nepal. The filters are constructed on the basis of As-removal with corroding zero-valent iron (ZVI), with water flowing through a filter bed of iron nails placed above a sand filter. According to several studies, the performance of Kanchan filters varies greatly and depends on the size of the iron nails, filter design, water composition, and operating conditions, leading to concerns about their actual efficiency. This study examined 38 Kanchan household filters for which insufficient As-removal was reported, to evaluate the reasons for limited removal efficiency and to define measures for improved performance. The measured arsenic removal ranged from 6.3% to 98.5%. The most relevant factors were the concentrations of As and Fe in the raw water, with the best removal efficiency observed for water with low As (123 µg/L) and high Fe (5.0 mg/L). Although the concentrations of other elements, pH, flow rates, and contact time with ZVI also played a role, the combined evidence indicated that the reactivity of the frequently drying nail beds between filtrations was insufficient for efficient As-removal. Optimized filters with added top layers of sand and raised water outlets with flow restrictions to keep nails permanently immersed and to increase contact times, should be able to achieve higher and more consistent arsenic removal efficiencies.

Arsenic and Other Geogenic Contaminants in Groundwater - A Global Challenge.

Groundwater is a much safer and more dependable source of drinking water than surface water. However, natural (geogenic) hazardous elements can contaminate groundwater and lead to severe health problems in consumers. Arsenic concentrations exceeding the WHO drinking water guideline of 10 µg/L globally affect over 220 million people and can cause arsenicosis (skin lesions and cancers). Fluoride, while preventing caries at low concentrations, has detrimental effects when above the WHO drinking water guideline of 1.5 mg/L and puts several hundred million people at risk of dental and skeletal fluorosis. In this article, we report on the geochemistry and occurrence of arsenic and fluoride in groundwater and on the development of global and regional risk maps that help alert governments and water providers to take appropriate mitigation measures for the provision of safe drinking water. We then summarize research on the removal of arsenic and fluoride from drinking water, focusing on adapted technologies for water treatment. Finally, we discuss the applicability of various measures in a larger context and future challenges in reaching the goal of access to safe drinking water for all.

Arsenic removal with zero-valent iron filters in Burkina Faso: Field and laboratory insights.

Groundwater contaminated with geogenic arsenic (As) is frequently used as drinking water in Burkina Faso, despite adverse health effects. This study focused on testing low-cost filter systems based on zero-valent iron (ZVI), which have not yet been explored in West Africa for As removal. The active ZVI bed was constructed using small-sized iron nails, embedded between sand layers. Household filters were tested for nine months in a remote village relying on tube well water with As concentrations of 400-1350 µg/L. Daily filtered volumes were 40-60 L, with flow rates of ~10 L/h. In parallel, downscaled laboratory filter columns were run to find the best set-up for optimal As removal, with special attention given to the influence of input pH, flow rate and water/nail contact time. Arsenic removal efficiencies in the field were 60-80% in the first six months of operation. The laboratory experiments revealed that trapped air in the nail layer greatly lowered As removal due to preferential flow and decreased water/nail contact time. Measures taken to avoid trapped air led to a partial improvement in the field filters, but effluent As remained >50 µg/L. Similar structural modifications were however very successful in the laboratory columns, where As removal efficiencies were consistently >95% and effluent concentrations frequently <10 µg/L, despite inflow As >1000 µg/L. A constantly saturated nail bed and careful flow control is necessary for optimal As removal. Slow flow and longer pauses between filtrations are important for sufficient contact times and for transformation of brown amorphous Fe-hydroxides to dense magnetite with incorporated As(V). This preliminary study has shown that nail-based filters have the potential to achieve As removal >90% in a field context if conditions (filter bed saturation, flow rate, pauses between filtrations) are well controlled.

Mercury loads and fluxes from wastewater: A nationwide survey in Switzerland.

Mercury (Hg) pollution threatens ecosystems and human health. Wastewater treatment plants (WWTPs) play a key role in limiting Hg discharges from wastewaters to rivers and lakes, but large-scale studies to estimate Hg loads and discharge at national levels are scarce. We assessed the concentration, flux, speciation, and removal of Hg in municipal wastewater throughout Switzerland by investigating 64 WWTPs in a pre-study and a subset of 28 WWTPs in the main study. We also studied the behavior and pathways of Hg along the various treatment steps in a state-of-the-art WWTP. The resulting dataset, representative of industrialized countries, provides an overview of (i) current Hg concentration ranges, (ii) average per capita loads, and (iii) wastewater Hg inputs into surface waters. The results allowed estimation of a total Hg (THg) load in Swiss wastewater of 130 ± 30 kg THg/year (15.7 mg/capita/y), of which 96 ± 4% is retained in sewage sludge. About 4.7 ± 0.5 kg THg/year (0.57 mg/capita/y) is discharged with the treated wastewater into surface waters. This corresponds to only 1.5-3% of the THg load carried by the major Swiss rivers, indicating that >95% of riverine Hg originates from other sources. Extrapolation to the population of Europe would yield a total amount of 11,700 kg THg/year in raw wastewater, with some 480 kg THg/year discharged to surface waters. Monomethyl mercury on average accounted for 0.23% of THg, and its fraction remained constant along the different treatment steps.

Linking Isotope Exchange with Fe(II)-Catalyzed Dissolution of Iron(hydr)oxides in the Presence of the Bacterial Siderophore Desferrioxamine-B.

Dissolution of Fe(III) phases is a key process in making iron available to biota and in the mobilization of associated trace elements. Recently, we have demonstrated that submicromolar concentrations of Fe(II) significantly accelerate rates of ligand-controlled dissolution of Fe(III) (hydr)oxides at circumneutral pH. Here, we extend this work by studying isotope exchange and dissolution with lepidocrocite (Lp) and goethite (Gt) in the presence of 20 or 50 µM desferrioxamine-B (DFOB). Experiments with Lp at pH 7.0 were conducted in carbonate-buffered suspensions to mimic environmental conditions. We applied a simple empirical model to determine dissolution rates and a more complex kinetic model that accounts for the observed isotope exchange and catalytic effect of Fe(II). The fate of added tracer 57Fe(II) was strongly dependent on the order of addition of 57Fe(II) and ligand. When DFOB was added first, tracer 57Fe remained in solution. When 57Fe(II) was added first, isotope exchange between surface and solution could be observed at pH 6.0 but not at pH 7.0 and 8.5 where 57Fe(II) was almost completely adsorbed. During dissolution of Lp with DFOB, ratios of released 56Fe and 57Fe were largely independent of DFOB concentrations. In the absence of DFOB, addition of phenanthroline 30 min after tracer 57Fe desorbed predominantly 56Fe(II), indicating that electron transfer from adsorbed 57Fe to 56Fe of the Lp surface occurs on a time scale of minutes to hours. In contrast, comparable experiments with Gt desorbed predominantly 57Fe(II), suggesting a longer time scale for electron transfer on the Gt surface. Our results show that addition of 1-5 µM Fe(II) leads to dynamic charge transfer between dissolved and adsorbed species and to isotope exchange at the surface, with the dissolution of Lp by ligands accelerated by up to 60-fold.

Reductive dissolution of As(V)-bearing Fe(III)-precipitates formed by Fe(II) oxidation in aqueous solutions.

Iron(III)-precipitates formed by the oxidation of dissolved Fe(II) are important sorbents for major and trace elements in aquatic and terrestrial systems. Their reductive dissolution in turn may result in the release of associated elements. We examined the reductive dissolution kinetics of an environmentally relevant set of Fe(II)-derived arsenate-containing Fe(III)-precipitates whose structure as function of phosphate (P) and silicate (Si) content varied between poorly-crystalline lepidocrocite, amorphous Fe(III)-phosphate, and Si-containing ferrihydrite. The experiments were performed with 0.2-0.5 mM precipitate-Fe(III) using 10 mM Na-ascorbate as reductant, 5 mM bipyridine as Fe(II)-complexing ligand, and 10 mM MOPS/5 mM NaOH as pH 7.0 buffer. Times required for the dissolution of half of the precipitate (t50%) ranged from 1.5 to 39 h; spanning a factor 25 range. At loadings up to ~ 0.2 P/Fe (molar ratio), phosphate decreased the t50% of Si-free precipitates, probably by reducing the crystallinity of lepidocrocite. The reductive dissolution of Fe(III)-phosphates formed at higher P/Fe ratios was again slower, possibly due to P-inhibited ascorbate binding to precipitate-Fe(III). The slowest reductive dissolution was observed for P-free Si-ferrihydrite with ~ 0.1 Si/Fe, suggesting that silicate binding and polymerization may reduce surface accessibility. The inhibiting effect of Si was reduced by phosphate. Dried-resuspended precipitates dissolved 1.0 to 1.8-times more slowly than precipitates that were kept wet after synthesis, most probably because drying enhanced nanoparticle aggregation. Variations in the reductive dissolution kinetics of Fe(II) oxidation products as reported from this study should be taken into account when addressing the impact of such precipitates on the environmental cycling of co-transformed nutrients and contaminants.

Low Fe(II) Concentrations Catalyze the Dissolution of Various Fe(III) (hydr)oxide Minerals in the Presence of Diverse Ligands and over a Broad pH Range.

Dissolution of Fe(III) (hydr)oxide minerals by siderophores (i.e., Fe-specific, biogenic ligands) is an important step in Fe acquisition in environments where Fe availability is low. The observed coexudation of reductants and ligands has raised the question of how redox reactions might affect ligand-controlled (hydr)oxide dissolution and Fe acquisition. We examined this effect in batch dissolution experiments using two structurally distinct ligands (desferrioxamine B (DFOB) and  N, N'-di(2-hydroxybenzyl)ethylene-diamine- N, N'-diacetic acid (HBED)) and four Fe(III) (hydr)oxide minerals (lepidocrocite, 2-line ferrihydrite, goethite and hematite) over an environmentally relevant pH range (4-8.5). The experiments were conducted under anaerobic conditions with varying concentrations of (adsorbed) Fe(II) as the reductant. We observed a catalytic effect of Fe(II) on ligand-controlled dissolution even at submicromolar Fe(II) concentrations with up to a 13-fold increase in dissolution rate. The effect was larger for HBED than for DFOB. It was observed for all four Fe(III) (hydr)oxide minerals, but it was most pronounced for goethite in the presence of HBED. It was observed over the entire pH range with the largest effect at pH 7 and 8.5, where Fe deficiency typically occurs. The occurrence of this catalytic effect over a range of environmentally relevant conditions and at very low Fe(II) concentrations suggests that redox-catalyzed, ligand-controlled dissolution may be significant in biological Fe acquisition and in redox transition zones.

Fe(II)-Catalyzed Ligand-Controlled Dissolution of Iron(hydr)oxides.

Dissolution of iron(III)phases is a key process in soils, surface waters, and the ocean. Previous studies found that traces of Fe(II) can greatly increase ligand controlled dissolution rates at acidic pH, but the extent that this also occurs at circumneutral pH and what mechanisms are involved are not known. We addressed these questions with infrared spectroscopy and 57Fe isotope exchange experiments with lepidocrocite (Lp) and 50 µM ethylenediaminetetraacetate (EDTA) at pH 6 and 7. Addition of 0.2-10 µM Fe(II) led to an acceleration of the dissolution rates by factors of 7-31. Similar effects were observed after irradiation with 365 nm UV light. The catalytic effect persisted under anoxic conditions, but decreased as soon as air or phenanthroline was introduced. Isotope exchange experiments showed that added 57Fe remained in solution, or quickly reappeared in solution when EDTA was added after 57Fe(II), suggesting that catalyzed dissolution occurred at or near the site of 57Fe incorporation at the mineral surface. Infrared spectra indicated no change in the bulk, but changes in the spectra of adsorbed EDTA after addition of Fe(II) were observed. A kinetic model shows that the catalytic effect can be explained by electron transfer to surface Fe(III) sites and rapid detachment of Fe(III)EDTA due to the weaker bonds to reduced sites. We conclude that the catalytic effect of Fe(II) on dissolution of Fe(III)(hydr)oxides is likely important under circumneutral anoxic conditions and in sunlit environments.

Climatic variations and de-coupling between arsenic and iron in arsenic contaminated ground water in the lowlands of Nepal.

As widely known, in several countries in South East Asia, arsenic concentrations in ground water extracted from Quaternary alluvial sediments frequently exceed the World Health Organization (WHO) drinking water guideline of 10 µg/L. The broadly accepted hypothesis states that reductive dissolution of Fe-bearing minerals releases As-oxyanions contained within these minerals. According to the results presented in this article, As and Fe concentrations in ground water in the lowlands (Terai) of Nepal are highly variable as a function of location and there is a de-coupling of As and Fe concentrations resulting in a loss of correlation between these two elements. The mean concentrations of As and of Fe in 35 wells were slightly higher in the post-monsoon than in the pre-monsoon season. Even though As is mainly associated with iron(hydr)oxides, a substantial portion of As and Fe can be retained by clay minerals (including micas). During pre-monsoon (dry season) clayey sediments are chemically weathered losing Na and K thus remaining relatively enriched in less mobile elements such as Fe and Al. As long as reducing conditions persist, As remains relatively mobile. This article includes a detailed discussion referring to the very weak correlation or decoupling between aqueous As and Fe in the ground water and addresses possible consequences for water treatment. It sheds light on the original reservoir of arsenic being incorporated and released from clay minerals as well as from iron(hydr)oxides.

Long-term trends in Swiss rivers sampled continuously over 39 years reflect changes in geochemical processes and pollution.

Long-term changes of 14 water constituents measured in continuously and water discharge proportionally collected samples of four Swiss rivers over a period of 39 years are analyzed using several statistical techniques. Possible drivers and causes for the identified trends and shifts are explained by consideration of catchment characteristics and anthropogenic activities. Water temperatures increased by 0.8-1.3 °C, whereas water discharges remained largely unchanged. Concentrations of alkalinity, total hardness, Ca, and Mg regulated by dominant carbonate lithologies in catchments increased by up to 10%. We attribute this change to an increase in the partial pressure of CO2 in the subsurface, provoked by increasing temperatures. Re-oligotrophication processes in lakes also influence the behavior of alkalinity and silicic acid. In contrast to concentrations, most loads did not change significantly, due to their large variances. Therefore, no changes in overall weathering rates of carbonate rocks can be detected. The outgassing of CO2 in rivers from the place of carbonate dissolution to measurement stations amounts up to 6% (mean) of CO2 sequestered (mean 1.1 mol m-2 a-1) by the weathering of rock minerals. Changes in alkalinity/Ca/Mg ratios indicate an increase in calcite precipitation over time. Total nitrogen concentrations and loads peaked at the end of the 1980s and then decreased up to 50%, while NO3 concentrations showed almost no changes. This dynamic matches the changes in the agricultural N balance. Concentrations and loads of Na and Cl increased up to 60% due to an increase in the various uses of rock salt.

Monothioarsenate Occurrence in Bangladesh Groundwater and Its Removal by Ferrous and Zero-Valent Iron Technologies.

In most natural groundwaters, sulfide concentrations are low, and little attention has been paid to potential occurrence of thioarsenates (AsVS n-IIO4- n3- with n = 1-4). Thioarsenate occurrence in groundwater could be critical with regard to the efficiency of iron (Fe)-based treatment technologies because previous studies reported less sorption of thioarsenates to preformed Fe-minerals compared to arsenite and arsenate. We analyzed 273 groundwater samples taken from different wells in Bangladesh over 1 year and detected monothioarsenate (MTA), likely formed via solid-phase zero-valent sulfur, in almost 50% of all samples. Concentrations ranged up to >30 µg L-1 (21% of total As). MTA removal by locally used technologies in which zero-valent or ferrous Fe is oxidized by aeration and As sorbs or coprecipitates with the forming Fe(III)hydroxides was indeed lower than for arsenate. The presence of phosphate required up to three times as much Fe(II) for comparable MTA removal. However, in contrast to previous sorption studies on preformed Fe minerals, MTA removal, even in the presence of phosphate, was still higher than that of arsenite. The more efficient MTA removal is likely caused by a combination of coprecipitation and adsorption rendering the tested Fe-based treatment technologies suitable for As removal also in the presence of MTA.

Arsenate co-precipitation with Fe(II) oxidation products and retention or release during precipitate aging.

The co-precipitation of arsenate (As(V)) with Fe(III)-precipitates is of great importance in water treatment and critically affects the fate of As in environmental systems. We studied the effects of dissolved phosphate (P; 0-1 mM), silicate (Si; 0 or 0.5 mM) and Ca (0, 0.5 and 4 mM) on the sequestration of 7 µM As(V) by Fe(III)-precipitates formed by the oxidation of 0.5 mM Fe(II) in aerated bicarbonate-buffered solutions with an initial pH of 7.0 as well as the retention or release of As(V) after precipitate aging for 30 d at 40 °C. Dissolved As(V) concentrations in fresh precipitate suspensions greatly varied as a function of the initial dissolved P/Fe ratio ((P/Fe)init) and the concentrations of Ca and Si. Limited As(V) removal was observed at (P/Fe)init that exceeded the critical ratio (P/Fe)crit above which exclusively (Ca-)Fe(III)-phosphate forms. Effective As(V) removal was observed at (P/Fe)init < (P/Fe)crit, where initial formation of (Ca-)Fe(III)-phosphate is followed by the formation of Si-ferrihydrite in Si-containing electrolytes and of poorly-crystalline lepidocrocite and hydrous ferric oxide in the Si-free electrolytes. The retention of As(V) and P by fresh Fe(III)-precipitates was most effective in systems containing both Ca and Si. In the Si- and Ca-free electrolytes at (P/Fe)init of ∼0.2-0.6, the rapid onset of precipitate aging with conversion of Fe(III)-phosphate to ferrihydrite resulted in a substantial remobilization of As(V) (up to 55% of initially precipitated As(V)). Ca reduced As remobilization during aging by stabilizing Ca-Fe(III)-phosphate and promoting Ca-phosphate formation, and Si by stabilizing Si-ferrihydrite against transformation. Consequently, also after aging, the lowest dissolved As(V) and P fractions were observed in precipitate suspensions containing both Ca and Si.

Quantification of Element Fluxes in Wastewaters: A Nationwide Survey in Switzerland.

The number and quantities of trace elements used in industry, (high-tech) consumer products, and medicine are rapidly increasing, but the resulting emissions and waste streams are largely unknown. We assessed the concentrations of 69 elements in digested sewage sludge and effluent samples from 64 municipal wastewater treatment plants as well as in major rivers in Switzerland. This data set, representative of an entire industrialized country, presents a reference point for current element concentrations, average per-capita fluxes, loads discharged to surface waters, and economic waste-stream values. The spatial distribution of many individual elements could be attributed either to predominant geogenic or to anthropogenic inputs. Per-capita element fluxes ranged from <10 µg day-1 (e.g., Au, In, and Lu) to >1 mg day-1 (e.g., Zn, Sc, Y, Nb, and Gd) and >1 g day-1 (e.g., for P, Fe, and S). Effluent loads of some elements contributed significantly to riverine budgets (e.g., 24% for Zn, 50% for P, and 83% for Gd), indicating large anthropogenic inputs via the wastewater stream. At various locations, precious metal concentrations in sludge were similar to those in profitable mining ores, with total flux values of up to 6.8 USD per capita per year or 15 USD per metric ton of dry sludge.

Enhanced As(III) oxidation and removal by combined use of zero valent iron and hydrogen peroxide in aerated waters at neutral pH values.

The oxidation and removal of As(III) by commercially available micro-scale zero-valent iron (mZVI) was studied in aerated synthetic groundwater with initially 6.7 µM As(III) at neutral pH values. Batch experiments were performed to investigate the influence of ZVI and H2O2 concentrations on As(III) oxidation and removal. Oxidation and removal kinetics was significantly increased by increasing ZVI concentration or by adding H2O2 in micromolar concentrations slightly higher than that of initial As(III). Observed half-lifes for arsenic removal without added H2O2 were 81-17 min at ZVI concentrations of 0.15-2.5 g/L, respectively. X-ray absorption spectroscopy (XAS) confirmed that almost all As(III) was converted to As(V) after 2 h of reaction in the pH range 5-9. Addition of 9.6 µM H2O2 to 0.15 g/L ZVI suspensions diminished half-lifes for arsenic removal from 81 to 32 min and for As(III) oxidation from 77 to 8 min, i.e., by approximately a factor of 10. The increased rate of As(III) oxidation is attributable to enhanced formation of oxidants by the Fenton reaction with higher initial concentrations of H2O2. In practice, results of this study suggest that addition of small amounts (<1 mg/L) of H2O2 in various forms (e.g. stable and widely available Na-percarbonate) to water prior to treatment could significantly enhance As(III) oxidation and removal with ZVI.

Enhancing arsenic mitigation in Bangladesh: findings from institutional, psychological, and technical investigations.

As part of a trans-disciplinary research project, a series of surveys and interventions were conducted in different arsenic-affected regions of rural Bangladesh. Surveys of institutional stakeholders identified deep tubewells and piped water systems as the most preferred options, and the same preferences were found in household surveys of populations at risk. Psychological surveys revealed that these two technologies were well-supported by potential users, with self-efficacy and social norms being the principal factors driving behavior change. The principal drawbacks of deep tubewells are that installation costs are too high for most families to own private wells, and that for various socio-cultural-religious reasons, people are not willing to walk long distances to access communal tubewells. In addition, water sector planners have reservations about greater exploitation of the deep aquifer, out of concern for current or future geogenic contamination. Groundwater models and field studies have shown that in the great majority of the affected areas, the risk of arsenic contamination of deep groundwater is small; salinity, iron, and manganese are more likely to pose problems. These constituents can in some cases be avoided by exploiting an intermediate depth aquifer of good chemical quality, which is hydraulically and geochemically separate from the arsenic-contaminated shallow aquifer. Deep tubewells represent a technically sound option throughout much of the arsenic-affected regions, and future mitigation programs should build on and accelerate construction of deep tubewells. Utilization of deep tubewells, however, could be improved by increasing the tubewell density (which requires stronger financial support) to reduce travel times, by considering water quality in a holistic way, and by accompanying tubewell installation with motivational interventions based on psychological factors. By combining findings from technical and social sciences, the efficiency and success of arsenic mitigation in general - and installation of deep tubewells in particular - can be significantly enhanced.

Photo-redox reactions of dicarboxylates and α-hydroxydicarboxylates at the surface of Fe(III)(hydr)oxides followed with in situ ATR-FTIR spectroscopy.

Colloidal mineral-phases play an important role in the adsorption, transport and transformation of organic and inorganic compounds in the atmosphere and in aqueous environments. Artificial UV-light and sunlight can induce electron transfer reactions between metal ions of the solid phases and adsorbed compounds, leading to their transformation and degradation. To investigate different possible photo-induced oxidation pathways of dicarboxylates adsorbed on iron(III)(hydr)oxide surfaces, we followed UV-A induced photoreactions of oxalate, malonate, succinate and their corresponding α-hydroxy analogues tartronate and malate with in situ ATR-FTIR spectroscopy in immersed particle layers of lepidocrocite, goethite, maghemite and hematite at pH 4. UV-A light (365 ± 5 nm) lead to fast degradation of oxalate, tartronate and malate, while malonate and succinate were photo-degraded at much slower rates. Efficient generation of OH-radicals can be excluded, as this would lead to fast and indiscriminate degradation of all tested compounds. Rapid photo-degradation of adsorbed oxalate and the α-hydroxydicarboxylates must be induced by direct ligand-to-metal charge transfer (LMCT) or by selectively oxidizing valence band holes, both processes requiring inner-sphere coordination with direct ligand-to-metal bonds to enable efficient electron-transfer. The slow photo-degradation of malonate and succinate can be explained by low-yield production of OH-radicals at the surface of the iron(III)(hydr)oxides.