Arsenic dynamics in porewater of an intermittently irrigated paddy field in Bangladesh

In Bangladesh, irrigation of dry season rice (boro) with arsenic-contaminated groundwater is leading to increased As levels in soils and rice, and to concerns about As-induced yield reduction. Arsenic concentrations and speciation in soil porewater are strongly influenced by redox conditions, and thus by water management during rice growth. We studied the dynamics of As, Fe, P, Si, and other elements in porewater of a paddy field near Sreenagar (Munshiganj), irrigated according to local practice, in which flooding was intermittent. During early rice growth, As porewater concentrations reached up to 500 μg L(-1) and were dominated by As(III), but As release was constrained to the lower portion of the soil above the plow pan. In the later part of the season, soil conditions were oxic throughout the depth range relevant to rice roots and porewater concentrations only intermittently increased to ～150 μg L(-1) As(V) following irrigation events. Our findings suggest that intermittent irrigation, currently advocated in Bangladesh for water-saving purposes, may be a promising means of reducing As input to paddy soils and rice plant exposure to As.     

Assessing the labile arsenic pool in contaminated paddy soils by isotopic dilution techniques and simple extractions

Arsenic (As) contamination of paddy soils threatens rice cultivation and the health of populations relying on rice as a staple crop. In the present study, isotopic dilution techniques were used to determine the chemically labile (E value) and phytoavailable (L value) pools of As in a range of paddy soils from Bangladesh, India, and China and two arable soils from the UK varying in the degree and sources of As contamination. The E value accounted for 6.2-21.4% of the total As, suggesting that a large proportion of soil As is chemically nonlabile. L values measured with rice grown under anaerobic conditions were generally larger than those under aerobic conditions, indicating increased potentially phytoavailable pool of As in flooded soils. In an incubation study, As was mobilized into soil pore water mainly as arsenite under flooded conditions, with Bangladeshi soils contaminated by irrigation of groundwater showing a greater potential of As mobilization than other soils. Arsenic mobilization was best predicted by phosphate-extractable As in the soils.     

Antimony (Sb) and arsenic (As) in Sb mining impacted paddy soil from Xikuangshan, China: differences in mechanisms controlling soil sequestration and uptake in rice

Foods produced on soils impacted by antimony (Sb) mining activities are a potential health risk due to plant uptake of the contaminant metalloids (Sb) and arsenic (As). Here we report for the first time the chemical speciation of Sb in soil and porewater of flooded paddy soil, impacted by active Sb mining, and its effect on uptake and speciation in rice plants (Oryza sativa L. cv Jiahua). Results are compared with behavior and uptake of As. Pot experiments were conducted under controlled conditions in a climate chamber over a period of 50 days. In pots without rice plants, flooding increased both the concentration of dissolved Sb (up to ca. 2000 μg L(-1)) and As (up to ca. 1500 μg L(-1)). When rice was present, Fe plaque developing on rice roots acted as a scavenger for both As and Sb, whereby the concentration of As, but not Sb, in porewater decreased substantially. Dissolved Sb in porewater, which occurred mainly as Sb(V), correlated with Ca, indicating a solubility governed by Ca antimonate. No significant differences in bioaccumulation factor and translocation factor between Sb and As were observed. Greater relative concentration of Sb(V) was found in rice shoots compared to rice root and porewater, indicating either a preferred uptake of Sb(V) or possibly an oxidation of Sb(III) to Sb(V) in shoots. Adding soil amendments (olivine, hematite) to the paddy soil had no effect on Sb and As concentrations in porewater.     

Effect of oxide formation mechanisms on lead adsorption by biogenic manganese (hydr)oxides, iron (hydr)oxides, and their mixtures

The effects of iron and manganese (hydr)oxide formation processes on the trace metal adsorption properties of these metal (hydr)oxides and their mixtures was investigated by measuring lead adsorption by iron and manganese (hydr)oxides prepared by a variety of methods. Amorphous iron (hydr)oxide formed by fast precipitation at pH 7.5 exhibited greater Pb adsorption (gamma(max) = 50 mmol of Pb/mol of Fe at pH 6.0) than iron (hydr)oxide formed by slow, diffusion-controlled oxidation of Fe(II) at pH 4.5-7.0 or goethite. Biogenic manganese(III/IV) (hydr)oxide prepared by enzymatic oxidation of Mn(II) by the bacterium Leptothrix discophora SS-1 adsorbed five times more Pb (per mole of Mn) than an abiotic manganese (hydr)oxide prepared by oxidation of Mn(II) with permanganate, and 500-5000 times more Pb than pyrolusite oxides (betaMnO2). X-ray crystallography indicated that biogenic manganese (hydr)oxide and iron (hydr)oxide were predominantly amorphous or poorly crystalline and their X-ray diffraction patterns were not significantly affected by the presence of the other (hydr)oxide during formation. When iron and manganese (hydr)oxides were mixed after formation, or for Mn biologically oxidized with iron(III) (hydr)oxide present, observed Pb adsorption was similar to that expected for the mixture based on Langmuir parameters for the individual (hydr)oxides. These results indicate that interactions in iron/manganese (hydr)oxide mixtures related to the formation process and sequence of formation such as site masking, alterations in specific surface area, or changes in crystalline structure either did not occur or had a negligible effect on Pb adsorption by the mixtures.     

Spatial distribution and temporal variability of arsenic in irrigated rice fields in Bangladesh. 2. Paddy soil

Arsenic-rich groundwater from shallow tube wells is widely used for the irrigation of boro rice in Bangladesh and West Bengal. In the long term this may lead to the accumulation of As in paddy soils and potentially have adverse effects on rice yield and quality. In the companion article in this issue, we have shown that As input into paddy fields with irrigation water is laterally heterogeneous. To assess the potential for As accumulation in soil, we investigated the lateral and vertical distribution of As in rice field soils near Sreenagar (Munshiganj, Bangladesh) and its changes over a 1 year cycle of irrigation and monsoon flooding. At the study site, 18 paddy fields are irrigated with water from a shallow tube well containing 397 +/- 7 microg L(-1) As. The analysis of soil samples collected before irrigation in December 2004 showed that soil As concentrations in paddy fields did not depend on the length of the irrigation channel between well and field inlet. Within individual fields, however, soil As contents decreased with increasing distance to the water inlet, leading to highly variable topsoil As contents (11-35 mg kg(-1), 0-10 cm). Soil As contents after irrigation (May 2005) showed that most As input occurred close to the water inlet and that most As was retained in the top few centimeters of soil. After monsoon flooding (December 2005), topsoil As contents were again close to levels measured before irrigation. Thus, As input during irrigation was at least partly counteracted by As mobilization during monsoon flooding. However, the persisting lateral As distribution suggests net arsenic accumulation over the past 15 years. More pronounced As accumulation may occur in regions with several rice crops per year, less intense monsoon flooding, or different irrigation schemes. The high lateral and vertical heterogeneity of soil As contents must be taken into account in future studies related to As accumulation in paddy soils and potential As transfer into rice.     

Arsenic mobilization through microbially mediated deflocculation of ferrihydrite

This study examined the potential impact of microbially mediated reduction of Fe in the Fe(III)-(hydr)oxide mineral ferrihydrite on the mobility of As in natural waters. In microcosm experiments, the obligately anaerobic bacterium Geobacter metallireducens reduced on average 10% of the Fe(III) in ferrihydrite with varying sorbed As(V) surface coverages, which resulted in deflocculation of initially micron-sized As-bearing ferrihydrite aggregates to nanometersized colloids. No reduction of As(V) to As(III) was observed in microcosm samples. Measurement of Fe and As within operationally defined particulate, colloidal, and dissolved fractions of microcosm slurry samples revealed that little Fe or As was released from ferrihydrite as dissolved species. Microbially induced deflocculation of ferrihydrite in the presence of G. metallireducens was correlated with more negative zeta potential of ferrihydrite nanoparticles suggesting that G. metallireducens mediated As mobilization through alteration of ferrihydrite surface charge. TEM analysis and solution chemistry conditions suggested formation of a magnetite surface layer through topotactic recrystallization of ferrihydrite (2LFH) driven by sorbed Fe(II). The formation of nanometer-sized As-bearing colloids through microbially mediated reduction of Fe-(hydr)oxides has the potential to increase human As exposure by enhancing As mobility in natural waters and hindering As removal during subsequent drinking water treatment.     

Spatial distribution and temporal variability of arsenic in irrigated rice fields in Bangladesh. 1. Irrigation water

Around 38% of the area of Bangladesh is irrigated with groundwater to grow dry season crops, most importantly boro rice. Due to high As concentrations in many groundwaters, over 1000 tons of As are thus transferred to arable soils each year, creating a potential risk for future food production. We studied the reactions and changing speciation of As, Fe, P, and other elements in initially anoxic water during and after irrigation and the resulting spatial distribution of As input to paddy soils near Sreenagar (Munshiganj), 30 km south of Dhaka, in January and April 2005 and February 2006. The irrigation water had a constant concentration of 397 +/- 7 microg L(-1) As (approximately 84% As(III)), 11 +/- 0.1 mg L(-1) Fe, and 2 +/- 0.1 mg L(-1) P. During the fast flow along the longest irrigation channel (152 m) As, Fe, and P speciation changed, but total concentrations did not decrease significantly, indicating that As input to fields was independent of the length of the irrigation channels. In contrast, during slow water flow across the fields, As, Fe, and P concentrations decreased strongly with increasing distance from the water inlet, due to formation and settling of As- and P-bearing Fe aggregates and by adsorption to soil minerals. Total As concentrations in field water were approximately 3 times higher close to the inlet than in the opposite field corner shortly after irrigation, and decreased to below 35 microg L(-1) over the next 72 h. The laterally heterogeneous transfer of As, Fe, and P from irrigation waterto soil has important consequences for their distribution in irrigated fields and needs to be considered in sampling and in assessing the dynamics and mass balances of As fluxes among irrigation water, soil, and floodwater.     

Contrasting effects of dissimilatory iron (III) and arsenic (V) reduction on arsenic retention and transport

Reduction of arsenate As(V) and As-bearing Fe (hydr)- oxides have been proposed as dominant pathways of As release within soils and aquifers. Here we examine As elution from columns loaded with ferrihydrite-coated sand presorbed with As(V) or As(III) at circumneutral pH upon Fe and/or As reduction; biotic stimulated reduction is then compared to abiotic elution. Columns were inoculated with Shewanella putrefaciens strain CN-32 or Sulfurospirillum barnesii strain SES-3, organisms capable of As (V) and Fe (III) reduction, or Bacillus benzoevorans strain HT-1, an organism capable of As(V) but not Fe(III) reduction. On the basis of equal surface coverages, As(III) elution from abiotic columns exceeded As(V) elution by a factor of 2; thus, As(III) is more readily released from ferrihydrite under the imposed reaction conditions. Biologically mediated Asreduction induced by B. benzoevorans enhances the release of total As relative to As (V) under abiotic conditions. However, under Fe reducing conditions invoked by either S. barnesii or S. putrefaciens, approximately three times more As (V or III) was retained within column solids relative to the abiotic experiments, despite appreciable decreases in surface area due to biotransformation of solid phases. Enhanced As sequestration upon ferrihydrite reduction is consistent with adsorption or incorporation of As into biotransformed solids. Our observations indicate that As retention and release from Fe (hydr)oxide(s) is controlled by complex pathways of Fe biotransformation and that reductive dissolution of As-bearing ferrihydrite can promote As sequestration rather than desorption under conditions examined here.     

Iron and arsenic cycling in intertidal surface sediments during wetland remediation

The accumulation and behavior of arsenic at the redox interface of Fe-rich sediments is strongly influenced by Fe(III) precipitate mineralogy, As speciation, and pH. In this study, we examined the behavior of Fe and As during aeration of natural groundwater from the intertidal fringe of a wetland being remediated by tidal inundation. The groundwater was initially rich in Fe(2+) (32 mmol L(-1)) and As (1.81 μmol L(-1)) with a circum-neutral pH (6.05). We explore changes in the solid/solution partitioning, speciation and mineralogy of Fe and As during long-term continuous groundwater aeration using a combination of chemical extractions, SEM, XRD, and synchrotron XAS. Initial rapid Fe(2+) oxidation led to the formation of As(III)-bearing ferrihydrite and sorption of >95% of the As(aq) within the first 4 h of aeration. Ferrihydrite transformed to schwertmannite within 23 days, although sorbed/coprecipitated As(III) remained unoxidized during this period. Schwertmannite subsequently transformed to jarosite at low pH (2-3), accompanied by oxidation of remaining Fe(2+). This coincided with a repartitioning of some sorbed As back into the aqueous phase as well as oxidation of sorbed/coprecipitated As(III) to As(V). Fe(III) precipitates formed via groundwater aeration were highly prone to reductive dissolution, thereby posing a high risk of mobilizing sorbed/coprecipitated As during any future upward migration of redox boundaries. Longer-term investigations are warranted to examine the potential pathways and magnitude of arsenic mobilization into surface waters in tidally reflooded wetlands.     

Arsenic contamination of Bangladesh paddy field soils: implications for rice contribution to arsenic consumption

Arsenic contaminated groundwater is used extensively in Bangladesh to irrigate the staple food of the region, paddy rice (Oryza sativa L.). To determine if this irrigation has led to a buildup of arsenic levels in paddy fields, and the consequences for arsenic exposure through rice ingestion, a survey of arsenic levels in paddy soils and rice grain was undertaken. Survey of paddy soils throughout Bangladesh showed that arsenic levels were elevated in zones where arsenic in groundwater used for irrigation was high, and where these tube-wells have been in operation for the longest period of time. Regression of soil arsenic levels with tube-well age was significant. Arsenic levels reached 46 microg g(-1) dry weight in the most affected zone, compared to levels below l0 microg g(-1) in areas with low levels of arsenic in the groundwater. Arsenic levels in rice grain from an area of Bangladesh with low levels of arsenic in groundwaters and in paddy soils showed that levels were typical of other regions of the world. Modeling determined, even these typical grain arsenic levels contributed considerably to arsenic ingestion when drinking water contained the elevated quantity of 0.1 mg L(-1). Arsenic levels in rice can be further elevated in rice growing on arsenic contaminated soils, potentially greatly increasing arsenic exposure of the Bangladesh population. Rice grain grown in the regions where arsenic is building up in the soil had high arsenic concentrations, with three rice grain samples having levels above 1.7 microg g(-1).     

Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations

Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.     

Water management impacts on arsenic speciation and iron-reducing bacteria in contrasting rice-rhizosphere compartments

Rice cultivated on arsenic (As) contaminated-soils will accumulate variable grain-As concentrations, as impacted by varietal differences, soil variables, and crop management. A field-scale experiment was conducted to study the impact of intermittent and continuous flooding on As speciation and microbial populations in rice rhizosphere compartments of soils that were either historically amended with As pesticide or unamended with As. Rhizosphere-soil, root-plaque, pore-water and grain As were quantified and speciated, and microbial populations in rhizosphere soil and root-plaque were characterized. Total-As concentrations in rhizosphere and grain were significantly lower in intermittently flooded compared to the continuously flooded plots (86% lower in pore-water, 55% lower in root-plaque and 41% lower in grain samples). iAs(V), iAs(III), and DMAs(V) were the predominant As species detected in rhizosphere-soil and root-plaque, pore-water and grain samples, respectively. Relative proportions of Archaea and iron-reducing bacteria (FeRB) were higher in rhizosphere soil compared to root-plaque. In rhizosphere soil, the relative abundance of FeRB was lower in intermittently flooded compared to continuously flooded plots, but there were no differences between root-plaque samples. This study has demonstrated that reductions in dissolved As concentrations in the rhizosphere and subsequent decreases in grain-As concentration can be attained through water management.     

Geochemical cycling of arsenic in a coastal aquifer

Biogeochemically modified pore waters from subterranean estuaries, defined as the mixing zone between freshwater and saltwater in a coastal aquifer, are transported to coastal waters through submarine groundwater discharge (SGD). SGD has been shown to impact coastal and perhaps global trace metal budgets. The focus of this study was to investigate the biogeochemical processes that control arsenic cycling in subterranean estuaries. Total dissolved As, as well as a suite of other trace metals and nutrients, were measured in a series of wells and sediment cores at the head of Waquoit Bay, MA. Dissolved As ranged from below detection to 9.5 microg/kg, and was associated with plumes of dissolved Fe, Mn, and P in the groundwater. Sedimentary As, ranging from 360 to 7500 microg/kg, was highly correlated with sedimentary Fe, Mn, and P. In addition, amorphous Fe (hydr)oxides were more efficient scavengers of dissolved As than the more crystalline forms of solid-phase Fe. Given that dissolved As in the surface bay water was lower than within the subterranean estuary, our results indicate that the distribution and type of Fe and Mn (hydr)oxides in coastal aquifers exert a major influence on the biogeochemical cycling of As in subterranean estuaries and, ultimately, the fate of groundwater-derived As in marine systems influenced by SGD.     

Seasonal and interannual mobility of arsenic in a lake impacted by metal mining

Detailed examination of the water column, sediments, and interstitial waters was conducted in Balmer Lake, Ontario, Canada, in 1993-1994 and 1999 in order to assess the seasonal and interannual controls governing the behavior of As. High-resolution profiles of dissolved (<0.45 microm) Fe, Mn, SO4(2-), and sigmaH2S across the sediment-water interface indicate the presence of reducing conditions in close proximity to the benthic boundary during ice-free periods, which are characterized by fully oxygenated bottom waters. Dissolved As is remobilized as As(III) in suboxic sediment horizons via the redox-controlled dissolution of Fe (and perhaps Mn) oxide phases. During 1993-1994, As fluxes to the water column were relatively low (2-15 microg cm(-2) year(-1)) and contributed between 2 and 18% of the water column inventory. Dissolved As in the lake waters was derived primarily from external mining-related loadings during this period. Between 1993 and 1999, external loadings of As to Balmer Lake decreased while [As]aq within the lake increased, suggesting an increase in the proportion of sediment-derived As. Indeed, benthic dissolved As fluxes in 1999 ranged from 179 to 380 microg cm(-2) year(-1), representing approximately 33-60% of the water column burden. The relatively recent importance of sedimentary arsenic sources is suggested to reflect changes to sediment redox conditions associated with a postulated increase in lake primary productivity. Ironically, the increased contribution of dissolved arsenic to the water column appears to have resulted from an otherwise improvement in water quality. Reduced loadings of Cu, Zn, and Ni to the lake since 1994 appear to have allowed increased phytoplankton production that has stimulated arsenic release.     

Arsenic bioavailability to rice is elevated in Bangladeshi paddy soils

Some paddy soils in the Bengal delta are contaminated with arsenic (As) due to irrigation of As-laden groundwater, which may lead to yield losses and elevated As transfer to the food chain. Whether these soils have a higher As bioavailability than other soils containing either geogenic As or contaminated by mining activities was investigated in a pot experiment. Fourteen soils varying in the source and the degree (4-138 mg As kg 1?1) of As contamination were collected, 10 from Bangladeshi paddy fields (contaminated by irrigation water) and two each from China and the UK (geogenic or mining impacted), for comparison. Bangladeshi soils had higher percentages of the total As extractable by ammonium phosphate (specifically sorbed As) than other soils and also released more As into the porewater upon flooding. Porewater As concentrations increased with increasing soil As concentrations more steeply in Bangladeshi soils, with arsenite being the dominant As species. Rice growth and grain yield decreased markedly in Bangladeshi soils containing > 13 mg As kg 1?1, but not in the other soils. Phosphate-extractable or porewater As was a better indicator of As bioavailability than total soil As. Rice straw As concentrations increased with increasing soil As concentrations; however, As phytotoxicity appeared to result in lower grain As concentrations. The relative proportions of inorganic As and dimethylarsinic acid (DMA) in grain varied among soils, and the percentage DMA was larger in greenhouse-grown plants than grain samples collected from the paddy fields of the same soil and the same rice cultivar, indicating a strong environmental influence on As species found in rice grain. This study shows that Bangladeshi paddy soils contaminated by irrigation had a higher As bioavailability than other soils, resulting in As phytotoxicity in rice and substantial yield losses.     

Comparison of antimony behavior with that of arsenic under various soil redox conditions

The oxidation states and host phases of Sb and As in soil samples of mine tailing (Ichinokawa mine, Ehime, Japan) and in laboratory soil-water systems were determined by X-ray absorption fine structure (XAFS) spectroscopy. HPLC-ICP-MS was used for speciation of Sb and As in soil water. In the Ichinokawa soil water system, Sb was present exclusively as the oxidized form, Sb(V), over a wide redox range (from Eh = 360 to -140 mV, pH 8), while As was present as a mixture of As(III) and As(V). This finding was confirmed in the laboratory experiments. These results suggest that Sb(V) is a very stable form in the environment and that Sb is oxidized at more negative Eh than As. Combining the results of Fe and Mn XAFS analyses and a positive correlation among Sb, As, and Fe abundances in the soil, the host phases of Sb and As in soil were Fe(III) hydroxide. XAFS analyses of Sb and As are also consistent with this finding. Under reducing conditions, the concentration of As in the soil water increased whereas that of Sb decreased in both the Ichinokawa and laboratory systems. This suggests that this contrasting behavior is controlled mainly by the different redox properties of Sb and As.     

Groundwater or floodwater? Assessing the pathways of metal exports from a coastal acid sulfate soil catchment

Daily observations of dissolved aluminum, iron, and manganese in an estuary downstream of a coastal acid sulfate soil (CASS) catchment provided insights into how floods and submarine groundwater discharge drive wetland metal exports. Extremely high Al, Fe, and Mn concentrations (up to 40, 374, and 8 mg L(-1), respectively) were found in shallow acidic groundwaters from the Tuckean Swamp, Australia. Significant correlations between radon (a natural groundwater tracer) and metals in surface waters revealed that metal loads were driven primarily by groundwater discharge. Dissolved Fe, Mn, and Al loads during a 16-day flood triggered by a 213 mm rain event were respectively 80, 35, and 14% of the total surface water exports during the four months of observations. Counter clockwise hysteresis was observed for Fe and Mn in surface waters during the flood due to delayed groundwater inputs. Groundwater-derived Fe fluxes into artificial drains were 1 order of magnitude higher than total surface water exports, which is consistent with the known accumulation of monosulfidic black ooze within the wetland drains. Upscaling the Tuckean catchment export estimates yielded dissolved Fe fluxes from global acid sulfate soil catchments on the same order of magnitude of global river inputs into estuaries.     

Photoirradiation of dissolved humic acid induces arsenic(III) oxidation

The fate of arsenic in aquatic systems is influenced by dissolved natural organic matter (DOM). Using UV-A and visible light from a medium-pressure mercury lamp, the photosensitized oxidation of As(III) to As(V) in the presence of Suwannee River humic acid was investigated. Pseudo-first-order kinetics was observed. For 5 mg L(-1) of dissolved organic carbon (DOC) and 1.85 mEinstein m(-2) s(-1) UV-A fluence rate, the rate coefficient k degrees exp was 21.2 +/- 3.2 10(-5) s(-1), corresponding to a half-life <1 h. Rates increased linearly with DOC and they increased by a factor of 10 from pH 4 to 8. Based on experiments with radical scavengers, heavy water, and surrogates for DOM, excited triplet states and/or phenoxyl radicals seem to be important photooxidants in this system (rather than singlet oxygen, hydrogen peroxide, hydroxyl radicals, and superoxide). Photoirradiation of natural samples from freshwater lakes, rivers, and rice field water (Bangladesh) showed similar photoinduced oxidation rates based on DOC. Fe(III) (as polynuclear Fe(III)-(hydr)oxo complexes or Fe(III)-DOC complexes) accelerates the rate of photoinduced As(III) oxidation in the presence of DOC by a factor of 1.5-2.     

Impacts of Shewanella putrefaciens strain CN-32 cells and extracellular polymeric substances on the sorption of As(V) and As(III) on Fe(III)-(hydr)oxides

We investigated the effects of Shewanella putrefaciens cells and extracellular polymeric substances on the sorption of As(III) and As(V) to goethite, ferrihydrite, and hematite at pH 7.0. Adsorption of As(III) and As(V) at solution concentrations between 0.001 and 20 μM decreased by 10 to 45% in the presence of 0.3 g L(-1) EPS, with As(III) being affected more strongly than As(V). Also, inactivated Shewanella cells induced desorption of As(V) from the Fe(III)-(hydr)oxide mineral surfaces. ATR-FTIR studies of ternary As(V)-Shewanella-hematite systems indicated As(V) desorption concurrent with attachment of bacterial cells at the hematite surface, and showed evidence of inner-sphere coordination of bacterial phosphate and carboxylate groups at hematite surface sites. Competition between As(V) and bacterial phosphate and carboxylate groups for Fe(III)-(oxyhydr)oxide surface sites is proposed as an important factor leading to increased solubility of As(V). The results from this study have implications for the solubility of As(V) in the soil rhizosphere and in geochemical systems undergoing microbially mediated reduction and indicate that the presence of sorbed oxyanions may affect Fe-reduction and biofilm development at mineral surfaces.     

Reductive dissolution and biomineralization of iron hydroxide under dynamic flow conditions

Iron cycling and the associated changes in solid phase have dramatic implications for trace element mobility and bioavailability. Here we explore the formation of secondary iron phases during microbially mediated reductive dissolution of ferrihydrite-coated sand under dynamic flow conditions. An initial period (10 d) of rapid reduction, indicated by consumption of lactate and production of acetate and Fe-(II) to the pore water in association with a darkening of the column material, is followed by much lower rate of reduction to the termination of the experiment after 48 d. Although some Fe (<25%) is lost to the effluent pore water, the majority remains within the column as ferrihydrite (20-70%) and the secondary mineral phases magnetite (0-70%) and goethite (0-25%). Ferrihydrite converts to goethite in the influent end of the column where dissolved Fe(II) concentrations are low and converts to magnetite toward the effluent end where Fe(III) concentrations are elevated. A decline in the rate of Fe(II) production occurs concurrent with the formation of goethite and magnetite; at the termination of the experiment, the rate of reduction is <5% the initial rate. Despite the dramatic decrease in the rate of reduction, greater than 80% of the residual Fe remains in the ferric state. These results highlight the importance of coupled flow and water chemistry in controlling the rate and solid-phase products of iron (hydr)oxide reduction.