Reductive Dissolution Of Iron Oxides Research Articles

Effects of citric acid on arsenic transformation and microbial communities in different paddy soils

Root exudate is a major source of soil organic matter and can significantly affect arsenic (As) migration and transformation in paddy soils. Citric acid is the main component of rice root exudate, however, the impacts and rules of citric acid on As bioavailability and rhizobacteria in different soils remains unclear. This study investigated the effects of citric acid on As transformation and microbial community in ten different paddy soils by flooded soil culture experiments. The results showed that citric acid addition increased total As and arsenate (As(V)) in the soil porewater by up to 41-fold and 65-fold, respectively, after 2-h incubation. As(V) was the main As species in soil porewater within 10 days with the addition of citric acid. Non-specifically sorbed As of soils, total Fe and total As were the main environmental factors affecting the soil microbial communities. High-throughput sequencing analysis demonstrated that citric acid addition significantly altered the soil microbial community structure, shifting the Proteobacteria-related reducing bacteria to Firmicutes-related reducing bacteria in different paddy soils. The relative abundance of Firmicutes was promoted by 174–196%. Clostridium-related bacteria belonging to Firmicutes became the dominant genera, which is believed to regulate As release through the reductive dissolution of iron oxides or the direct reduction of As(V) to arsenite (As(III)). However, citric acid addition significantly decreased the relative abundance of Geobacter and Anaeromyxobacter, which are also typical active As(V)- and ferric-reducing bacteria. Real-time quantitative polymerase chain reaction (qPCR) also revealed that the addition of citric acid significantly decreased the relative abundances of Geobacter in the different soils by 8–28 times while the relative abundances of Clostridium increased by 2–5 times. These results provide significant insight on As transformation in different types of rice rhizospheric soils and guidance for the application of rice varieties with low citric acid exuding to restrict As accumulation.

Removal of arsenic from contaminated soils by combining tartaric acid with dithionite: An efficient composite washing agent

In the context of the increasing global problem of arsenic (As) contamination in soils, an efficient remediation method is urgently needed to alleviate it. In this study, a composite washing agent consisting of 0.2 mol L−1 dithionite and 0.05 mol L−1 tartaric acid (TA) in a 1:1 mixing volume ratio was prepared and used in the remediation of arsenic-contaminated soils. The results showed that the removal efficiency of arsenic was 62.47% in soil 1 at a concentration of 134 mg kg−1 and 70.08% in soil 2 at a concentration of 70 mg kg−1. Dithionite achieved greater release of the arsenic associated with amorphous hydrous oxides of iron and aluminium (F3) and arsenic associated with crystalline hydrous oxides of iron and aluminium (F4) forms of arsenic by the reductive dissolution of iron oxides, while also reducing Fe3+. TA released some arsenic in the specifically adsorbed (F2) and F3 forms through acidic effects. The mechanism of arsenic removal from the composite washing agent was found to be a synergistic effect between dithionite and TA. The TA complexation formed Fe-TA complexes with Fe2+ in solution, preventing the formation of new iron mineral phases and reducing the readsorption or precipitation of arsenic to the soil surface. Meanwhile, the formation of Fe-TA complexes kept the iron oxides dissolved, allowing more iron oxide-bound arsenic (F3 +F4) to be released. This study showed that combining TA with dithionite is a promising technology for remediating arsenic-contaminated soils because of its high efficiency.

Coupled effects of sedimentary iron oxides and organic matter on geogenic phosphorus mobilization in alluvial-lacustrine aquifers

The organic matter (OM) biodegradation and reductive dissolution of iron oxides have been acknowledged as key factors in the release of geogenic phosphorus (P) to groundwater. However, the coupled effects of natural OM with iron oxides on the mobilization of geogenic P remain unclear. Groundwater with high and low P concentrations has been observed in two boreholes in the alluvial-lacustrine aquifer system of the Central Yangtze River Basin. Sediment samples from these boreholes were examined for their P and Fe species as well as their OM properties. The results show that sediments from borehole S1 with high P levels contain more bioavailable P, particularly iron oxide bound P (Fe-P) and organic P (OP) than those from borehole S2 with low P levels. Regarding borehole S2, Fe-P and OP show positive correlations with total organic carbon as well as amorphous iron oxides (FeOX1), which indicate the presence of Fe-OM-P ternary complexes, further evidenced by FTIR results. In a reducing environment, the protein-like component (C3) and terrestrial humic-like component (C2) will biodegrade. In the process of C3 biodegradation, FeOX1 will act as electron acceptors and then undergo reductive dissolution. In the process of C2 biodegradation, FeOX1 and crystalline iron oxides (FeOX2) will act as electron acceptors. FeOX2 will also act as conduits in the microbial utilization pathway. However, the formation of stable P-Fe-OM ternary complexes will inhibit the reductive dissolution of iron oxides and OM biodegradation, thus inhibiting the mobilization of P. This study provides new insights into the enrichment and mobilization of P in alluvial-lacustrine aquifer systems.

Effect of ascorbic acid and combination with fulvic acid on the electrokinetic remediation of paddy soil contaminated by arsenic-containing acid mine drainage

Electrokinetic remediation (EKR) of soil contaminated by arsenic-containing acid mine drainage is usually challenging due to the strong adsorption capacity of iron oxides to arsenic. To solve this problem, ascorbic acid and fulvic acid were used as additives to enhance the mobility of arsenic in this study. Both ascorbic acid (EK-AA) and its combination with fulvic acid (EK-AF) increase soil water content and conductivity, forming more conducive reducing conditions, and augmenting the reduction and removal of iron, especially in the EK-AF treatment. After 14 days of EKR, the arsenic removal efficiency in EK-AF treatment reached 29.1%, while the control group was only 5.5%. The removal of arsenic in this study was attributed to the reductive dissolution of iron oxides and the activation of residual arsenic. The co-existing heavy metals antimony, copper, lead, and zinc could also be removed, with the highest antimony removal efficiency of 31.7%. Our results demonstrated that ascorbic and fulvic acids can be ideal green additives to achieve the reductive dissolution of iron oxides and activate arsenic, while maintaining soil physicochemical properties favorable to EKR, which effectively improves the removal of arsenic and co-existing heavy metals.

Identification of arsenic spatial distribution by hydrogeochemical processes represented by different ion ratios in the Hohhot Basin, China.

The Hohhot Basin, a typical inland basin of the Yellow River Basin in China, has high concentrations of arsenic (As) in its shallow groundwater, while the factors dominating the distribution of high arsenic levels remain to be further identified. An analysis of the ratio of hydrogeochemical compositions can help to reveal the spatial characteristics of the shallow groundwater environmental conditions and the distribution of high-arsenic water (As >10 μg/L). In this study, a total of 170 samples of shallow groundwater in the Hohhot Basin were collected and water samples with As >10 μg/L accounted for 29.4% of the total. Based on the slope changes of the cumulative frequency curves of (HCO3- + CO32-)/SO42-, Ca2+/(HCO3- + CO32-), Ca2+/Mg2+, and Na+/Ca2+, the groundwater in the study area can be categorized into six different zones according to the environmental characteristics including redox condition, water recharge intensity, and cation exchange level. The result shows that the groundwater in the front of the piedmont alluvial plain and platform is in a weak reducing condition with high lateral recharge intensity, fast runoff, and weak cation exchange. In the Dahei River alluvial plain, which serves as the groundwater discharge zone, the groundwater runoff is sluggish with poor lateral recharge, sufficient exchange between cations in the groundwater and the aquifer matrix, and enhanced reducibility. The degree of oxidation increased in the groundwater near the Hasuhai Lake and the drainage canal, which adverse to the arsenic enrichment. High-arsenic groundwater is mainly distributed in aquifers of (HCO3- + CO32-)/SO42 > 10, Na+/Ca2+ > 13, and Ca2+/(HCO3- + CO32-) < 0.1, which represent the strong reducing condition, low surface water recharge intensity, and strong cation exchange condition. Reductive dissolution of iron oxide, strong evaporation and concentration process, and competition from phosphate in aquifers jointly lead to the release of arsenic into groundwater.

Arsenic extraction from seriously contaminated paddy soils with ferrihydrite-loaded sand columns

Reductive dissolution of iron oxides in flooded paddy soils is the most important cause of arsenic (As) release into soil aqueous solution and thus entry into rice. From the perspective of soil cleanup, however, As release under flooded condition could facilitate labile As removal. In this study, a porous column pre-loaded with ferrihydrite (Fh) was constructed, and its efficiency of soil As extraction was investigated using a purpose-designed mesocosm coupled with diffusive gradients in thin films (DGT) for in situ visualization. With Fh-column deployed in aqueous solution, >90% removal of As(III) was achieved within 5 days at initial As (100 mg L−1) of two orders of magnitude higher than in most paddy soil solutions (1–1538 μg L−1). By applying Fh-column in a seriously contaminated paddy soil (102 mg As kg−1), porewater As showed stepwise decreases from 2727 μg L−1 to 129–1455 μg L−1 at a distance-dependent manner over four intermittent extractions during 91 days. Soil DGT-As exhibited similar spatiotemporal changes to porewater As. After four extractions, 17.8% of total soil As was removed by Fh-column in a 10 cm radius range on average and ∼1/3 of As bound to amorphous and crystalline Fe/Al oxides was depleted, which accounted for 88.7% of decline in total soil As. With the post-extracted soil, a 48% lower As accumulation in rice seedlings and a 65% decline in bulk soil DGT-As were attained. This study provides a conceptual foundation for rapid removal of high soluble As by Fh-columns from flooded soils, improving seriously As-contaminated paddies to sustainable resources for safe food production.

Unraveling the impact of iron oxides-organic matter complexes on iodine mobilization in alluvial-lacustrine aquifers from central Yangtze River Basin

The biodegradation of organic matter triggers the reductive dissolution of iron oxides with the transformation among iodine species has been mostly accepted as the key iodine mobilization process in groundwater system. However, molecular characteristics of natural organic matter (NOM) and their interaction with iron oxides on geogenic iodine enrichment remain unclear. We used Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to characterize the molecular composition of both dissolved organic matter (DOM) in groundwater and water-soluble organic matter (WSOM) in aquifer sediments being depth-matched with groundwater from monitoring wells in typical iodine-affected aquifers within the central Yangtze River Basin. The results show that WSOM in high-iodine sediments contains more high molecular weight (HMW) organic compounds with higher aromaticity and nominal oxidation state of carbon (NOSC), including polycyclic aromatics, polyphenols and highly unsaturated compounds. These compounds are mostly positively associated with amorphous iron oxides (Feox1) in aquifer sediments. The association between iodine and WSOM is highly consistent with that between amorphous Feox1 and WSOM, but is contrary to that between crystalline iron oxides (Feox2) and WSOM. DOM in groundwater with higher iodine concentration contains more aliphatic compounds and less polyphenols. The complexation of HMW organic compounds of WSOM to iodine-bearing amorphous Feox1 plays an important role in iodine mobilization, which could inhibit the amorphous Feox1 transformation to crystalline Feox2. These observations indicate the biodegradation of HMW organic matter (polycyclic aromatics, polyphenols and highly unsaturated compounds) in WSOM fueling the reductive dissolution of amorphous Feox1 predominantly promotes the release of iodine from aquifer sediments into groundwater. This research provides new insights into the mobilization mechanisms of iodine in alluvial-lacustrine groundwater system controlled by the Fe-OM complexation at the molecular level.

Factors controlling iodine enrichment in a coastal plain aquifer in the North Jiangsu Yishusi Plain, China

Iodine is an essential micronutrient in the human diet and an appropriate human iodine intake level is important for population health. Excessive iodine intake is often associated with high iodine groundwater which serves as an important drinking water source in many regions. This study aims to identify the source and key hydrogeochemical processes for iodine accumulation and mobility in the groundwaters of the Northern Jiangsu Yishusi Plain. Combined hydrogeochemical and statistical analyses, specifically random forest modeling and factor analysis, were used to explore the mechanisms affecting the spatial distribution of iodine. The concentration of iodine in the investigated groundwaters was found to vary widely and to range between 4.8 and 4750 μg/L, with 48.9% of the total samples (674) exceeding the threshold value of 100 μg/L for toxic exposure, as defined by the Chinese high‑iodine standard guideline. High iodine concentrations are shown to mainly occur in the marine plain and the shallow aquifer associated with the floodplains of the Old Yellow River. The marine or lagoons-facies sediments were identified as the most plausible iodine source. In addition, mixing of groundwater with paleo-seawater might also have played a role in the coastal area. In contrast, the flood sediments of the Old Yellow River are shown to be an unlikely source. However, they serve as a cover layer that favored the development of reducing hydrogeochemical conditions that can trigger iodine mobilization via the reductive dissolution of iron oxides and the degradation of organic matter. Slow groundwater flow rates also appear to favor iodine release from sediments.

Redox-active antibiotics enhance phosphorus bioavailability.

Microbial production of antibiotics is common, but our understanding of their roles in the environment is limited. In this study, we explore long-standing observations that microbes increase the production of redox-active antibiotics under phosphorus limitation. The availability of phosphorus, a nutrient required by all life on Earth and essential for agriculture, can be controlled by adsorption to and release from iron minerals by means of redox cycling. Using phenazine antibiotic production by pseudomonads as a case study, we show that phenazines are regulated by phosphorus, solubilize phosphorus through reductive dissolution of iron oxides in the lab and field, and increase phosphorus-limited microbial growth. Phenazines are just one of many examples of phosphorus-regulated antibiotics. Our work suggests a widespread but previously unappreciated role for redox-active antibiotics in phosphorus acquisition and cycling.

Phenazines liberate phosphate

Microbiology Bacteria secrete a wide range of small molecules with chemical reactivity that offers multiple functions in different contexts. Phenazines are commonly considered to be antibiotics, but they can also participate in environmental redox reactions, especially with iron. McRose and Newman found that phenazines, when added exogenously or made by bacteria in situ, can liberate phosphorous (P) in the form of phosphate from mineral surfaces, and that the production of these molecules is regulated by signaling pathways that respond to P limitation. Strains unable to produce these molecules grew more slowly under P limitation but could be rescued by the addition of exogenous phenazines. The authors hypothesize that reductive dissolution of iron oxides has the benefit of liberating P, and that this could be one mechanism of microbial P acquisition in some environments. Science , this issue p. [1033][1] [1]: /lookup/doi/10.1126/science.abd1515

Impact process of the aquitard to regional arsenic accumulation of the underlying aquifer in Central Yangtze River Basin.

The clayey aquitard has the potential to release geogenic poisonous chemicals such as arsenic (As) to the adjacent aquifer owing to complex hydrologic or biogeochemical processes. However, it remains unclear whether the aquitard has effect on As enrichment in the underlying aquifer in regions without extensive groundwater pumping, and the related processes have been poorly known. Based on piezometer water chemistry, stable water isotopes, sediment chemistry and reactive-transport model, this study aims to reveal the impact process of the aquitard to As accumulation of underlying aquifer from central Yangtze River Basin, a As-affected area without extensive groundwater pumping. On the whole, As migrated from top to bottom of the aquitard (especially the depth over 10m) and significantly influenced the As accumulation in the underlying aquifer. Nonetheless, the results of three topical boreholes showed two different hydrogeological conditions affected As release in the aquitard and enrichment in the underlying aquifer. Different hydrogeological conditions could result in the input of different species organic carbon and then impact As concentrations in the aquifer. When the aquitard was near surface water bodies, the reductive dissolution of iron oxides was the main driver for As release and the aquitard had a significant influence on the enrichment of arsenic in the aquifer. At areas without surface water bodies nearby, the desorption of As(V) from minerals was the main source of As and the concentrations of As in pore water were quite low; this pattern had little effect on the enrichment of arsenic in the aquifer.

Arsenic contamination of Bangladesh aquifers exacerbated by clay layers

Confining clay layers typically protect groundwater aquifers against downward intrusion of contaminants. In the context of groundwater arsenic in Bangladesh, we challenge this notion here by showing that organic carbon drawn from a clay layer into a low-arsenic pre-Holocene (>12 kyr-old) aquifer promotes the reductive dissolution of iron oxides and the release of arsenic. The finding explains a steady rise in arsenic concentrations in a pre-Holocene aquifer below such a clay layer and the repeated failure of a structurally sound community well. Tritium measurements indicate that groundwater from the affected depth interval (40–50 m) was recharged >60 years ago. Deeper (55–65 m) groundwater in the same pre-Holocene aquifer was recharged only 10–50 years ago but is still low in arsenic. Proximity to a confining clay layer that expels organic carbon as an indirect response to groundwater pumping, rather than directly accelerated recharge, caused arsenic contamination of this pre-Holocene aquifer.

Photo-induced redox coupling of dissolved organic matter and iron in biochars and soil system: Enhanced mobility of arsenic

Dissolved organic matter (DOM) elucidated from biochars enhances the dissolution of iron oxides and reduction of iron. However, given that reduction mechanism of iron (Fe(III)) in the practical biochar applications for soil amendment and environmental remediation have not been fully elucidated, this study laid great emphasis on the photo-induced Fe(II) liberated from DOM-Fe(III) complexes. Thus, pyrolysis of biomass was carried out at 300 °C to maximize DOM release from biochars. Moreover, three different biomass samples (rice straw (R), granular sludge (G) from an anaerobic digester, and spent coffee grounds (C)) were chosen as carbon substrates for biochars preparation. To demonstrate the transformation of Fe(III), 1 and 5 wt% biochar was applied to the clean (S1) and arsenic-contaminated (S2) soil with/without the light. The results indicate that the light condition produces more Fe(II). The amount of Fe(II) accounts for 25.3, 28.6, and 30.7% of total iron under the light with 5 wt% GB, RB, and CB in S1, and 10.6, 13.1, and 13.8% in S2. This study demonstrates that Fe(II) is generated more under ultraviolet irradiation than visible light and dark condition. In addition, a control experiment without biochar showed that DOM plays an important role in the reduction of Fe(III). The mobility of arsenic increased under the light condition since the intermediates of DOM photo-degradation accelerates the dissolution of iron oxides and arsenic competes with DOM for the adsorption. Therefore, there was no significant correlation between the elution of arsenic and the formation of Fe(II) during the reductive dissolution of iron oxide under the light condition.

Coupled Kinetics Model for Microbially Mediated Arsenic Reduction and Adsorption/Desorption on Iron Oxides: Role of Arsenic Desorption Induced by Microbes.

The dynamic behavior of arsenic (As) species is closely associated with iron mineral dissolution/transformation in the environment. Bacterially induced As(V) desorption from iron oxides may be another important process that facilitates As(V) release from iron oxides without significant reductive dissolution of iron oxides. Under the impact of bacterially induced desorption, As kinetic behavior is controlled by both the microbial reduction of As(V) and the As(III)&As(V) reactions on iron oxide surfaces. However, there is still a lack of quantitative understanding on the coupled kinetics of these processes in complex systems. We developed a quantitative model that integrated the time-dependent microbial reduction of As(V) with nonlinear As(III)&As(V) adsorption/desorption kinetics on iron oxides under the impact of bacterially induced As(V) desorption. We collected and modeled literature data from 11 representative studies, in which microbial reduction reactions occurred with minimal iron oxide dissolution/transformation. Our model highlighted the significance of microbially induced As(V) desorption and time-dependent changes of microbial reduction rates. The model can quantitatively assess the roles and the coupling of individual reactions in controlling the overall reaction rates. It provided a basis for developing comprehensive models for As cycling in the environment by coupling with other chemical, physical, and microbial processes.

Digestive solubilization of particle-associated arsenate by deposit-feeders: The roles of proteinaceous and surfactant materials

Solubilization of arsenate in guts of deposit-feeders is a key process for their dietary uptake of arsenate from contaminated sediments. The present study explored this digestive solubilization with in vitro extraction experiments that quantified arsenic (As) release from substrates (natural sediment and As-enriched iron oxides) in the presence of various digestive agents (proteins, amino acids and surfactants collected from gut fluid of a sipunculan worm). To investigate potential mechanisms for the influence of digestive agents, analyses determined correlations between As and Fe concentrations, the size distribution of the As bound to the digestive agents, and the adsorption of the digestive agents on the substrates. Both the digestive surfactants and proteinaceous materials increased arsenate mobilization, with the surfactants enhancing the effects of the proteinaceous materials. Arsenate reduction and reductive dissolution of iron oxides were not observed and correlations between the concentrations of released As and Fe were weak. These findings indicate that dissolution release of Fe did not appear to be the main route by which the digestive agents mobilized particle-associated As. Most of the released As (>70%) was distributed in the <10 kDa fraction of the digestive agents, showing that the As mobilization was also not caused by complexation with proteins in the digestive agents. In contrast, adsorption of the digestive agents occurred along with the release of arsenate from the arsenate-rich substrates, suggesting that competitive adsorption was the mechanism by which the digestive agents mobilized sedimentary arsenate. Our work demonstrated that the presence of digestive surfactants significantly enhances arsenate availability during deposit feeding.

Oxygenated Mesoproterozoic lake revealed through magnetic mineralogy

Terrestrial environments have been suggested as an oxic haven for eukaryotic life and diversification during portions of the Proterozoic Eon when the ocean was dominantly anoxic. However, iron speciation and Fe/Al data from the ca. 1.1-billion-year-old Nonesuch Formation, deposited in a large lake and bearing a diverse assemblage of early eukaryotes, are interpreted to indicate persistently anoxic conditions. To shed light on these distinct hypotheses, we analyzed two drill cores spanning the transgression into the lake and its subsequent shallowing. While the proportion of highly reactive to total iron (FeHR/FeT) is consistent through the sediments and typically in the range taken to be equivocal between anoxic and oxic conditions, magnetic experiments and petrographic data reveal that iron exists in three distinct mineral assemblages resulting from an oxycline. In the deepest waters, reductive dissolution of iron oxides records an anoxic environment. However, the remainder of the sedimentary succession has iron oxide assemblages indicative of an oxygenated environment. At intermediate water depths, a mixed-phase facies with hematite and magnetite indicates low oxygen conditions. In the shallowest waters of the lake, nearly every iron oxide has been oxidized to its most oxidized form, hematite. Combining magnetics and textural analyses results in a more nuanced understanding of ambiguous geochemical signals and indicates that for much of its temporal duration, and throughout much of its water column, there was oxygen in the waters of Paleolake Nonesuch.

Rapid Ferric Transformation by Reductive Dissolution of Schwertmannite for Highly Efficient Catalytic Degradation of Rhodamine B

In this study, reductive dissolution of iron oxides was considered for the acceleration of the transformation from Fe(III) to Fe(II) to improve the degradation of rhodamine B (RhB) by potassium persulfate (PS) activation on schwertmannite. The addition of hydroxylamine (HA) showed an enhancement effect on the degradation at pH 3 and 5, but insignificant efficiency of the addition was obtained at pH 9. The surface reduction from Fe(III)-OH to Fe(II)-OH by HA was considered dominant for the acceleration of PS activation through the reductive dissolution process, and the hydroxyl and sulfate radicals generated by the decomposition of surface complexes were main primary reactive oxidants that contributed to the degradation of RhB.

Effect of dissolved organic carbon from sludge, Rice straw and spent coffee ground biochar on the mobility of arsenic in soil

To date, studies on the mobility of arsenic (As) in soil amended with biochar have primarily relied on broad empirical observations, resulting in a gap between the behavior of As in amended soil and the chemical mechanisms controlling that behavior. This study focuses on the influence of abiotic factors in As mobility in As-contaminated soils amended with biochar. In order to understand the leaching of DOC and phosphate across a range of biomass feedstock and pyrolysis temperature, rice straw and granular sludge from an anaerobic digester were pyrolyzed at 300, 550, and 700 °C, and subjected to leaching studies by mixing air dried soil with 10 wt% of biochar at a soil: water ratio of 1:1(w/v). The concentration of DOC in the presence of granular sludge biochar and rice straw biochar increased from 190 mg L−1 to 2605 mg L−1 and 1192 mg L−1, respectively, which considerable accelerated the mobilization of Fe and As. More specifically, DOC drove the reduction of Fe(III) to Fe(II). Our results suggest enhanced release of As via the reductive dissolution of iron oxides, including by the chelating-enhanced dissolution of Fe oxides, and competitive desorption by DOC and phosphate from biochar. The influence of DOC and phosphate was further evaluated using realistic application amounts (1, 3, and 5 wt%) of biochars derived from pyrolysis of granular sludge, rice straw and spent coffee ground at 300 and 550 °C. The results from these experiments further confirm that DOC is a key factor for influencing the mobility of As in the amendment of biochar to As-contaminated soil, which indicates that biochar having low levels of leachable carbon should be amended to As-contaminated soils, and with caution.

In-situ mobilization and transformation of iron oxides-adsorbed arsenate in natural groundwater

Although reductive dissolution of Fe(III) oxides has been well accepted for As mobilization in alluvial aquifers, the key factors controlling this process are poorly understood. Arsenic(V)-adsorbing ferrihydrite, goethite and hematite were used to examine in-situ mobilization and transformation of adsorbed As(V) and Fe(III) oxides. In the Hetao basin, seven wells with wide ranges of groundwater As were selected to host As(V)-Fe(III) oxides sand. During 80 d experiments, As was firstly desorbed and then released via reductive dissolution of iron oxide from ferrihydrite, while only desorption was observed from goethite/hematite sand. Desorbed As was predominantly controlled by groundwater HCO3− and DOC, while reductive dissolution-related As release was mainly regulated by ORP values, DOC and Fe(II) concentrations. Mineral transformation from ferrihydrite to lepidocrocite and goethite/or mackinawite would also contribute to As release. Arsenic species was transformed from As(V) to As(III) on ferrihydrite, but remained unchanged on goethite and hematite. Arsenic partition between As-Fe(III) oxide sand and real groundwater ranged between 0.012 and 0.102L/g. Kd-sand between As-goethite sand/As-hematite sand and groundwater fell within the ranges observed between sediments and groundwater. This study suggests that As desorption, reductive dissolution and mineral transformation of ferrihydrite would be the major processes controlling As mobility.

Numerical Modeling of Arsenic Mobility during Reductive Iron-Mineral Transformations.

Millions of individuals worldwide are chronically exposed to hazardous concentrations of arsenic from contaminated drinking water. Despite massive efforts toward understanding the extent and underlying geochemical processes of the problem, numerical modeling and reliable predictions of future arsenic behavior remain a significant challenge. One of the key knowledge gaps concerns a refined understanding of the mechanisms that underlie arsenic mobilization, particularly under the onset of anaerobic conditions, and the quantification of the factors that affect this process. In this study, we focus on the development and testing of appropriate conceptual and numerical model approaches to represent and quantify the reductive dissolution of iron oxides, the concomitant release of sorbed arsenic, and the role of iron-mineral transformations. The initial model development in this study was guided by data and hypothesized processes from a previously reported,1 well-controlled column experiment in which arsenic desorption from ferrihydrite coated sands by variable loads of organic carbon was investigated. Using the measured data as constraints, we provide a quantitative interpretation of the processes controlling arsenic mobility during the microbial reductive transformation of iron oxides. Our analysis suggests that the observed arsenic behavior is primarily controlled by a combination of reductive dissolution of ferrihydrite, arsenic incorporation into or co-precipitation with freshly transformed iron minerals, and partial arsenic redox transformations.