Different effects of vitamin supplementation on arsenic bioaccessibility in contaminated soils using multiple in vitro methods and their relevant mechanisms.

Exposure to arsenic (As) induces adverse effects on human health. Vitamins B1, B6, and C, as indispensable micronutrients for humans, have been proven to influence the metabolism and toxicity of ingested As. To determine the effect of vitamins on health risks associated with soil exposure, As bioaccessibility in 14 soil samples using four in vitro methods of IVG, PBET, SBRC, and UBM was measured with the addition of vitamins B1, B6, and C. With vitamins B1 and B6 addition, the gastric As bioaccessibility in 14 soil samples was reduced by 1.14-3.52 and 1.14-5.02 fold, respectively, and instead an increase in the intestinal bioaccessibility was presented in some cases. Vitamin C supplementation yielded higher As bioaccessibility in the gastric (1.13-13.02 fold) and small intestinal (1.21-33.35 fold) phases, respectively. As evidenced by the X-ray absorption near-edge spectroscopy (XANES) and Fourier transform infrared spectroscopy (FTIR) analysis, arsenic dissolution was promoted by Fe-As and hindered by the formation of Al-As fractions. Soil As dissolution in the simulated gastrointestinal tract was strongly influenced by soil minerals and ingested vitamins, due to the chelation of arsenic with vitamins and soil minerals such as Fe (hydr)oxides, and Fe(III) reductive dissolution to enhance As release by vitamin C as an iron reducer. These findings will expand the knowledge of health risks of exposure to As-contaminated soils and nutritional interventions aiming at the mitigation of As toxicity.

Effect of vitamin C supplement on lead bioaccessibility in contaminated soils using multiple in vitro gastrointestinal assays: Mechanisms and health risks.

Effects of vitamin C supplementation on the oral bioaccessibility of lead (Pb) present in contaminated soils were examined using a number of in vitro assays (PBET, SBRC, UBM and IVG). In the presence of vitamin C, an increase in Pb bioaccessibility was observed in the gastric phase by 1.3-fold (30.5%-85.5%) and in the intestinal phase by 3.1-fold (0.9%-58.9%). Lead mobilization was regulated by reductive dissolution of Fe(III) and sequestration of Pb on secondary Fe minerals. Sequential extraction by the Bureau Community of Reference (BCR) provided more evidence that reducible fraction and residual fraction were major contributor of gastric Pb bioaccessibility, as well as reduced fractions in intestinal Pb bioaccessibility. In addition, higher non-carcinogenic risks may occur based on target hazard quotient (THQ ≥ 1). For people exposed to Pb present in soil, the management of vitamin C supplements is of serious concern.

Impact of Organic Matter on Microbially-Mediated Reduction and Mobilization of Arsenic and Iron in Arsenic(V)-Bearing Ferrihydrite.

Under anoxic conditions, the interactions between As-bearing ferrihydrite (Fh) and As(V)-reducing bacteria are known to cause Fh transformations and As mobilization. However, the impact of different types of organic matter (OM) on microbial As/Fe transformation in As-bearing Fh-organic associations remains unclear. In our study, we therefore exposed arsenate-adsorbed ferrihydrite, ferrihydrite-PGA (polygalacturonic acid), and ferrihydrite-HA (humic acid) complexes to two typical Fe(III)- and As(V)-reducing bacteria, and followed the fate of Fe and As in the solid and aqueous phases. Results show that PGA and HA promoted the reductive dissolution of Fh, resulting in 0.7-1.6 and 0.8-1.9 times more As release than in the OM-free Fh, respectively. This was achieved by higher cell numbers in the presence of PGA, and through Fe-reduction via electron-shuttling facilitated by HA. Arsenic-XAS results showed that the solid-phase arsenite fraction in Fh-PGA and Fh-HA was 15-19% and 27-28% higher than in pure Fh, respectively. The solid-associated arsenite fraction likely increased because PGA promoted cell growth and As(V) reduction, while HA provided electron shuttling compounds for direct microbial As(V)-reduction. Collectively, our findings demonstrate that As speciation and partitioning during microbial reduction of Fh-organic associations are strongly influenced by PGA and HA, as well as the strains' abilities to utilize electron-shuttling compounds.

Differences in nitrification and ammonium-oxidising prokaryotes in the process of wetland restoration.

Ammonia-oxidising archaea (AOA) and ammonia-oxidising bacteria (AOB) are ammonium oxidising prokaryotes that can drive soil nitrification in wetlands. During the restoration of wetlands, different types of land use soils (agricultural soil [AS], restored wetland soil [RS], and natural wetland soil [NWS]) are present. However, studies on the effects of changes in the types of land use in wetlands during restoration on nitrification and the community composition of AOA and AOB are still not well understood. In this study, the differences in the potential nitrification rate (PNR) and community composition of AOA and AOB in AS, RS, and NWS were compared and discussed. The results indicated that the PNRs in the AS, RS, and NWS were on the same order of magnitude. Nitrification was mainly driven by AOB. High-throughput sequencing results showed that the genus Nitrososphaera of AOA and unclassified_o_Nitrosomonadales of AOB were only detected in the AS. Redundancy analysis (RDA) results indicated that the community composition of AOA was mostly influenced by pH, while TC was the most influential variable on the community composition of AOB. Our study provides a basis for distinguishing the roles of ammonium-oxidising prokaryotes in nitrification and further understanding the changes in nitrifying activity in wetlands during restoration.

In Vitro Assessment of Arsenic Release and Transformation from As(V)-Sorbed Goethite and Jarosite: The Influence of Human Gut Microbiota.

The importance of arsenic metabolism by gut microbiota has been evidenced in risk characterization from As exposures. In this study, we evaluated the metabolic potency of human gut microbiota toward As(V)-sorbed goethite and jarosite, presenting different behaviors of As release, and the solid-liquid transformation and partitioning. The release of As occurred mainly in the small intestinal phase for jarosite and in the colon phase for goethite, respectively. We found higher degree of As(V) and Fe(III) reduction by human gut microbiota in the colon digests of goethite than jarosite. Speciation analysis using high-performance liquid chromatography coupled with inductively coupled plasma mass spectrometry and X-ray absorption near-edge spectroscopy, revealed that 43.2% and 8.5% of total As was present as As(III) in the liquid and solid phase, respectively, after goethite incubation, whereas almost all generated As(III) was in the colon digests of jarosite. Therefore, As bioaccessibility in human gastrointestinal tract was predominantly contributed to Fe(III) dissolution in jarosite, and to microbial reduction of Fe(III) and As(V) in goethite. It expanded our knowledge on the role of Fe minerals in human health risk assessment associated with soil As exposures.

Assessment of nutrients effect on the bioaccessibility of Cd and Cu in contaminated soil.

Soil is considered as a sink for heavy metals. Human health is severely affected by the continuous intake of toxic heavy metals even in a very low concentration. In the present experiment, we determined the influence of nutritional status including control (fasted condition), glucose (fed state), plant protein (fed state), animal protein (fed state) and calcium (fed state) on soil cadmium (Cd) and copper (Cu) bioaccessibility using physiologically-based extraction test (PBET) method together with simulator of the human intestinal microbial ecosystem (SHIME) model. The bioaccessibility of Cd was 1.06-73.58%, 0.44-54.79% and 0-17.78% and Cu was 3.81-67.32%, 4.98-71.14%, and 0-17.54% in the phase-I, phase-II and Phase-III respectively (in this study gastric phase, small intestinal phase and colon phase were considered as phase-I, phase-II and Phase-III respectively). The outcomes showed that, the average Cd bioaccessibility was higher with animal protein addition compared with other treatments in different phases. So, the effect of animal protein on Cd bioaccessibility was higher than other treatments in the phase-I, phase-II and phase-III. Due to the addition of plant protein, the higher average bioaccessibility of Cu was noticed in phase-I and phase-II in comparison to other treatments. However, in phase-III, the higher average bioaccessibility of Cu was found due to control treatment comparing with other treatments. Therefore, the influence of plant protein was higher than other nutrients on Cu bioaccessibility in the phase-I and phase-II. Moreover, other nutrients showed variable influence on Cd and Cu bioaccessibility. So, nutritional status has a significant effect on bioaccessibility as well as human health risk assessment.

Shifts of the nirS and nirK denitrifiers in different land use types and seasons in the Sanjiang Plain, China.

Denitrification is a key nitrogen removal process that involves many denitrifying bacteria. In this study, the denitrification performance was estimated for soil samples from different land use types including farmland soil, restored wetland soil, and wetland soil. The quantitative real-time polymerase chain reaction results showed that the average abundance of nirS and nirK genes was notably affected by seasonal changes, increasing from 2.34 × 10 6 and 2.81 × 10 6 to 1.97 × 10 6 and 4.55 × 10 6 gene copies/g of dry soil, respectively, from autumn to spring. This suggests that the abundance of nirS and nirK denitrifiers in spring is higher than those in autumn. Furthermore, the abundance of nirS and nirK genes was higher in the farmland soil than in restored wetland soil and wetland soil in both seasons. According to the analyses of MiSeq sequencing of nirS and nirK genes, Halobacteriaceae could be used as a special strain to distinguish wetland soil from farmland soil and restored wetland soil. Furthermore, redundancy analysis indicated that the soil environmental variables of total carbon, total nitrogen, moisture content, and organic matter were the main factors affecting the community structures of nirS and nirK denitrifiers existing in wetland soil. These findings could contribute to understanding the differences in nirS and nirK denitrifiers between different land use types during seasonal changes.

Arsenic redox transformation by Pseudomonas sp. HN-2 isolated from arsenic-contaminated soil in Hunan, China.

A mesophilic, Gram-negative, arsenite[As(III)]-oxidizing and arsenate[As(V)]-reducing bacterial strain, Pseudomonas sp. HN-2, was isolated from an As-contaminated soil. Phylogenetic analysis based on 16S rRNA gene sequencing indicated that the strain was closely related to Pseudomonas stutzeri. Under aerobic conditions, this strain oxidized 92.0% (61.4µmol/L) of arsenite to arsenate within 3hr of incubation. Reduction of As(V) to As(III) occurred in anoxic conditions. Pseudomonas sp. HN-2 is among the first soil bacteria shown to be capable of both aerobic As(III) oxidation and anoxic As(V) reduction. The strain, as an efficient As(III) oxidizer and As(V) reducer in Pseudomonas, has the potential to impact arsenic mobility in both anoxic and aerobic environments, and has potential application in As remediation processes.

In Vitro Method To Assess Soil Arsenic Metabolism by Human Gut Microbiota: Arsenic Speciation and Distribution.

Arsenic (As) speciation and distribution are two important factors in assessing human health risk from As-contaminated soil. In this study, we used the combination of physiologically based extraction test (PBET) and Simulator of Human Intestinal Microbial Ecosystem (SHIME) to determine soil As metabolism by human gut microbiota. The results showed that the percentage of soil arsenate [As(V)] transformation reached 22.1-38.2%, while that of arsenite [As(III)] attained 66.5-92.0%; 30.1-56.4% of As(V) transformed was attached to the soil solid phase. In comparison to sequential extraction results, almost all amorphous Fe/Al-oxide-bound As was liberated in the colon phase. An X-ray absorption near-edge structure (XANES) showed that the As(III) percentage in the soil solid phase reached 16.6-26.9% and reached 73.4% (soil 1) in the colon phase. Additionally, plenty of As(III) and different extents of methylation were also observed in colon extraction solution. As bioaccessibility in the colon phase was 1.8-2.8 times that in the small intestinal phase. Our results indicated that human gut microbiota increased As bioaccessibility, and large amounts of As(III) were adsorbed onto the soil solid phase as a result of microbial reduction. Determining As speciation and distribution in extraction solution and soil solid phases will allow for an accurate assessment of the risk to human health upon soil As exposure.

Bioaccessibility assessment of arsenic and cadmium in polished and unpolished rice: Comparison of three in vitro methods.

INFOGEST is a standardized in vitro digestion method suitable for foods, but rarely used to study the bioaccessibility of heavy metals in food. This study aimed to explore the differences between INFOGEST and the extensively used Physiologically Based Extraction Test (PBET) and Unified Bioaccessibility Research Group of Europe Method (UBM) methods for determining the bioaccessibility of As and Cd in rice. Intestinal As (79.3 ± 8.5 %, 75.8 ± 12.7 %, and 72.3 ± 12.2 % for INFOGEST, PBET, and UBM, respectively) and Cd (47.0 ± 6.4 %, 40.7 ± 13.8 %, and 38.1 ± 15.7 % for INFOGEST, PBET, and UBM, respectively) bioaccessibilities in the rice samples determined by the three methods were generally similar (p > 0.1, except for As bioaccessibility between INFOGEST and UBM). Furthermore, PBET was significantly correlated with INFOGEST for As bioaccessibility (R2 = 0.416) and with UBM for Cd bioaccessibility (R2 = 0.879). Additionally, PBET indicated that the bioaccessibilities of As and Cd in the polished rice were 17.0 % and 19.8 % higher, respectively, than that in the unpolished rice. This study highlights the influence of in vitro methods and rice matrices on heavy metal bioaccessibility values, necessitating a more accurate assessment of health risks associated with rice consumption.

Assessment of the stabilization effect of ferrous sulfate for arsenic-contaminated soils based on chemical extraction methods and in vitro methods: Methodological differences and linkages.

Stabilization of arsenic-contaminated soils with ferrous sulfate has been reported in many studies, but there are few stabilization effects assessments simultaneously combined chemical extraction methods and in vitro methods, and further explored the corresponding alternative relationships. In this study, ferrous sulfate was added at FeAs molar ratio of 0, 5, 10 and 20 to stabilize As in 10 As spiked soils. Stabilization effects were assessed by 6 chemical extraction methods (toxicity characteristic leaching procedures (TCLP), HCl, diethylenetriamine pentaacetic acid (DTPA), CaCl2, CH3COONH4, (NH4)2SO4), and 4 in vitro methods (physiologically based extraction test (PBET), in vitro gastrointestinal method (IVG), Solubility Bioaccessibility Research Consortium (SBRC) method, and the Unified Bioaccessibility Research Group of Europe method (UBM)). The results showed that the HCl method provides the most conservative assessment results in non-calcareous soils, and in alkaline calcareous soils, (NH4)2SO4 method provides a more conservative assessment. In vitro methods provided significantly higher As concentrations than chemical extraction methods. The components of the simulated digestion solution as well as the parameters may have contributed to this result. The small intestinal phase of PBET and SBRC method produced the highest and lowest ranges of As concentrations, and in the range of 127-462 mg/kg and 68-222 mg/kg when the FeAs molar ratio was 5. So the small intestinal phase of PBET method may provide the most conservative assessment results, while the same phase of SBRC may underestimate the human health risks of As in stabilized soil by 51 %(at a FeAs molar ratio of 5). Spearman correlation analysis indicated that the small intestinal phase of PBET method correlated best with HCl method (correlation coefficient: 0.71). This study provides ideas for the assessment of stabilization efforts to ensure that stabilization meets ecological needs while also being less harmful to humans.

The pH-dependent role of different manganese oxides in the fate of arsenic during microbial reduction of arsenate-bearing goethite.

Manganese oxides reduce arsenic (As) toxicity by promoting aqueous-phase As(III) oxidation and immobilization in natural aquatic ecosystems. In anaerobic water-sediment systems, arsenic exists both in a free state in the liquid phase and in an adsorbed state on iron (Fe) minerals. However, the influence of different manganese oxides on the fate of As in this system remains unclear. Therefore, in this study, we constructed an anaerobic microbial As(V) reduction environment and investigated the effects of three different manganese oxides on the fate of both aqueous-phase and goethite-adsorbed As under different pH conditions. The results showed that δ-MnO2 had a superior As(III) oxidation ability in both aqueous and solid phase due not only to the higher SSA, but also to its wrinkled crystalline morphology, less favorable structure for bacterial reduction, structure conducive to ion exchange, and less interference caused by the formation of secondary Fe-minerals compared to α-MnO2 and γ-MnO2. Regarding aqueous-phase As, δ-MnO2, α-MnO2, and γ-MnO2 required an alkaline condition (pH 9) to exhibit their strongest As(III) oxidation and immobilization capability. For goethite-adsorbed As, under microbial-reducing conditions, all manganese oxides had the highest As immobilization effect in neutral pH environments and the strongest As oxidation effect in alkaline environments. This was because at pH 7, Fe(II) and Mn(II) formed hydrated complexes, which was more favorable for As adsorption. At pH 9, the negatively charged state of goethite hindered As adsorption but promoted the adsorption and oxidation of As by the manganese oxides. Our research offers new insights for optimizing As removal from water using various manganese oxides and for controlling the mobilization of As in water-sediment system under different pH conditions.

Immobilisation remediation of arsenic-contaminated soils with promising CaAl-layered double hydroxide and bioavailability, bioaccessibility, and speciation-based health risk assessment.

Arsenic (As)-contaminated soil poses great health risk to human mostly through inadvertent oral exposure. We investigated CaAl-layered double hydroxide (CaAl-LDH), a promising immobilising agent, for the remediation of As-contaminated Chinese soils. The effects on specific soil properties and As fractionation were analyzed, and changes in the health risk of soil As were accurately assessed by means of advanced in vivo mice model and in vitro PBET-SHIME model. Results showed that the application of CaAl-LDH significantly increased soil pH and concentration of Fe and Al oxides, and effectively converted active As fractions into the most stable residual fraction, guaranteeing long-term remediation stability. Based on in vivo test, As relative bioavailability was significantly reduced by 37.75%. Based on in vitro test, As bioaccessibility in small intestinal and colon phases was significantly reduced by 25.65% and 28.57%, respectively. Furthermore, As metabolism (reduction and methylation) by the gut microbiota inhabiting colon was clearly observed. After immobilisation with CaAl-LDH, the concentration of bioaccessible As(Ⅴ) in the colon fluid was significantly reduced by 61.91%, and organic As (least toxic MMA(V) and DMA(V)) became the main species, which further reduced the health risk of soil As. In summary, CaAl-LDH proved to be a feasible option for immobilisation remediation of As-contaminated soils, and considerable progress was made in relevant health risk assessment.

Arsenate and phosphate adsorption in relation to oxides composition in soils: LCD modeling.

The pH dependent solid-solution distribution of arsenate and phosphate in five Dutch agricultural soil samples was measured in the pH range 4-8, and the results were interpreted using the LCD (ligand and charge distribution) adsorption modeling. The pH dependency is similar for both oxyanions, with a minimum soluble concentration observed around pH 6-8. This pH dependency can be successfully described with the LCD model and it is attributed mainly to the synergistic effects from Ca adsorption. The solubility of phosphate is much lower than that of arsenate. This big difference cannot be sufficiently explained by the reduction of small amount of As(V) into As(III), neither by slow desorption/adsorption. The difference between phosphate and arsenate in their solid-solution distribution becomes larger with the increase of aluminum (hydr)oxides (Al-oxides) contribution to the total amount of metal (Al and Fe) (hydr)oxides. The influence of Al-oxides is much larger than its relative amount extracted from the soils. When Al-oxides account for >40% of the soil oxides, the whole adsorbents behave apparently similarly to that of pure Al-oxides. These results indicated that surface coating and substitution may have modified significantly oxyanion adsorption to Fe-oxides in soils, and how to account for this complexity is a challenge for geochemical modeling.

Effect of two biogas residues' application on copper and zinc fractionation and release in different soils.

Biogas residue (BR) is widely used as a new green fertilizer in agriculture in China. However, it often contains a high concentration of heavy metals so its application should cause our concern. An incubation experiment was conducted to study the risk of pig biogas residue (PBR) and chicken biogas residue (CBR) application on Liuminying soil (LS) and Yixing soil (YS). The soils were incubated for one, three and six months with 0, 2%, 4% and 6% addition of BRs. According to BCR extraction results, the PBR and CBR applications induced an increase in the concentration of exchangeable fraction of Zn. As for the concentration of exchangeable fraction of Cu, an increase was only observed in the treatments with PBR application. The heavy metal binding intensity also showed a similar trend. With the PBR application, for the LS and YS, the highest concentrations of exchangeable Zn increased 3.6 and 9.5 times, respectively, while the exchangeable Cu was increased by 52.6% and 187.1%. Dissolved organic carbon was the limiting factor for the exchangeable Cu while the exchangeable Zn was controlled by soil pH. PBR presented more agricultural risk than CBR when used as fertilizer. Meanwhile, BRs were more adaptable to LS than YS according to the heavy metal release results.

Effects of foods and food components on the in vitro bioaccessibility of total arsenic and arsenic species from Hizikia fusiforme seaweed.

Seaweed is an important food source, especially in many Asian countries, because of its high nutritional value; however, increasing arsenic (As) accumulation may pose serious hazards to human health. The influence of food components on As bioaccessibility and transformation in the high As-containing seaweed Hizikia fusiforme was determined using an in vitro gastrointestinal digestion method. The results showed that co-digestion with several daily foods (such as celery, broccoli, onion, green chili, tomato) produced a higher As bioaccessibility (approximately 6-11 % increase) compared with that of seaweed alone. Vegetables such as fennel (Foeniculum valgare Mill.), celery (Apium grareolens L.), blanched garlic leaves (Allium sativum L.), scallions (Allium fistulosum L.), ginger (Zingiber officinale Rosc.), and green pepper (Capsicum frutescens L. vat. grussum Bailey) decreased bioaccessible inorganic As (18-35 %) in both the gastric and small intestinal phases. Meanwhile, the process of reducing As(V) to As(III) also occurred during co-digestion with some food matrices. Egg white and other animal proteins were the most effective reducing agents, transforming >70 % As(V) into As(III) in the solution system. These results may have important implications for health risk assessment via co-consumption. The present study provides the first evidence showing that the co-consumption of some vegetables and proteins leads to a higher toxicity of inorganic arsenic-containing food. In addition, the positive and negative effects of co-digestion on the bioaccessibility of essential metals (iron, manganese) compared to single digestion were evaluated in this study.

Arsenic and iron bioavailability in Caco-2 cells: The influence of their co-existence and concentration.

Arsenic (As) exposure in humans is primarily caused through food and drinking water. Iron (Fe) is one of the most common element of the human and can influence the toxicity and bioavailability of As. However, information on the interaction between As and Fe when present together is limited. In this study, the interaction effects of Fe(III) (0, 3, and 10 mg/L) and As (As(III) at 0, 0.05, 0.1 mg/L, and As(V) at 0, 0.1, and 2 mg/L, respectively) on their absorption and bioavailability in Caco-2 cells were analyzed. As(III) absorption significantly decreased with the addition of Fe, while Fe absorption significantly increased. Compared with 0.1 mg/L As(III) addition alone, 3 and 10 mg/L Fe(III) addition significantly reduced the As(III) absorption by 8.6 and 11 µg/L, respectively. The absorption of As and Fe(III) and the bioavailability of Fe(III) significantly increased with the addition of As(III/V). Compared with 10 mg/L Fe(III) alone, the absorption of As(III) was significantly increased by 1 and 1.3 mg/L with 0.05 and 0.1 mg/L As(III) addition, respectively. Furthermore, the absorption and bioavailability of Fe(III) were significantly increased by 1.2 mg/L and 8% and 1.2 mg/L and 8.2%, respectively, after adding 0.1 and 2 mg/L As(V).

Effect of manganese oxides on arsenic speciation and mobilization in different arsenic-adsorbed iron-minerals under microbially-reducing conditions.

The oxidation and immobilization of arsenic (As) by manganese oxides have been shown to reduce As toxicity and bioavailability under abiotic conditions. In this study, we investigate the impact of manganese oxide (δ-MnO2) on the fate of different Fe-minerals-adsorbed As in the presence of As(V)-reducing bacteria Bacillus sp. JQ. Results showed that in the absence of δ-MnO2, As release in goethite was much higher than in ferrihydrite and hematite during microbial reduction. Adding 3.1 mM Mn reduced As release by 0.3%, 46.3%, and 6.7% in the ferrihydrite, goethite, and hematite groups, respectively. However, aqueous As was dominated by As(III) in the end, because the oxidation effect of δ-MnO2 was limited and short-lived. Additionally, the fraction of solid-phase As(V) increased by 9.8% in ferrihydrite, 39.4% in goethite, and 7.4% in hematite in the high-Mn treatments, indicating that δ-MnO2 had the most significant oxidation and immobilization effect on goethite-adsorbed As. This was achieved because goethite particles were evenly distributed on δ-MnO2 surface, which supported As(III) oxidation by δ-MnO2; while ferrihydrite strongly aggregated, which hindered the oxidation of As(III). Our study shows that As-oxidation and immobilization by manganese oxides cannot easily be assessed without considering the mineral composition and microbial conditions of soils.

Role of microbial iron reduction in arsenic metabolism from soil particle size fractions in simulated human gastrointestinal tract.

Gut microbiota provides protection against arsenic (As) induced toxicity, and As metabolism is considered an important part of risk assessment associated with soil As exposures. However, little is known about microbial iron(III) reduction and its role in metabolism of soil-bound As in the human gut. Here, we determined the dissolution and transformation of As and Fe from incidental ingestion of contaminated soils as a function of particle size (<250 µm, 100-250 µm, 50-100 µm and < 50 µm). Colon incubation with human gut microbiota yielded a high degree of As reduction and methylation of up to 53.4 and 0.074 µg/(log CFU/mL)/hr, respectively; methylation percentage increased with increasing soil organic matter and decreasing soil pore size. We also found significant microbial Fe(III) reduction and high levels of Fe(II) (48 %-100 % of total soluble Fe) may promote the capacity of As methylation. Although no statistical change in Fe phases was observed with low Fe dissolution and high molar Fe/As ratios, higher As bioaccessibility of colon phase (avg. 29.4 %) was mainly contributed from reductive dissolution of As(V)-bearing Fe(III) (oxy)hydroxides. Our results suggest that As mobility and biotransformation by human gut microbiota (carrying arrA and arsC genes) are strongly controlled by microbial Fe(III) reduction coupled with soil particle size. This will expand our knowledge on oral bioavailability of soil As and health risks from exposure to contaminated soils.

Effects of calcium supplements on oral bioavailability of fluoride in soil based on In Vivo and In Vitro methods.

Dietary calcium (Ca) intake can alleviate fluoride (F) induced fluorosis to maintain bone health. However, it is unclear whether calcium supplements can reduce the oral bioavailability of F present in contaminated soils. Here we evaluated the effects of Ca supplements on F bioavailability in three soils using an in vitro method (Physiologically Based Extraction Test) and an in vivo mouse model. Seven Ca salts, commonly used in calcium supplements, significantly reduced the F bioaccessibility in the gastric and small intestinal phases. Particularly for Ca phosphate at 150 mg Ca supplementation, F bioaccessibility in the small intestinal phase was reduced from 35.1-38.8% to 0.7-1.9% where soluble F concentrations were less than 1 mg/L. Overall, the eight Ca tablets tested in this study showed greater efficiency at decreasing F solubility. The in vitro bioaccessibility after Ca supplementation was consistent with the relative bioavailability of F. As supported by X-ray photoelectron spectroscopy, a possible mechanism is that freed F can be bound by Ca to form insoluble CaF2 and exchanged with OH groups from Al/Fe hydroxide to strongly adsorb F. These findings provide evidence of Ca supplementation in reducing health risks associated soil F exposure.