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.

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.

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.

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.

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).

Atypical patterns of tone production in tone-language-speaking children with autism.

Speakers with autism spectrum disorder (ASD) are found to exhibit atypical pitch patterns in speech production. However, little is known about the production of lexical tones (T1, T2, T3, T4) as well as neutral tones (T1N, T2N, T3N, T4N) by tone-language speakers with ASD. Thus, this study investigated the height and shape of tones produced by Mandarin-speaking children with ASD and their age-matched typically developing (TD) peers. A pronunciation experiment was conducted in which the participants were asked to produce reduplicated nouns. The findings from the acoustic analyses showed that although ASD children generally produced both lexical tones and neutral tones with distinct tonal contours, there were significant differences between the ASD and TD groups for tone height and shape for T1/T1N, T3/T3N, and T4/T4N. However, we did not find any difference in T2/T2N. These data implied that the atypical acoustic pattern in the ASD group could be partially due to the suppression of the F0 range. Moreover, we found that ASD children tended to produce more errors for T2/T2N, T3/T3N than for T1/T1N, T4/T4N. The pattern of tone errors could be explained by the acquisition principle of pitch, similarities among different tones, and tone sandhi. We thus concluded that deficits in pitch processing could be responsible for the atypical tone pattern of ASD children, and speculated that the atypical tonal contours might also be due to imitation deficits. The present findings may eventually help enhance the comprehensive understanding of the representation of atypical pitch patterns in ASD across languages.

Stabilization of fluorine-contaminated soil in aluminum smelting site with biochar loaded iron-lanthanide and aluminum-lanthanide bimetallic materials.

Trivalent metals-modified-biochar (BC) has been widely used for the removal of fluorine (F) in water, but little is known about its effects on the stability and mobility of F-contaminated soil. Two types of modified-BC materials (BC-loaded iron-lanthanide (BC/Fe-La) and BC-loaded aluminum-lanthanide (BC/Al-La)) were synthesized and used for the remediation of F-contaminated soil. The forms of BC/LaxFe3x(OH)y in BC/Fe-La and BC/LaxAl3x(OH)y in BC/Al-La were identified by spectroscopy, X-ray dispersion, thermogravimetric, and pore diameter/volume analyses. Following application (4-12%, w/w) to F-contaminated soil for 30 d, water soluble fluoride (WSF) decreased significantly. The modified-BC with a 1:1:1 molar ratio (BC: Al3+ or Fe3+: La3+) were more effective than those at 1:0.5:0.5. The BC/Al-La were the most effective to stabilize F. In particular, the highest decrease in WSF (by 91.75%) was obtained with the application of 12% BC/Al-La-2, while 8% BC/Al-La-2% and 12% BC/Al-La-1 reduced the WSF by 87.58% and 90.17%, respectively; all values obtained were lower than the national standard of China (< 1.5 mg/L). In addition, the sequential extraction results showed that modified-BC promoted the transformation of the other chemical speciation to the Fe/Mn-F.

Dynamic changes in the intestinal microbial community of two time-aged soils under combined cadmium and ciprofloxacin contaminated conditions.

The effects of combined contaminated soils containing cadmium (Cd) and ciprofloxacin (CIP) on the human gut microbiota are demonstrated using an in vitro test. Uncontaminated soil samples were artificially polluted with Cd and CIP using three different treatments (CK: 0 mg·kg-1; CIPI: 5 mg·kg-1, CIPII: 25 mg·kg-1, and Cd: 80 mg·kg-1). An experiment was performed to investigate the effect of Cd and CIP on the human colon microbiota using two aging times (D30: Day 30; D60: Day 60), and then the method of high-throughput 16S rRNA gene sequencing was used. In this study, we observed five phyla: Proteobacteria, Firmicutes, Synergistetes, Bacteroidetes, and Actinobacteria in colon microbial community. In addition, our results indicated that the relative abundances of the gut bacteria varied at the phylum level. Nevertheless, a slight decline in the relative abundance of Bacteroidetes among all the sets (compared to the D30-CK + Cd set) was revealed, and the lowest decline percentage of 90% was observed in the D60-CIPI + Cd set. Our results validated that the relative abundance of Rhodococcus increased with an increase in the CIP concentration in D30. In addition, this may disrupt normal physiological functions of the intestine after exposure to contaminated soil via the mouth. This study provides a theoretical basis for human risk assessment of oral exposure to Cd and CIP contaminated soils.