To identify the role of gut microbiota in human health risk assessment, the bioaccessibility of heavy metals in 14 soil samples were determined in simulated gastrointestinal fluids. Compared to the small intestinal phase, the bioaccessibility values of the colon phase varied, either increased by 3.5-fold for As, by 2.2-fold for Cr, and by 1.6-fold for Ni, or reduced by 4.4-fold for Cu, respectively. The colon incubation with adult gut microbiota yielded higher bioaccessibility value of As (1.3 times) and Fe (3.4 times) than that of the child in most soil samples. Colon bioaccessibility was about 60% greater of Cd for the adult and 30% higher of Cr for the child. Congruent data on the bioaccessibility of Cu and Ni was observed. In addition, correlation analysis indicated that in vitro bioaccessibility was primarily related to total concentrations of heavy metals in soils, followed by soil pH and active Fe/Mn oxide. Significantly, risk assessment calculated based on colon bioaccessibility indicated that the target hazard quotient (THQ > 1) of As was presented in 3 soil samples for the adult (1.05–3.35) and in 9 soil samples for the child (1.06–26.93). The hazard index (HI) of the child was 4.00 on average, greater than that of the adult (0.62), primarily due to the contribution of As and Cd. It suggested non-carcinogenic risks are likely to occur in children through typical hand-to-mouth behavior. The adjustment of colon bioaccessibility will result in more accurate risk assessment of human exposure to heavy metals from oral ingestion of contaminated soils.

Hexavalent chromium has aroused a series of environmental concerns due to its high mobility and toxicity. Iron and manganese oxides usually coexist in the environments and influence the speciation and geochemical cycling of chromium. However, the interaction mechanism of iron-manganese oxides with dissolved Cr(VI) remains largely unknown. In this work, the interaction processes of dissolved Cr(VI) and manganite in the presence of goethite coating were investigated, and the effects of pH (2.0–9.0) and iron oxide content were also studied. Manganite-goethite composites were formed with uniform micromorphologies in the system of manganite and Fe(II). In the reaction system of single manganite and Cr(VI), manganite could only adsorb but not reduce Cr(VI), with the adsorption amount decreasing at higher pHs. In the reaction system of manganite-goethite composites and Cr(VI), adsorbed Cr(VI) was reduced to Cr(III) by Fe(II) on composites surface. The generated Cr(III) was then retained as Cr(OH)₃ on the mineral surface. Goethite coating suppressed the re-oxidation of newly formed Cr(III) by manganite. The amounts of adsorbed Cr(VI) and generated Cr(III) increased with increasing iron oxide content, and increased first and then decreased with increasing pH. The Cr(III) formation and Cr(VI) adsorption amount reached the maximum at pH 5.0–6.0. The present work highlights the transformation and retention of Cr(VI) by iron-manganese oxides and provides potential implications for the use of such oxides in the remediation of Cr(VI) polluted waters and soils.

Periphyton plays a significant role in heavy metal transfer in wetlands, but its contribution to cadmium (Cd) bioavailability in paddy fields remains largely unexplored. The main aim of this study was to investigate the effect of periphyton on Cd behavior in paddy fields. Periphyton significantly decreased Cd concentrations in paddy waters. Non-invasive micro-test technology analyses indicated that periphyton can absorb Cd from water with a maximum Cd²⁺ influx rate of 394 pmol cm⁻² s⁻¹ and periphyton intrusion significantly increased soil Cd concentrations. However, soil Cd bioavailability declined significantly due to soil pH increase and soil redox potential (Eh) decrease induced by periphyton. With periphyton, more Cd was adsorbed and immobilized on organic matter, carbonates, and iron and manganese oxides in soil. Consequently, Cd content in rice decreased significantly. These findings give insights into Cd biogeochemistry in paddy fields with periphyton, and may provide a novel strategy for reducing Cd accumulation in rice.

Enhancing metals phytoextraction using gentile mobilizing agents might be an appropriate approach to increase the phytoextraction efficiency and to shorten the phytoremediation duration. The effect of sulfur-impregnated organoclay (SIOC) on the redistribution of potentially toxic elements (PTEs) among their geochemical fractions in soils and their plant uptake has not yet been studied. Therefore, our aim is to investigate the role of different SIOC application doses (1%, 3% and 5%) on operationally defined geochemical fractions (soluble + exchangeable; bound to carbonate; manganese oxide; organic matter; sulfide; poorly- and well-crystalline Fe oxide; and residual fraction) of Cd, Cr, Cu, Ni, Pb, and Zn, and their accumulation by pea (Pisum sativum) and corn (Zea mays) in a greenhouse pot experiment using a polluted floodplain soil. The SIOC caused a significant decrease in soil pH, and an increase in organic carbon and total sulfur content in the soil. The addition of SIOC increased significantly the soluble + exchangeable fraction and bioavailability of the metals. The SIOC leads to a transformation of the residual, organic, and Fe-Mn oxide fractions of Cd, Cu, Ni, and Zn to the soluble + exchangeable fraction. The SIOC addition increased the potential mobile (non-residual) fraction of Cr and Pb. The SIOC increased the sulfide fraction of Cr, Ni, and Zn, while it decreased the same fraction for Cd, Cu, and Pb. The effect of SIOC on the redistribution of metal fractions increased with enhancing application dosages. Pea accumulated more metals than corn with greater accumulation in the roots than shoots. Application of the higher dose of SIOC promoted the metals accumulation by roots and their translocation to shoots of pea and corn. Our results suggest the potential suitability of SIOC for enhancing the phytomanagement of PTEs polluted soils and reducing the environmental risk of these pollutants.

A composite material comprising of nanoscale zero-valent iron (nZVI) supported on vinegar residue (nZVI@VR) was prepared and applied for remediation of soils contaminated by hexavalent chromium (Cr(VI)). Sedimentation test results revealed that the nZVI@VR displayed enhanced stability in comparison to the bare-nZVI. Remediation experiments exhibited the immobilization efficiency of Cr(VI) and Crtotal was 98.68% and 92.09%, respectively, when using 10 g nZVI@VR (nZVI 5%) per 200 g Cr-contaminated soil (198.20 mg kg−1 Cr(VI), 387.24 mg kg−1 Crtotal) after two weeks of incubation. Further analyses demonstrated that almost all the exchangeable Cr was transformed into Fe–Mn oxide bound and organic matter bound. Moreover, the application of nZVI@VR enhanced soil organic carbon content and reduced redox potential. After granulation, the immobilization efficiency of Cr(VI) and Crtotal achieved 100% and 91.83% at a dosage of 10% granular nZVI@VR. Granular nZVI@VR also accelerated the transform of more available Cr (exchangeable and bound to carbonates) into less available fractions (Fe–Mn oxide bound and organic matter bound), thus resulting in a remarkable reduction in the Cr bioavailability. These results prove that nZVI@VR can be an effective remediation reagent for soils contaminated by Cr(VI).

Thallium (Tl) and its compounds are non-essential and highly toxic for living organisms, even at low concentrations. In this paper, we analyzed the presence and geochemical distribution of Tl in different mining-metallurgical and sediment samples collected from several mining zones of Mexico. A modified BCR sequential extraction procedure was also applied to the samples to investigate the geochemical behavior and potential environmental risk of Tl according to types of ore deposit and mineral processing method applied. Results revealed the presence of Tl in the majority of the mining-metallurgical samples, with labile concentrations reaching up to values of 184.4 mg kg⁻¹, well above the environmental standards. A comparison of Tl partitioning in different samples showed that Tl was usually found associated with labile fractions instead of entrapped in the environmentally-passive residual fraction. Specifically, high levels of Tl were extracted from the exchangeable/acid-extractable and poorly-crystalline reducible fractions, suggesting its association with both soluble and amorphous Fe-Mn oxyhydroxides, respectively. Besides, Tl was also frequently found associated with the crystalline reducible fraction, presumably bonded to manganese oxides and jarosite-like minerals. Lastly, little amounts of Tl were extracted from the oxidizable fraction. Considering the fractionation of Tl in these mining-metallurgical samples, they may pose a significant environmental hazard. This study provides useful insights into the potential sources of Tl pollution in Mexico and emphasizes the need for further research to determine the extent of its impact and to develop effective remediation protocols to protect the environment from Tl toxicity.

Mining and metallurgy generate residues that may contain thallium (Tl), a highly toxic metal, for which it is currently not feasible to determine its geochemical speciation through X-ray absorption spectroscopy due to a combination of very low contents and the interference of accompanying high arsenic contents. Therefore, fractionation studies in residues and soils are required to analyze the mobility and bioavailability of this metal, which in turn provide information to infer its speciation. For this purpose, in this work a modification of the BCR procedure was applied to residues and contaminated soils from three mining zones of Mexico and two mining zones of Spain, spanning samples with acidic to alkaline pH values.The Tl extraction procedure consisted of the following fractions: (1) water-extractable, (2) easily exchangeable and associated to carbonates, associated to (3) poorly-crystalline and (4) crystalline Fe and Mn oxyhydroxides, and (5) associated to organic matter and sulfides; and finally a residual fraction as associated to refractory primary and other secondary minerals. The extracted contents were analyzed by Inductively-Coupled Plasma with Mass Spectrometry.Surprisingly, water-soluble, in Tl(I) oxidation state, was detected in most areas, regardless of the pH, a fact that has not been reported before in these environments, and alerts to potential health risks not previously identified. Most of the samples from a metallurgy area showed high levels of Tl in non-residual fractions and a strong correlation was obtained between extracted Mn and Tl in the third fraction, suggesting its association to poorly crystalline manganese oxides. In the majority of samples from purely mining environments, most of the Tl was found in the residual fraction, most probably bound to alumino-silicate minerals. The remaining Tl fractions were extracted mainly associated to the reducible mineral fractions, and in one case also in the oxidizable fraction (presumably associated to sulfides).Capsule: Soluble Tl(I) was found in all soil samples contaminated with either mining or metallurgical wastes. Additionally, in those affected by metallurgical wastes a very strong Tl-Mn correlation was found.

Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO₂ at mild conditions (pH 4–9 and 22 °C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg²⁺ or Ca²⁺. Experimental results of TTC indicate that MnO₂ promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO₂ generate little iso-OTC, but occur mainly at the A ring’s dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO₂, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines.

The degradation of 17b-estradiol (E2) in sterile soil and Mn-free soil slurries was determined. In 0.075 g ml⁻¹ soil slurry, E2 with an initial concentration of 0.0267 mmol g⁻¹ was rapidly degraded and near equimolar estrone (E1) accumulated. A mass balance involving E2 and E1 existed throughout the reaction. The E2 degradation was thus an oxidation process and E1 was the only product. The concurrent release of Mn(II) during E2 oxidation and a lack of E2 oxidation in Mn-free soil slurry together demonstrated that soil manganese oxides were responsible for E2 oxidation. The degree of E2 oxidation was higher at high pH than at low pH, consistent with the fact that the reaction released protons. This study suggests that manganese oxides may be used as soil amendments to effectively oxidize E2 to less potent E1 in soil.

Triclinic birnessite (TB), a typical layered Mn oxide which is abundant naturally occurring minerals with a vital impact on the transformation of arsenite (As(III)) by adsorption and oxidation. As one of the most common critical metalloids, ammonium ion (NH₄⁺) universally coexists with birnessite in marine, sediments or groundwater where are contaminated with As(III). In this study, we investigated the impacts of NH₄⁺ on TB towards the transformation of As(III). Compared with the original TB (40.1%), the As(III) removal efficiencies of three different concentration (0.5 M, 1 M and 2 M) NH₄⁺ impressed triclinic birnessite (TB-0.5 N, TB-1N and TB-2N) are increased rapidly in the order of: TB-2N (80.4%) > TB-1N (75.8%) > TB-0.5 N (71.5%). In addition, TB-2N exhibited the highest initial oxidation rate of 0.0031 min⁻¹ which exceeds twice as much as this of TB (0.0014 min⁻¹). And TB-2N could reach the max oxidation efficiency when the As concentration is 0.08 mM. Due to two different mechanisms of As(III) oxidation on birnessites under acidic and alkaline conditions, TB-2N showed a higher removal efficiency than TB at pH 3.0, 5.0, 7.0 and 9.0. Hence, there are two main reasons for the advanced As(III) oxidation capacity of TB-2N. One is the improvement of the average oxidation state of Mn, the other is the increase of oxygen vacancy with the coexistence of NH₄⁺. Moreover, the larger specific surface area of TB-2N also contribute to enhancing As(III) oxidation capacity. This study holds a fundamental understanding of the behavior of triclinic birnessite which is coexisted with ammonium ion towards the transformation of As(III) in the environment.