Cadmium reduced methane emissions by stimulating methane oxidation in paddy soils.

Flooded rice paddy fields are a significant source of anthropogenic methane (CH4) emissions. Cadmium (Cd) is one of the most common and toxic contaminants in paddy soils. However, little is known about how the soil microbial communities associated with CH4 emissions respond to the increasing Cd-stress in paddies. In this study, we employed isotopically 13C-labelled CH4, high-throughput sequencing analysis, and gene quantification analysis to reveal the effect and mechanism of Cd on CH4 emissions in paddy soils. Results showed that 4.0 mg kg-1 Cd addition reduced CH4 emissions by 16-99% in the four tested paddy soils, and significantly promoted the transformation of 13CH4 to 13CO2. Quantitative polymerase chain reaction (qPCR) demonstrated that Cd addition increased the abundances of pmoA gene, the ratios of methanogens to methanotrophs (mcrA/pmoA) showed a positive correlation with CH4 emissions (R2 = 0.798, p < 0.01). Furthermore, the composition of the microbial community containing the pmoA gene was barely affected by Cd addition (p > 0.05). This observation was consistent with the findings of a pure incubation experiment where methanotrophs exhibited high tolerance to Cd. We argue that microbial feedback to Cd stress amplifies the contribution of methanotrophs to CH4 oxidation in rice fields through the complex interactions occurring among soil microbes. Our study highlights the overlooked association between Cd and CH4 dynamics, offering a better understanding of the role of rice paddies in global CH4 cycling.

Sustainable removal of soil arsenic by naturally-formed iron oxides on plastic tubes.

Arsenic (As) pollution in paddy fields is a major threat to rice safety. Existing As remediation techniques are costly, require external chemical addition and degrade soil properties. Here, we report the use of plastic tubes as a recyclable tool to precisely extract As from contaminated soils. Following insertion into flooded paddy soils, polyethylene tube walls were covered by thin but massive Fe coatings of 76.9-367 mg Fe m-2 in 2 weeks, which adsorbed significant amounts of As. The formation of tube-wall Fe oxides was driven by local Fe-oxidizing bacteria with oxygen produced by oxygenic phototrophs (e.g., Cyanobacteria) or diffused from air through the tube wall. The tubes with As-bound Fe oxides can be easily separated from soil and then washed and reused. We tested the As removal efficiency in a pot experiment to remove As from ~ 20 cm depth/40 kg soils in a 2-year experiment and achieved an overall removal efficiency of 152 mg As m-2 soil year-1, comparable to phytoremediation with the As hyperaccumulator Pteris vittata. The cost of Fe hooks was estimated at 8325 RMB ha-1 year-1, and the profit of growing rice (around 16080 RMB ha-1 year-1 can be still maintained. The As accumulated in rice tissues was markedly decreased in the treatment (>11.1 %). This work provides a low-cost and sustainable soil remediation method for the targeted removal of As from soils and a useful tool for the study and management of the biogeochemical Fe cycle in paddy soils.

Iron-based passivator mitigates the coupling process of anaerobic methane oxidation and arsenate reduction in paddy soils.

Arsenic (As) is a toxic metalloid that is ubiquitous in paddy soils, where passivation is the most widely used method for remediating As contamination. Recently, anaerobic methane oxidation coupled with arsenate (As(V)) reduction (AOM-AsR) has been shown to act as a critical driver for As release in paddy fields. However, the effect and mechanism of the passivators on the AOM-AsR process remain unclear. In this study, we incubated arsenate-contaminated paddy soils under anaerobic conditions. Using isotopically labelled methane and different passivators, we found that an iron-based passivator containing calcium sulfate and iron oxide (9:1, m/m) named IBP showed a much better performance than the other passivators. Adding IBP decreased the arsenite (As(III)) concentration in the soil solution by 78% and increased the AOM rate by 55%. Furthermore, we employed high-throughput sequencing and real-time quantitative polymerase chain reaction (qPCR) to investigate the ability of IBP to control As release mediated by AOM-AsR in paddy fields, as well as its underlying mechanism. Our results showed that IBP addition significantly increased anaerobic methanotrophic (ANME) archaea (ANME-2a-c, ANME-2d, and ANME-3) by 91%, and increased the methane-oxidizing bacterium Methylobacter by 262%. Similarly, IBP addition significantly increased the Fe(III) concentration in soil solution by 39% and increased the absolute abundance of Fe(III)-reducing bacteria (Geobacteraceae) by 21 times in soil. Adding IBP may significantly promote AOM coupled with Fe(III) reduction, significantly reducing electron transfer from AOM to As(V) reduction. Hence, IBP may be used as an efficient passivator to remediate As-contaminated soil using an active AOM-AsR process. These results provide a novel insight into controlling soil As release by regulating an active and critical As mobilization pathway in the environment.

Arsenic and cadmium bioavailability to rice (Oryza sativa L.) plant in paddy soil: Influence of sulfate application.

Arsenic (As) and cadmium (Cd) accumulate easily in rice grains that pose a non-negligible threat to human health worldwide. Sulfur fertilizer has been shown to affect the mobilization of As and Cd in paddy soil, but the effect of co-contamination by As and Cd has not been explored. This study selected three soils co-contaminated with As and Cd from Shangyu (SY), Tongling (TL) and Ma'anshan (MA). Incubation experiments and pot experiments were carried out to explore the effect of sulfate supply (100 mg kg-1) on the bioavailability of As and Cd in soil and the rice growth. The results showed that the exogenous sulfate decreased As concentrations in porewater of SY and TL by 51.1% and 29.2% through forming arsenic-sulfide minerals. The exchangeable Cd in soil also declined by 25.6% and 18.6% and transformed into Fe and Mn oxides-bound Cd. The relative abundance of Desulfotomaculum, Desulfurispora and dsr gene increased remarkably indicated that sulfate addition stimulated the activity of sulfate-reducing bacteria. In MA soil, sulfate addition immobilized Cd but had little effect on As solubility, which was speculated to be related to the high sulfate background of the soil. Further pot experiments showed that sulfate application significantly increased rice tillers, biomass, chlorophyll content in shoots, and decreased electrolyte leakage in root. Finally, sulfate significantly reduced As and Cd in SY rice shoots by 60.2% and 40.8%, respectively, while As decreased by 39.6% in TL rice shoots and Cd decreased by 23.0% in MA rice shoots. These results indicate that the application of sulfate can reduce the bioavailability of As and Cd in the soil-rice system and promote rice growth, and it is possible to reduce the accumulation of As and Cd in rice plants simultaneously.

Biochar-supported nanoscale zero-valent iron can simultaneously decrease cadmium and arsenic uptake by rice grains in co-contaminated soil.

Cadmium (Cd) and Arsenic (As) in rice grains are a primary exposure source for human beings. However, the simultaneous stabilization of Cd and As in soil becomes difficult due to the opposite properties of those. In this study, we investigated the simultaneous effects of biochar-supported nanoscale zero-valent iron (nZVI-BC) and water management on the decrease of Cd and As bioaccumulation in rice grain. Compared to the control, 0.25-1.00% nZVI-BC coupled with alternate wetting and drying (AWD) management simultaneously decreased the bioaccumulation of Cd and As in rice grains by 15.85-69.16% and 23.06-59.45%, respectively. The cancer risk associated with rice consumption effectively reduced by 15.60-52.41% after the application of nZVI-BC, and the lowest cancer risk was detected in 1.00% nZVI-BC under AWD management. Furthermore, rice cultivated under AWD management had a lower total cancer risk than that cultivated under continuous flooded (CF) management with the same amendment of type and dose. The reduction of soil Cd and As availability and the formation of iron plaque dominated the decrease of Cd and As uptake by rice grains. The elevated soil pH was responsible for Cd adsorption, and the dominant mechanism for As immobilization was the formation of complexes. The iron plaque was double-edged, promoting and inhibiting Cd uptake by rice, wherein the inhibition was predominant under aerobic conditions. In addition, iron plaque was a barrier to preventing the As accumulation by rice, a larger amount of As was immobilized on the iron plaque with nZVI-BC treatment. This study sheds new insights on the simultaneous remediation of Cd and As co-contaminated paddy fields.

[Simultaneous Immobilization of Arsenic, Lead, and Cadmium in Paddy Soils Using Two Iron-based Materials].

Two iron-based materials, Fe-Ca composite (FeCa) and Fe-Mn binary oxide (FMBO), were applied to immobilize As, Pb, and Cd in heavy metal contaminated paddy soils. Seven kinds of paddy soil (tidal soil) contaminated by arsenic, lead and cadmium were collected from Shangyu, Shaoxing (SY), Foshan, Guangdong (FS), Shaoguan, Guangdong (SG), LiuYang, Hunan (LY), Ganzhou, Jiangxi (GZ), Dushan, Guizhou (DS), and Ma'anshan, Anhui (MAS). The effects of iron-based materials on the dynamic changes of As, Pb, and Cd concentration in soil solution, the stabilization efficacy of available As, Pb, and Cd in soil, and the effects of soil types and properties on stabilization efficacy were studied through soil incubation experiment. The results showed that the content of soil dissolved As, Pb, and Cd were lower in iron-based material treatments than in control throughout the incubation. The addition of two iron-based materials significantly reduced the availability of Cd, Pb, and As. Moreover, the stabilization efficiency of FeCa for As was higher than FMBO, but no significant difference was found in the stabilization efficiency of Pb and Cd between two materials. The stabilization efficiency of As, Pb, and Cd in FeCa treatments could be ordered as GZ > SG > DS and MAS; FS>SY, LY, and SG>MAS; SY, GZ, and DS>MAS, respectively. While the stabilization efficiency for As, Pb, and Cd in FMBO could be ordered as SY, LY, and GZ > DS > FS; FS > GZ > SY; DS > LY > MAS, respectively. In addition, the statistical results showed that the stabilization efficiencies of various soils under the treatment of iron-based materials were significantly correlated with sand content (negatively correlated for As), soil pH (positively correlated for Pb), and clay content (negatively correlated for Cd). In conclusion, the two iron-based materials evaluated in this study may be effective stabilization agents for remediating different types of arsenic-, lead-, and cadmium-contaminated soils.

Arsenic (III) removal by mechanochemically sulfidated microscale zero valent iron under anoxic and oxic conditions.

The interaction of As(III) with micron-sized, mechanochemically sulfidated zero-valent iron (S-mZVIbm) has been studied under both anoxic and oxic conditions. The As(III) removal capacity varied with the increase of S/Fe molar ratio under anoxic conditions, while it continuously decreased under oxic conditions. A series of sequential extractions, X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) spectroscopy analyses were used to investigate As(III) removal mechanisms. In the absence of oxygen, As(III) was removed from solution primarily through the formation of As4S4 with less than half of the removal resulting from the adsorption of As(III)/As(V) and FeAsS precipitation. Under oxic conditions, adsorption onto iron (oxyhydr)oxides was the dominant mechanism of As(III) removal. Increasing sulfidation decreased particle Fe(0) content, which resulted in less production of iron (oxyhydr)oxides and therefore lower As(III) removal capacities. Column experiments showed that less than 2 wt% of S-mZVIbm in sand was able to rapidly reduce the As(III) concentration in a real groundwater from 300 to 10 µg/L, the Chinese drinking water standard, for up to 750 BV with an EBCT of 2.54 min. This study demonstrates that S-mZVIbm is an efficient and cost-effective material in treating As-contaminated water to ensure water safety.

Increase in arsenic methylation and volatilization during manure composting with biochar amendment in an aeration bioreactor.

Biochar is widely used as an amendment to optimize the composting process. In this study, we firstly investigated the effects of biochar amendment on methylation and volatilization of arsenic (As), and the microbial communities during manure composting. Biochar amendment was found to increase the concentrations of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) during mesophilic (days 0-10) and early thermophilic (days 11-15) phases, and promote As volatilization during the maturing phase (days 60-80) of composting. In addition, the abundances of As(V) reductase (arsC) and As(III) S-adenosyl-L-methionine methyltransferase (arsM) genes were higher in the biochar treatment than that in the control. Moreover, biochar amendment influenced the microbial communities by promoting As methylation and volatilization via Ensifer and Sphingobium carrying arsC genes, and Rhodopseudomonas and Pseudomonas carrying arsM genes. This study emphasized the considerable role of biochar on methylation and volatilization of As during manure composting and provided an overall characterization of the community compositions of arsC and arsM genes during manure composting. It will broaden our insights in As biogeochemical cycle during manure composting with biochar amendment, which will facilitate the regulation of As during manure composting and its application in agricultural soil.

Zinc oxide nanoparticles alleviate the arsenic toxicity and decrease the accumulation of arsenic in rice (Oryza sativa L.).

BACKGROUND: Rice is particularly effective, compared to other cereals, at accumulating arsenic (As), a nonthreshold, class 1 human carcinogen in shoot and grain. Nano-zinc oxide is gradually used in agricultural production due to its adsorption capacity and as a nutrient element. An experiment was performed to explore the effects of zinc oxide nanoparticles (nZnO) on arsenic (As) toxicity and bioaccumulation in rice. Rice seedlings were treated with different levels of nZnO (0, 10, 20, 50, 100 mg/L) and As (0, and 2 mg/L) for 7 days. RESULTS: The research showed that 2 mg/L of As treatment represented a stress condition, which was evidenced by phenotypic images, seedling dry weight, chlorophyll, and antioxidant enzyme activity of rice shoot. The addition of nZnO (10-100 mg/L) enhanced the growth and photosynthesis of rice seedlings. As concentrations in the shoots and roots were decreased by a maximum of 40.7 and 31.6% compared to the control, respectively. Arsenite [As (III)] was the main species in both roots (98.5-99.5%) and shoots (95.0-99.6%) when exposed to different treatments. Phytochelatins (PCs) content up-regulated in the roots induced more As (III)-PC to be complexed and reduced As (III) mobility for transport to shoots by nZnO addition. CONCLUSION: The results confirmed that nZnO could improve rice growth and decrease As accumulation in shoots, and it performs best at a concentration of 100 mg/L.

Attapulgite and processed oyster shell powder effectively reduce cadmium accumulation in grains of rice growing in a contaminated acidic paddy field.

Heavy-metal contamination is widespread in agricultural soils worldwide, especially paddy soils contaminated by Cd. Amendment-induced immobilization of heavy metals is an attractive and effective technique, provided that cost-effective materials are used. This field experiment compared three alkaline passivators (attapulgite, processed oyster shell powder, and mixed soil conditioner) at a rate of 2.25 t ha-1 for their effectiveness in decreasing Cd bioavailability in soils and accumulation in rice plants in a paddy field contaminated by Cd (0.38 Cd mg kg-1). The utilization of attapulgite and processed oyster shell powder decreased labile fractions but increased stable fractions of Cd in soils through ion exchange, precipitation and complexation. The addition of attapulgite decreased the concentration of bioavailable Cd in both bulk and rhizosphere soils, whereas the amendment of processed oyster shell powder decreased it only in bulk soil. The Cd accumulation in rice plants correlated significantly with acid-soluble and residual Cd fractions in the rhizosphere soil but not in the bulk soil. The addition of attapulgite and processed oyster shell powder decreased Cd accumulation in rice grains from 0.26 mg kg-1 to 0.14 and 0.19 mg kg-1, respectively, meeting the National Food Safety Standard (< 0.20 mg kg-1). However, the mixed soil conditioner did not decrease the Cd accumulation in rice shoots or grains. This study demonstrated that attapulgite and processed oyster shell powder were economic agents in reducing Cd accumulation in rice grains.

Nanoscale zero-valent iron reduction coupled with anaerobic dechlorination to degrade hexachlorocyclohexane isomers in historically contaminated soil.

Hexachlorocyclohexane (HCH) isomers pose potential threats to the environment and to public health due to their persistence and high toxicity. In this study, nanoscale zero-valent iron (nZVI) coupled with microbial degradation by indigenous microorganisms with and without biostimulation was employed to remediate soils highly polluted with HCH. The degradation efficiency of total HCHs in both the "nZVI-only" and "Non-amendment" treatments was approximately 50 %, while in the treatment amended with nZVI and acetate, 85 % of total HCHs was removed. Addition of nZVI and acetate resulted in enrichment of anaerobic microorganisms. The results of quantitative PCR (qPCR) and 16S rRNA gene amplicon sequencing revealed that Desulfotomaculum, Dehalobacter, Geobacter, and Desulfuromonas likely contributed to the depletion of HCH isomers. Moreover, some abiotic factors also favored this removal process, including pH, and the generation of iron sulfides as revealed by the result of Mössbauer spectrometer analysis. Our research provides an improved remediation strategy for soils polluted with HCH isomers and an understanding of the synergistic effect of nZVI and indigenous microorganisms.

Arsenic and cadmium removal from water by a calcium-modified and starch-stabilized ferromanganese binary oxide.

A new calcium-modified and starch-stabilized ferromanganese binary oxide (Ca-SFMBO) sorbent was fabricated with different Ca concentrations for the adsorption of arsenic (As) and cadmium (Cd) in water. The maximum As(III) and Cd(II) adsorption capacities of 1% Ca-SFMBO were 156.25 mg/g and 107.53 mg/g respectively in single-adsorption systems. The adsorption of As and Cd by the Ca-SFMBO sorbent was pH-dependent at values from 1 to 7, with an optimal adsorption pH of 6. In the dual-adsorbate system, the presence of Cd(II) at low concentrations enhanced As(III) adsorption by 33.3%, while the adsorption of As(III) was inhibited with the increase of Cd(II) concentration. Moreover, the addition of As(III) increased the adsorption capacity for Cd(II) up to two-fold. Through analysis by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR), it was inferred that the mechanism for the co-adsorption of Cd(II) and As(III) included both competitive and synergistic effects, which resulted from the formation of ternary complexes. The results indicate that the Ca-SFMBO material developed here could be used for the simultaneous removal of As(III) and Cd(II) from contaminated water.

Policy adjustment impacts Cd, Cu, Ni, Pb and Zn contamination in soils around e-waste area: Concentrations, sources and health risks.

Pollution control policies (PCP) have been implemented in some e-waste dismantling areas in China to curb metal contamination since 2012. We investigated the effects of policy intervention on the concentrations, sources and health risks of heavy metals in soils. Post-implementation, among Cd, Cu, Ni, Pb and Zn, Pb levels declined while the Cd, Cu, Ni and Zn concentrations in soils were not impacted. Changes in their pollution indices and health risks were also similar. After the PCP, the contribution of traffic emission significantly decreased, while natural and industrial contribution increased due to the heighten background input and relocation of small e-waste dismantling workshops. Risk assessment showed that total cancer risk of five metals also slightly increased. Thus, policy intervention might be effective in controlling the release of some metals from e-waste dismantling. However, the performance of control measures varied depending on both source emission and geochemical properties of the metals. This study reveal the ongoing need of stricter supervision, targeted emission reduction and more-effective soil remediation actions to alleviate soil contamination from e-waste dismantling.

Abundance and diversity of microbial arsenic biotransformation genes in the sludge of full-scale anaerobic digesters from a municipal wastewater treatment plant.

Arsenic (As) is a potential contaminant in sewage sludge that may affect waste treatment and limit the use of these waste materials as soil amendments. Anaerobic digestion (AD) is an important and effective process for the treatment of sewage sludge and the chemical speciation of As is particularly important in sludge AD. However, the biotransformation genes of As in sludge during AD has not been fully explored. In this study, the influent and effluent sludge of anaerobic digester in a wastewater treatment plant (WWTP) was collected to investigate the species transformations of As, the abundance and diversity of As biotransformation genes was explored by real-time PCR (qPCR) and metagenomic sequencing, separately. The results showed that arsenite [As(III)] and arsenate [As(V)] were predominant in the influent sludge, whereas the relative abundance of monomethylarsenic acid (MMA) increased by 25.7% after digestion. As biotransformation genes were highly abundant, and the As(III) S-adenosylmethionine methyltransferase (arsM) gene was the predominant which significantly increased after AD by qPCR analysis. Metagenomic analysis indicated that the diversity of the arsM-like sequences also increased significantly after AD. Most of the arsM-like sequences in all the influent and effluent sludge samples were related to Bacteroidetes and Alphaproteobacteria. Furthermore, co-occurrence network analysis indicated a strong correlation between the microbial communities and As. This study provides a direct and reliable reference on As biotransformation genes and microbial community in the AD of sludge.

Zeolite-supported nanoscale zero-valent iron for immobilization of cadmium, lead, and arsenic in farmland soils: Encapsulation mechanisms and indigenous microbial responses.

Zeolite-supported nanoscale zero-valent iron (Z-NZVI) has great potential for metal(loid) removal, but its encapsulation mechanisms and ecological risks in real soil systems are not completely clear. We conducted long-term incubation experiments to gain new insights into the interactions between metal(loid)s (Cd, Pb, As) and Z-NZVI in naturally contaminated farmland soils, as well as the alteration of indigenous bacterial communities during soil remediation. With the pH-adjusting and adsorption capacities, 30 g kg-1 Z-NZVI amendment significantly decreased the available metal(loid) concentrations by 10.2-96.8% and transformed them into strongly-bound fractions in acidic and alkaline soils after 180 d. An innovative magnetic separation of Z-NZVI from soils followed by XRD and XPS characterizations revealed that B-type ternary complexation, heterogeneous coprecipitation, and/or concurrent redox reactions of metal(loid)s, especially the formation of Cd3(AsO4)2, PbFe2(AsO4)2(OH)2, and As0, occurred only under specific soil conditions. Sequencing of 16S rDNA using Illumina MiSeq platform indicated that temporary shifts in iron-resistant/sensitive, pH-sensitive, denitrifying, and metal-resistant bacteria after Z-NZVI addition were ultimately eliminated because soil characteristics drove the re-establishment of indigenous bacterial community. Meanwhile, Z-NZVI recovered the basic activities of bacterial DNA replication and denitrification functions in soils. These results confirm that Z-NZVI is promising for the long-term remediation of metal(loid)s contaminated farmland soil without significant ecotoxicity.

Paddy periphyton reduced cadmium accumulation in rice (Oryza sativa) by removing and immobilizing cadmium from the water-soil interface.

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.

Simultaneous immobilization of the cadmium, lead and arsenic in paddy soils amended with titanium gypsum.

In situ immobilization of heavy metals in contaminated soils using industrial by-products is an attractive remediation technique. In this work, titanium gypsum (TG) was applied at two levels (TG-L: 0.15% and TG-H: 0.30%) to simultaneously reduce the uptake of cadmium (Cd), lead (Pb) and arsenic (As) in rice grown in heavy metal contaminated paddy soils. The results showed that the addition of TG significantly decreased the pH and dissolved organic carbon (DOC) in the bulk soil. TG addition significantly improved the rice plants growth and reduced the bioavailability of Cd, Pb and As. Particularly, bioavailable Cd, Pb and As decreased by 35.2%, 38.1% and 38.0% in TG-H treatment during the tillering stage, respectively. Moreover, TG application significantly reduced the accumulation of Cd, Pb and As in brown rice. Real-time PCR analysis demonstrated that the relative abundance of sulfate-reducing bacteria increased with the TG application, but not for the iron-reducing bacteria. In addition, 16S rRNA sequencing analysis revealed that the relative abundances of heavy metal-resistant bacteria such as Bacillus, Sulfuritalea, Clostridium, Sulfuricella, Geobacter, Nocardioides and Sulfuricurvum at the genus level significantly increased with the TG addition. In conclusion, the present study implied that TG is a potential and effective amendment to immobilize metal(loid)s in soil and thereby reduce the exposure risk of metal(loid)s associated with rice consumption.

Simultaneous adsorption of Cd(II)andAs(III)by a novel biochar-supported nanoscale zero-valent iron in aqueous systems.

Biochar-supported nanoscale zero-valent iron (nZVI-BC) is a promising material for Cd(II) and As(III) removal from aqueous systems. In this study, simplified nZVI-BC composites were successfully synthesized and characterized via scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectrometry (XPS), and Fourier transform infrared spectroscopy (FTIR) to understand the underlying adsorption mechanism. SEM and FTIR confirmed that nZVI particles were distributed evenly on the biochar surface. XRD and XPS revealed that metal ions were separated from solutions via electrostatic adsorption, complexation, oxidation, precipitation/co-precipitation, and the formation of type B ternary surface complex. Batch experiments showed that nZVI-BC (1:1) had a high removal efficiency in a wide pH range of 5.0-8.0 for Cd(II) and 3.0-8.0 for As(III), the maximum Cd(II) and As(III) adsorption capacities were 33.81 and 148.5 mg/g within 2 and 1 h, respectively. Additionally, synergisticeffects considerably enhanced the adsorption capacity of nZVI-BC(1:1) in mixed adsorption systems, the adsorption capacities of Cd(II) and As(III) reached 179.9 and 158.5 mg/g, respectively. Hence, nZVI-BC(1:1) is an ideal candidate for Cd(II) and As(III) pollution treatment.

Microbial Communities Associated with Sustained Anaerobic Reductive Dechlorination of α-, ß-, γ-, and δ-Hexachlorocyclohexane Isomers to Monochlorobenzene and Benzene.

Intensive historical and worldwide use of pesticide formulations containing hexachlorocyclohexane (HCH) has led to widespread contamination. We derived four anaerobic enrichment cultures from HCH-contaminated soil capable of sustainably dechlorinating each of α-, ß-, γ-, and δ-HCH isomers stoichiometrically to benzene and monochlorobenzene (MCB). For each isomer, the dechlorination rates, inferred from production rates of the dechlorinated products, MCB and benzene, increased progressively from <3 to ∼12 µM/day over 2 years. The molar ratio of benzene to MCB produced was a function of the substrate isomer and ranged from ß (0.77 ± 0.15), α (0.55 ± 0.09), γ (0.13 ± 0.02), to δ (0.06 ± 0.02) in accordance with pathway predictions based on prevalence of antiperiplanar geometry. Data from 16S rRNA gene amplicon sequencing and quantitative PCR revealed significant increases in the absolute abundances of Pelobacter and Dehalobacter, most notably in the α-HCH and δ-HCH cultures. Cultivation with a different HCH isomer resulted in distinct bacterial communities, but similar archaeal communities. This study provides the first direct comparison of shifts in anaerobic microbial communities induced by the dechlorination of distinct HCH isomers. It also uncovers candidate microorganisms responsible for the dechlorination of α-, ß-, γ-, and δ-HCH, a key step toward better understanding and monitoring of natural attenuation processes and improving bioremediation technologies for HCH-contaminated sites.

A multi-medium chain modeling approach to estimate the cumulative effects of cadmium pollution on human health.

Cadmium is a highly persistent and toxic heavy metal that poses severe health risks to humans. Diet is the primary source of human exposure to cadmium, especially in China. Soil, as the main medium that transfers cadmium to rice, can be used as a helpful indicator to predict human exposure to cadmium in soils. There is, however, very little work that links a soil-rice transfer model with a biokinetic model to assess health risks. In this work, we introduce a multi-medium chain model based upon a soil-rice-human continuum to address this issue. The model consists of three basic steps: (i) development and validation of a soil-rice transfer model for cadmium based on 189 pairs of measured data in Wenling of Zhejiang province in Southeast China; (ii) calculation of weekly exposure based on the nationwide monitoring and survey results; (iii) linking the exposure model with a modified biokinetic model proposed with a classic biokinetic model to predict urinary cadmium, which is a biomarker to assess the health risks. Results indicated that the developed soil-rice-human transfer model predicted well the urinary cadmium levels in humans subjected to age and exposure uncertainties. We observed a maximum of 0.71 µg g-1 creatinine in males and 1.53 µg g-1 creatinine in females at 70 years old under median cadmium exposure, which was consistent with previous studies. Sensitive analysis was also conducted to detect the sensitive parameters that have the most significant influences on the output of the model. The new risk assessment strategy proposed in this work is beneficial for predicting the cumulative cadmium levels in various exposed populations so that we can quickly identify the critical areas from basic soil properties.