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.

Antibiotics are contaminants of emerging concern due to their potential effect on antibiotic resistance and human health. Antibiotics tend to sorb strongly to organic materials, and biochar, a high efficient agent for adsorbing and immobilizing pollutants, can thus be used for remediation of antibiotic-contaminated soil and water. The effect of ionizable antibiotics on surface characteristics and transport of biochar colloids (BC) in the environment is poorly studied. Column experiments of BC were conducted in 1 mM NaCl solution under three pH (5, 7, and 10) conditions in the presence of sulfamethazine (SMT). Additionally, the adsorption of SMT by BC and the zeta potential of BC were also studied. The experimental results showed that SMT sorption to BC was enhanced at pH 5 and 7, but reduced at pH 10. SMT sorption reduced the surface charge of BC at pH 5 and 7 due to charge shielding, but increased surface charge at pH 10 due to adsorption of the negatively charged SMT species. The mobility of BC was inhibited by SMT under acidic or neutral conditions, while enhanced by SMT under alkaline conditions, which can be well explained by the change of electrostatic repulsion between BC and sand grains. These findings imply that pH conditions played a crucial role in deciding whether the transport of BC would be promoted by SMT or not. Biochar for antibiotics remediation will be more effective under acidic and neutral soil conditions, and the mobility of BC will be less than in alkaline soils.

Arsenite (As(III)) is more toxic, mobilizable and bioavailable than arsenate (As(V)). Hence, the transformations between As(III) and As(V) are crucial for the toxicity and mobility of arsenic (As). However, As transformation and microbial communities involved in alkaline soils are largely unknown. Here we investigate two major pathways of As transformation, i.e., As(III) oxidation and As(V) reduction, and identify the bacteria involved in the alkaline soil by combining stable isotope probing with shotgun metagenomic sequencing. As(III) oxidation and significant increase of the aioA genes copies were observed in the treatments amended with As(III) and NO₃⁻, suggesting that As(III) oxidation can couple with nitrate reduction and was mainly catalyzed by the microorganisms containing aioA genes. As(V) reduction was detected in the treatments amended with As(V) and acetate where the abundance of arrA gene significantly increased, indicating that microorganisms with arrA genes were the key As(V) reducers. Acidovorax, Hydrogenophaga, and Ramlibacter were the putative nitrate-dependent As(III) oxidizers, and Deinococcus and Serratia were the putative respiratory As(V) reducers. These findings will improve our understanding of As metabolism and are meaningful for mapping out bioremediation strategies of As contamination in alkaline environment.

Remediation of soil chromium (Cr) pollution is becoming more and more urgent. In this study, a multi-loaded nano-zero-valent iron (nZVI) material (CNH) was prepared by carboxymethyl cellulose (CMC) and humic acid (HA) as dispersant and support agent, respectively, and the remediation effect of CNH, HA and CN (CNH without HA) for Cr contaminated soil was investigated within 90 d cycle. After 7 d treatment of CNH, the HOAc-extractable Cr decreased significantly. After the 90 d remediation, the HOAc-extractable Cr decreased most in the treatment of 3% CNH, about 74.48% lower than control. All treatments eventually caused different decline of soil pH, with a range of 0.12–0.54, in which the CNH treatment group had the least depression. HA loading significantly weakened the toxicity of nZVI, resulting in the higher soil microbial quantity and enzyme activities compared with CN. Additionally, the improvement of soil microecology by CNH and HA was positively correlated with the ratio of application, while CN was negatively correlated (except FDA enzyme activity) with these indexes. These results emphasized the potential of the synthesized CNH as a promising material to remediate Cr contaminated soil. Furthermore, details of possible mechanistic insight into the Cr remediation were carefully discussed.

Land application of biomass-derived biochar has been increasingly recommended as a beneficial soil amendment for nutrients (such as N, P) retention. However, the small-scale biochar particles, especially those in the nano-scale range, may carry nutrients downward the soil profile, reducing nutrition retention and posing a potential risk to the groundwater. In this study, column experiments were conducted to investigate the retention and transport of phosphorus (P) in two acidic and two alkaline soils as affected by wood chip-derived biochar nanoparticles (NPs). In acidic paddy and red soils, biochar NPs facilitated the retention of P, increasing by about 24% and 16%, respectively, compared to the biochar absence. It is because biochar NPs stabilize soil Fe/Al oxides and dissolved organic carbon (DOC), thereby reducing the release of Fe/Al oxides- and DOC-associated P. In contrast, in alkaline huangmian and chao soils, retention of P was reduced in the presence of biochar NPs, decreasing by about 23% and 18%, respectively. It was mainly due to the increased transport of Fe/Al oxides-associated P in effluents. Moreover, biochar NPs could also act as a P carrier, mediating the retention of P. The diffusive gradients in thin films provided in-suit measurement of labile P in soil profiles, showing much lower labile P from retained P in acidic soils than that from alkaline soils though the labile P with biochar NPs presence was increased in all soils. Our findings indicate that biochar NPs have contrasting effects on the retention of P in acidic and alkaline soils, implying the cautious land applications of biochar for nutrients retention in soils with different acidities.

Continual efforts have been made to determine a simple and universal method of estimating heavy metal phytoavailability in terrestrial systems. In the present study, a mechanism-based multi-surface model (MSM) was developed to predict the partition of Ni(II) in soil–solution phases and its bioaccumulation in wheat (Triticum aestivum L.) in 19 Chinese soils with a wide range of soil properties. MSM successfully predicted the Ni(II) dissolution in 0.01 M CaCl2 extracting solution (R2 = 0.875). The two-site model for clay fraction improved the prediction, particularly for alkaline soils, because of the additional consideration of edge sites. More crucially, the calculated dissolved Ni(II) was highly correlated with the metal accumulation in wheat (R2 = 0.820 for roots and 0.817 for shoots). The correlation coefficients for the MSM and various chemical extraction methods have the following order: soil pore water > MSM ≈ diffuse gradient technique (DGT) > soil total Ni > 0.43 M HNO3 > 0.01 M CaCl2. The results suggested that the dissolved Ni(II) calculated using MSM can serve as an effective indicator of the bioavailability of Ni(II) in various soils; hence, MSM can be used as an supplement for metal risk prediction and assessment besides chemical extraction techniques.

Intensive and paired soil and rice grain survey and multiple-field liming experiments were conducted to assess soil acidification in the past 30 years, quantify the relationships of Cd phytoavailability with soil acidity, and determine efficacies of liming on soil acidity and Cd phytoavailability in paddy soils of central subtropical China at a regional scale. Soil pH, total and extractable Cd (Cdtot and Cdext), rice grain Cd were determined, and all measured data were analyzed separately in groups of 0.1 pH units intervals. Paddy soil pH averagely declined at 0.031 unit yr−1 between 1980s and 2014 (P < 0.01). Piecewise means of log Cd transfer ratio kept around −0.062 between soil pH 4.0 and 5.5 and around −1.31 between pH 6.9 and 7.3, whereas linearly decreased by a factor of 0.76 with pH 5.5–6.9, and by a factor of 1.38 with pH 7.3–8.2 (P < 0.01), respectively. Similar responses to soil pH were observed for soil Cdext to Cdtot ratio. However, the former exhibited a lag effect to soil acidification in the acidic soils and a leading effect in alkaline soils. Liming increased soil pH by 0.50 units, and decreased rice grain Cd by 35.3% and log Cd transfer ratio by a factor of 0.76 (P < 0.01). The piecewise relationship based on the survey precisely predicted the changes in Cd transfer ratio across the multiple-field liming experiments. In conclusion, soil acidification occurred and accelerated in the past 30 years, and piecewise-linearly increased Cd phytoavailability of paddy soils in central subtropical China. Mitigating soil acidification, i.e. liming, should be preferentially implemented to minimize Cd phytoavailability.

The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the 110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectroscopy. After two weeks of ageing the E-values for Ag decreased by 20–90% with a further decrease of 10–40% after six months. The overall decrease in labile Ag for all soils after the 6 month ageing period was 50–100%. The ageing was more rapid and pronounced in the alkaline soils. XANES results for Ag in soils indicated that for the majority of soils the added Ag+ was reduced to metallic Ag over time, and associations with Fe-oxohydroxides and reduced S groups in organic matter also decreased Ag lability. Strong positive correlations were found between metallic Ag and non-labile Ag and between organic carbon and Ag bonded with S species.

Cadmium (Cd) pollution in alkaline soil in some areas of northern China has seriously threatened wheat production and human health. However, there are still few effective amendments for alkaline soil, and the mechanism of amendments with a good immobilization effect remains unclear. In this study, soil sterilization experiments were conducted to investigate the effects of soil microorganisms on the immobilization of a novel amendment—mercapto palygorskite (MPAL) in Cd-contaminated alkaline soils. The results showed that the mercapto on the MPAL surface was not affected by autoclaving. Compared with the control, the available Cd concentration in 0.025% MPAL treatments decreased by 18.80-29.23% after 1 d of aging and stabled after 10 d of aging. Importantly, the immobilization of MPAL on Cd in sterilized soil was significantly better than that in natural soil due to the changes in Cd fractions. Compared with MPAL-treated natural soil, exchangeable Cd fraction and carbonate-bound Cd fraction in MPAL-treated sterilized soil decreased by 20.79–27.09% and 20.05–26.45%, while Fe/Mn oxide-bound Cd fraction and organic matter-bound Cd fraction increased by 17.77–22.68% and 18.85–27.32%. Phylogenetic investigation of communities by reconstruction of unobserved states (PICRUSt) analysis found that the potential functions of the microbial community in normal and sterilized soil were different significantly. Soil sterilization increased the soil pH and decreased the arylsulfatase activity, but did not change the soil zeta potential and available sulfur. The changes in Cd fractions in MPAL-treated sterilized soil may be related to the reduction in the bacterial community and the changes in function microbial, but not to the soil properties. In addition, MPAL application had little effects on the bacterial community, soil pH value, zeta potential, available sulfur, and arylsulfatase. These results showed that the immobilization of MPAL on Cd in alkaline soil was stable and effective, and was not affected by soil sterilization and soil microorganism reduction.