The biogeochemical cycling of sulfur in soil is closely associated with the mobility and bioavailability of heavy metals; however the influence of sulfur on the behavior of metal-based nanoparticles has not yet been studied. The influence of S fertilizer (S⁰ and Na₂SO₄) applied in paddy soils on CuO NPs behavior in soil pore water was explored in the present study. Synchrotron-based techniques were applied to investigate the migration and speciation transformation of CuO NPs in soil pore water colloids. The application of sulfur fertilizer increased the zeta potential of soil colloids from the rice rhizosphere region and reduced the size of the colloids. Sulfur fertilization decreased the concentration of Cu in soil pore water in the rice rhizosphere region. S⁰ fertilizer reduced the Cu concentration in soil colloids (by 55.8%–73.5%), while Na₂SO₄ increased the Cu concentration in soil colloids (by 173.8%–265.1%). Sulfur fertilization changed the spatial distribution of Fe³⁺ and Cu²⁺ in colloids, making these ions more likely to be aggregated on the edges of soil colloids. Speciation transformation of CuO NPs happened during the process of migration. The main Cu speciation in the soil colloids were CuO NPs, Cu-Cysteine, Cu₂S and Cu-Citrate. Sulfur fertilization increased the proportion of Cu₂S (by 40.5%) in soil pore water colloids from the rice rhizosphere region, while the proportion of CuO NPs was reduced (by 18.4%). Sulfur fertilization changed the morphology and elementary composition of colloids in soil pore water, thus influencing the migration of CuO NPs in the soil column through soil colloids.

Membrane concentrated landfill leachate (MCLL) contains large amounts of recalcitrant organic matter that cause potential hazards to the environment. Knowledge on the compositional variation of MCLL during treatment is important for a better understanding on the degradation pathway of organic pollutants. In this work, the structural change of MCLL during Fenton oxidation process was examined using spectroscopic techniques. The removal rates of COD, TOC and UV254 reached 78.9 ± 1.3%, 70.2 ± 1.4% and 90.64 ± 1.6%, respectively, under the optimal condition (i.e., dosage of H2O2 = 9.0 mL/200 mL, H2O2/Fe(II) molar ratio = 3.0, pH = 3.0, time = 40 min). Spectral analyses suggested that aromatic/CC structure and CO bonds in MCLL can be successfully destroyed by Fenton oxidation, resulting in a decrease in molecular weight. One fulvic-like and one humic-like components were identified in MCLL, both of which can be removed by Fenton treatment. In addition, two-dimensional correlation spectroscopic analyses suggested the oxidative changes of MCLL structure in the order of fulvic-like component/unsaturated conjugated bond > aromatic structure > humic-like component. The results may provide a new insight to the understanding on the structure variation of MCLL during treatment, which is beneficial for the design of cost-effective treatment strategies.

Environmental pollution by heavy metals (HMs) has raised considerable attention due to their toxic impacts on plants, animals and human beings. Thus, the environmental cleanup of these toxic (HMs) is extremely urgent both from the environmental and biological point of view. To remediate HMs-polluted environment, several nanoparticles (NPs) such as metals and its oxides, carbon materials, zeolites, and bimetallic NPs have been documented. Among these, Fe-based NPs have emerged as an effective choice for remediating environmental contamination, due to infinite size, high reactivity, and adsorption properties. This review summarizes the utilization of various Fe-based NPs such as nano zero-valent iron (NZVI), modified-NZVI, supported-NZVI, doped-NZVI, and Fe oxides and hydroxides in remediating the HMs-polluted environment. It presents a comprehensive elaboration on the possible reaction mechanisms between the Fe-based NPs and heavy metals, including adsorption, oxidation/reduction, and precipitation. Subsequently, the environmental factors (e.g., pH, organic matter, and redox) affecting the reactivity of the Fe-based NPs with heavy metals are also highlighted in the current study. Research shows that Fe-based NPs can be toxic to living organisms. In this context, this review points out the environmental hazards associated with the application of Fe-based NPs and proposes future recommendations for the utilization of these NPs.

The desorption rate is an important factor determining cadmium (Cd) ecotoxicity and pollution remediation in soils. The pedotransfer functions (PTFs) of desorption rate coefficients of fresh Cd in soils have been developed in literature. We hypothesized that the aging of Cd pollution would alter Cd desorption process. Taking historically polluted soils as the object, this study aimed at testing the hypothesis and developing new PTFs of desorption rate coefficients for historical Cd. 15 d batch extraction experiments and 13 kinetic models were employed to define Cd desorption rate coefficients in 27 historically polluted soil samples. Compared with fresh Cd, the desorption rate coefficients of historical Cd were lower, and the break time of biphasic desorption processes was retarded to 3 d (4320 min). Different with the usual models for fresh Cd desorption (e.g. parabolic diffusion and two constant rate models), the best models to mimic the historical Cd desorption processes were the pseudo first order, logarithmic, Elovich, and simple Elovich models. The rate-limiting step controlling Cd desorption was changed from the intraparticle diffusion to the interface reaction with aging of pollution. New PTFs of desorption rate coefficients of historical Cd were established (R² ≥ 0.71). Cd desorption rate coefficients increased with organic matter and clay contents, but decreased with oxalate extractable Fe content, solution pH, cation exchange capacity, and silt content. The key soil properties influencing desorption rate coefficients were not altered by the aging of pollution. The developed PTFs could guide us to adjusting the ecotoxicity and pollution remediation of Cd in historically polluted field soils.

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.

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.

Iron nanoparticles (Fe NPs) have often been used for in situ remediation of both groundwater and soil. However, the impact of Fe NPs on the distribution and transformation of As species in contaminated soil is still largely unknown. In this study, green iron oxide nanoparticles synthesized using a euphorbia cochinchinensis leaf extract (GION) were used to stabilize As in a contaminated soil. GION exhibited excellent As stabilization effects, where As in non-specifically-bound and specifically-bound fractions decreased by 27.1% and 67.3% after 120 days incubation. While both arsenate (As (V)) and arsenite (As (III)) decreased after GION application, As (V) remained the dominant species in soil. X-ray photoelectron spectroscopy (XPS) confirmed that As (V) was the dominant species in specifically-bound fractions, while As (III) was the dominant species in amorphous and poorly-crystalline hydrous oxides of Fe and Al. Correlation analysis showed that while highly available As fractions were negatively correlated to oxalate and DCB extractable Fe, they were positively correlated to Fe²⁺ content, which indicated that Fe cycling was the main process influencing changes in As availability. X-ray fluorescence (XRF) spectroscopy also showed that the Fe₂O₃ content increased by 47.9% following GION soil treatments. Overall, this work indicated that As would be transformed to more stable fractions during the cycling of Fe following GION application and that the application of GION, even in small doses, provides a low-cost and ecofriendly method for the stabilization of As in soil.

Contaminated groundwater is considered as one of the most important pathways of human exposure to the geogenic contaminants. Present study has been conducted in a part of Indus basin to investigate the presence and spatial distribution of arsenic (As) and other trace metals in groundwater. The As concentration varies from bdl-255.6 μg/L and 24.6% of the 73 collected groundwater samples have As above world health organization (WHO) guideline of 10 μg/L. High concentration of As is found along the newer alluvium of Ravi River. As is found with high bicarbonate (HCO3−) and Iron (Fe) and low nitrate (NO3−) indicating reductive dissolution of Fe bearing minerals. However, silicate weathering along with high sulphate (SO42) and positive oxidation-reduction potential (ORP) indicates mixed redox conditions. Weathering of minerals along with other major hydrogeochemical process are responsible for composition of groundwater. With 31.5% of the samples, sodium bicarbonate (Na–HCO3) is the major water facies followed by magnesium bicarbonate (Mg–HCO3) in 30% of samples. As, Fe and other trace metals including copper (Cu), cadmium (Cd), chromium (Cr), zinc (Zn) were used to calculate the health risk for children and adults in the region. Out of 73 samples, 58% has high Fe, 32.8% has high Zn, and 4.1% has high Cd which are above the prescribed limits of WHO guidelines. Health risk of the population has been assessed using chronic dose index (CDI), hazardous quotients (HQ) and hazardous index (HI) for children and adults. The mean CDI values follows the order as Fe > Zn > Cu > As > Cr > Cd, while the HQ values indicates high As hazards for both children and adults. 43.8% of the groundwater samples have high HI for adults, however, 49.3% has high HI for children indicating higher risk for children compared to adults. A large-scale testing should be prioritized to test the wells for As and other trace metals in the study region to reduce health risks.

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.

Livestock manure is a reservoir for antibiotic resistance genes (ARGs), and aerobic composting is used widely for recycling animal manure. This study investigated the effects of adding nano-zerovalent iron (nZVI) at 0, 100, and 1000 mg/kg on the fates of ARGs and mobile genetic elements (MGEs) during swine manure composting. Under nZVI at 100 mg/kg, the relative abundances of sul1, sul2, dfrA7, ermF, and ermX decreased by 33.26–99.31% after composting, and the relative abundances of intI2 and Tn916/1545 decreased by 95.59% and 97.65%, respectively. Most of the ARGs and MGEs co-occurred and they had strong correlations with each other. The bacterial community structure was significantly separated by the composting periods, and they clustered together under different treatments in the same phase. Network analysis showed that Solibacillus, Clostridium_sensu_stricto_1, Terrisporobacter, Romboutsia, Turicibacter, Lactobacillus, Planococcus, Dietzia, and Corynebacterium_1 were common potential hosts of ARGs and MGEs. Redundancy analysis suggested that MGEs had key effects on the variations in the relative abundances of ARGs. Adding 100 mg/kg nZVI could reduce the environmental risk of ARGs by decreasing the abundances of MGEs.