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.

The behaviour of arsenic (As) from geogenic soil exposed to aerobic conditions is critical to predict the impact of As on the environment, which processes remain unresolved. The current study examined the depth profile of As in geologically derived subsoil cores from Hong Kong and investigated the mobilization, plant availability, and bioaccessibility of As in As-contaminated soil at different depths (0–45.8 m). Results indicated significant heterogeneity, with high levels of As in three layers of soil reaching up to 505 mg/kg at a depth of 5 m, 404 mg/kg at a depth of 15 m, and 1510 mg/kg at a depth of 27–32 m. Arsenic in porewater samples was <11.5 μg/L in the study site. X-ray absorption spectroscopy (XAS) indicated that main As species in soil was arsenate (As(V)), as adsorbed fraction to Fe oxides (41–69% on goethite and 0–8% on ferrihydrite) or the mineral form scorodite (30–57%). Sequential extraction procedure demonstrated that 0.5 ± 0.4% of As was exchangeable. Aerobic incubation experiments exhibited that a very small amount (0.14–0.48 mg/kg) of As was desorbed from the soil because of the stable As(V) complex structure on abundant Fe oxides (mainly goethite), where indigenous microbes partly (59 ± 18%) contributed to the release of As comparing with the sterilized control. Furthermore, no As toxicity in the soil was observed with the growth of ryegrass. The bioaccessibility of As was <27% in the surface soil using simplified bioaccessibility extraction test. Our systematic evaluation indicated that As in the geogenic soil profile from Hong Kong is relatively stable exposing to aerobic environment. Nevertheless, children and workers should avoid incidental contact with excavated soil, because high concentration of As was present in the digestive solution (<0.1–268 μg/L).

Arsenic (As) behavior in paddy soils couples with the redox process of iron (Fe) minerals. When soil is flooded, Fe oxides are transformed to soluble ferrous ions by accepting the electrons from Fe reducers. This process can significantly affect the fate of As in paddy fields. In this study, we show a novel technique to manipulate the Fe redox processes in paddy soils by deploying soil microbial fuel cells (sMFC). The results showed that the sMFC bioanode can significantly decrease the release of Fe and As into soil porewater. Iron and As contents around sMFC anode were 65.0% and 47.0% of the control respectively at day 50. The observed phenomenon would be explained by a competition for organic substrate between sMFC bioanode and the iron- and arsenic-reducing bacteria in the soils. In the vicinity of bioanode, organic matter removal efficiencies were 10.3% and 14.0% higher than the control for lost on ignition carbon and total organic carbon respectively. Sequencing of the 16S rRNA genes suggested that the influence of bioanodes on bulk soil bacterial community structure was minimal. Moreover, during the experiment a maximum current and power density of 0.31 mA and 12.0 mWm−2 were obtained, respectively. This study shows a novel way to limit the release of Fe and As in soils porewater and simultaneously generate electricity.

Graphene oxide (GO) may strongly interact with toxic metal ions and mineral particles upon release into the soil environment. We evaluated the mutual effects between GO and Ni (Ni(II)) with regard to their adsorption and co-adsorption on two minerals (goethite and hematite) in aqueous phase. Results indicated that GO and Ni could mutually facilitate the adsorption of each other on both goethite and hematite over a wide pH range. Addition of Ni promoted GO co-adsorption mainly due to the increased positive charge of minerals and cation–π interactions, while the presence of GO enhanced Ni co-adsorption predominantly due to neutralization of positive charge and strong interaction with oxygen-containing functional groups on adsorbed GO. Increasing adsorption of GO and Ni on minerals as they coexist may thus reduce their mobility in soil. Extended X-ray absorption fine structure (EXAFS) spectroscopy data revealed that GO altered the microstructure of Ni on minerals, i.e., Ni formed edge-sharing surface species (at RNᵢ₋Fₑ∼3.2 Å) without GO, while a GO-bridging ternary surface complexes (at RNᵢ₋C∼2.49 Å and RNᵢ₋Fₑ∼4.23 Å) was formed with GO. These findings improved the understanding of potential fate and toxicity of GO as well as the partitioning processes of Ni ions in aquatic and soil environments.

Cadmium (Cd) availability can be significantly affected by soil properties. The effect of pH value on Cd availability has been confirmed. Paddy soils in South China generally contain high contents of iron (Fe). Thus, it is hypothesized that Fe fractions, in addition to pH value, may play an important role in the Cd bioavailability in paddy soil and this requires further investigation. In this study, 73 paired soil and rice plant samples were collected from paddy fields those were contaminated by acid mine drainage containing Cd. The contents of Fe in the amorphous and DCB-extractable Fe oxides were significantly and negatively correlated with the Cd content in rice grain or straw (excluding DCB-extractable Fe vs Cd in straw). In addition, the concentration of HCl-extractable Fe(II) derived from Fe(III) reduction was positively correlated with the Cd content in rice grain or straw. These results suggest that soil Fe redox could affect the availability of Cd in rice plant. Contribution assessment of soil properties to Cd accumulation in rice grain based on random forest (RF) and stochastic gradient boosting (SGB) showed that pH value should be the most important factor and the content of Fe in the amorphous Fe oxides should be the second most important factor in affecting Cd content in rice grain. Overall, compared with the studies from temperate regions, such as Europe and northern China, Fe oxide exhibited its unique role in the bioavailability of Cd in the reddish paddy soil from our study area. The exploration of practical remediation strategies for Cd from the perspective of Fe oxide may be promising.

This study was conducted to evaluate the effect of commercially available engineered iron oxide nanoparticles coated with a surfactant (ENPFₑ₋ₛᵤᵣf) on effluent water quality from a lab-scale sequencing batch reactor as a model secondary biological wastewater treatment. Results showed that ∼8.7% of ENPFₑ₋ₛᵤᵣf applied were present in the effluent stream. The stable presence of ENPFₑ₋ₛᵤᵣf was confirmed by analyzing the mean particle diameter and iron concentration in the effluent. Consequently, aqueous ENPFₑ₋ₛᵤᵣf deteriorated the effluent water quality at a statistically significant level (p < 0.05) with respect to soluble chemical oxygen demand, turbidity, and apparent color. This implied that ENPFₑ₋ₛᵤᵣf would be introduced into environmental receptors through the treated effluent and could potentially impact them.

This study, for the first time, investigates and quantifies the influence of slight changes in solution pH and ionic strength (IS) on colloidal microsphere deposition site coverage by Suwannee River Humic Acid (SRHA) in a column matrix packed with saturated iron-oxide coated sand. Triple pulse experimental (TPE) results show adsorbed SRHA enhances microsphere mobility more at higher pH and lower IS and covers more sites than at higher IS and lower pH. Random sequential adsorption (RSA) modelling of experimental data suggests 1 μg of adsorbed SRHA occupied 9.28 ± 0.03 × 10⁹ sites at pH7.6 and IS of 1.6 mMol but covered 2.75 ± 0.2 × 10⁹ sites at pH6.3 and IS of 20 mMol. Experimental responses are suspected to arise from molecular conformation changes whereby SRHA extends more at higher pH and lower ionic strength but is more compact at lower pH and higher IS. Results suggest effects of pH and IS on regulating SRHA conformation were additive.

The transformation of DDT was studied in an anaerobic system of dissimilatory iron-reducing bacteria (Shewanella decolorationis S12) and iron oxide (α-FeOOH). The results showed that S. decolorationis could reduce DDT into DDD, and DDT transformation rate was accelerated by the presence of α-FeOOH. DDD was observed as the primary transformation product, which was demonstrated to be transformed in the abiotic system of Fe2+ + α-FeOOH and the system of DIRB + α-FeOOH. The intermediates of DDMS and DBP were detected after 9 months, likely suggesting that reductive dechlorination was the main dechlorination pathway of DDT in the iron-reducing system. The enhanced reductive dechlorination of DDT was mainly due to biogenic Fe(II) sorbed on the surface of α-FeOOH, which can serve as a mediator for the transformation of DDT. This study demonstrated the important role of DIRB and iron oxide on DDT and DDD transformation under anaerobic iron-reducing environments.

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.

Colloid-sized microplastics (MPs) are ubiquitous in aquatic environments and can share the same transport route together with various crystalline, poorly crystalline and freshly formed iron oxides. However, the colloidal interactions between these colloid constituents are not fully understood. This study was designed to investigate the colloidal properties of polystyrene microplastics (PSMPs) under the influence of haematite, goethite, ferrihydrite and freshly formed Fe oxide (FFFO). Dynamic light scattering was coupled with a test tube method to observe changes in the surface charge and colloidal dynamics of suspensions of PSMPs and Fe oxides. The overall effects on the aggregation of PSMPs are found to decrease in the following order: FFFO > ferrihydrite > goethite > haematite. The effects of these Fe oxides are found to strongly depend on pH. While the crystalline oxides play a dominant role in the acidic environment, poorly crystalline oxides show greater effects on PSMP aggregation in an alkaline environment. Heteroaggregation due to decreasing electrostatic interactions is the major mechanism that governs the colloidal dynamics of PSMPs and Fe oxides. It can be inferred that the copresence of Fe oxides and MPs can delay the transport of MPs or even change the destination for MPs.