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.

The excessive arsenic (As) accumulation in plant tissues enforced toxic impacts on growth indices. So, the utilization of As-contaminated food leads to risks associated with human health. For the reduction of As concentrations in foods, it is obligatory to fully apprehend the take up, accretion, transportation and toxicity mechanisms of As within plant parts. This metalloid impairs the plant functions by disturbing the metabolic pathways at physio-biochemical, cellular and molecular levels. Though several approaches were utilized to reduce the As-accumulation and toxicity in soil-plant systems. Recently, engineered nanoparticles (ENPs) such a zinc oxide (ZnO), silicon dioxide or silica (SiO₂), iron oxide (FeO) and copper oxide (CuO) have emerged new technology to reduce the As-accumulation or phytotoxicity. But, the mechanistic approaches with systematic explanation are missing. By knowing these facts, our prime focus was to disclose the mechanisms behind the As toxicity and its mitigation by ENPs in higher plants. ENPs relives As toxicity and its oxidative damages by regulating the transporter or defense genes, modifying the cell wall composition, stimulating the antioxidants defense, phytochelatins biosynthesis, nutrients uptake, regulating the metabolic processes, growth improvement, and thus reduction in As-accumulation or toxicity. Yet, As-detoxification by ENPs depends upon the type and dose of ENPs or As, exposure method, plant species and experimental conditions. We have discussed the recent advances and highlight the knowledge or research gaps in earlier studies along with recommendations. This review may help scientific community to develop strategies such as applications of nano-based fertilizers to limit the As-accumulation and toxicity, thus healthy food production. These outcomes may govern sustainable application of ENPs in agriculture.

Nitrate is the most common contaminant in groundwater in Korea, as well as across the world. Reduction of nitrate to ammonia is one of the options available to remediate groundwater. In this study, nitrate in groundwater was removed using a zero-valent iron (ZVI) containing biochar synthesized by co-pyrolyzing iron oxide and sawdust biomass. Among the various biogases generated during the pyrolysis of biomass, CO and H₂ act as reducing agents to transform iron oxides to ZVI. Approximately 71% of nitrate was reduced to ammonium by ZVI-biochar at initial pH 2.0, and the reduction decreased sharply by the increase in pH. The mass of nitrate-N decreased is exactly same with the mass of ammonia-N formed. However, ammonium remained in the aqueous phase after reduction by ZVI-biochar, and the total nitrogen was not lowered. Acid-washed zeolite adsorbed most ammonium reduced by the ZVI-biochar and maintained the pH to acidic condition to facilitate the reduction of nitrate. The results of this study imply that nitrate-contaminated groundwater can be properly treated within the guidelines of water quality by synthesized ZVI-containing biochar.

Strategies for reducing cadmium (Cd) content in polluted farmland soils are currently limited. A type of composite with nanoparticles incorporated into a hydrogel have been developed to efficiently remove heavy metals from sewage, but their application in soils faces challenges, such as organic hydrogel degradation due to oxygen exposure and slow Cd²⁺ release from soil constituents. To overcome these challenges, a composite with superior stability for long-term application in soil is required. In this study, ferrous sulfide (FeS) nanoparticle@lignin hydrogel composites were developed. The lignin-based hydrogels inherited lignin’s natural mechanical and environmental stability and the FeS nanoparticles efficiently adsorbed Cd²⁺ and enhanced Cd²⁺ desorption from soils by producing H⁺. The high sorption capacity (833.3 g kg⁻¹) of the composite was attributed to four proposed mechanisms, including cadmium sulfide (CdS) precipitation via chemical reaction (84.06%), lignin complexation (13.19%), hydrogel swelling (0.61%), and nanoparticle sorption (2.15%). In addition, Fe²⁺ displaced from the composite was gradually oxidized to form solid iron oxide hydroxide, which increased Cd²⁺ sorption. The composite significantly reduced the total, surfactant-soluble, and fixed Cd in heavily and lightly polluted paddy soils by 22.4–49.6%, 13.5–68.6%, and 40.1–16.6%, respectively, in 7 days.

Effective and economically viable method to remove elevated metal(loid)s from farm and industrial lands remains a major challenge. In this study, magnetic biochar-based adsorbents with Fe₃O₄ particles embedded in a porous biochar matrix was synthesized via iron (Fe) treated biochar or thermal pyrolysis of Fe treated cedar sawdust. Application and separation of the adsorbent to a multi-contaminated soil slurry simultaneously removed 20–30% of arsenic, cadmium and lead within 24 h. Fast removal of multi-metal(loid)s result from the decrease in all operationally defined fractions of metal(loid)s, not limited to the exchangeable fraction. The direct removal of arsenic-enriched soil particles was observed via micro X-ray fluorescence maps. Furthermore, through comparison of biochars with different production methods, it has been found that magnetization after pyrolysis treatment leads to stronger metals/metalloids adsorption with a higher qₑ (bound sorbate) than other treatments but pyrolysis after magnetization stabilized Fe oxides on the biochar surface, indicating a higher biochar recovery rate (∼65%), and thus a higher metal(loid)s removal efficiency. The stability of Fe oxides on the surface of biochar is the determining factor for the removal efficiency of metal(loid)s from soil.

Condensed organic matters (COM) with black carbon-like structures are considered as long-term carbon sinks because of their high stability. It is difficult to distinguish COM from general organic matter by conventional chemical analysis, thus the contribution by and interaction mechanisms of organo-mineral complexes in COM stabilization are unclear and generally neglected. Molecular markers related to black carbon-like structures, such as benzene polycarboxylic acids (BPCAs), are promising tools for the qualitative and quantitative analysis of COM. In this study, one natural soil and two cultivated soils with 25 y- or 55 y-tillage activities were collected and the distribution characteristics of BPCAs were detected. All the investigated soils showed similar BPCA distribution pattern, and over 60% of BPCAs were detected in clay fraction. The extractable BPCA contents were substantially increased after mineral removal. The ratios of BPCA contents before and after mineral removal indicate the extent of COM-mineral particle interactions, and our results suggested that up to 73% COM were protected by mineral particles, and more stronger interactions were noted on clay than on silt. The initial cultivation dramatically decreased COM-clay interactions, and this interaction was recovered only slowly after 55-y cultivation. Kaolinite and muscovite are important for COM protection. But a possible negative correlation between BPCAs and reactive iron oxides of the cultivated soils suggested that iron may promote COM degradation when disturbed by tillage activities. This study provided a new angle to study the stabilization of COM and emphasized the importance of organo-mineral complexes for COM stabilization.

This article gives an overview of nanotechnologies applied in remediation of water contaminated by poly- and perfluoroalkyl substances (PFASs). The use of engineered nanomaterials (ENMs) in physical sorption and photochemical reactions offers a promising solution in PFAS removal because of the high surface area and the associated high reactivities of the ENMs. Modification of carbon nanotubes (CNTs) (e.g., oxidation, applying electrochemical assistance) significantly improves their adsorption rate and capacity for PFASs removal and opens a new door for use of CNTs in environmental remediation. Modified nanosized iron oxides with high adsorption capacity and magnetic property have also been demonstrated to be ideal sorbents for PFASs with great recyclability and thus provide an excellent alternative for PFAS removal under various conditions. Literature shows that PFOA, which is one of the most common PFASs detected at contaminated sites, can be effectively decomposed in the presence of either TiO₂-based, Ga₂O₃-based, or In₂O₃-based nano-photocatalysts under UV irradiation. The decomposition abilities and mechanisms of different nano-photocatalysts are reviewed and compared in this paper. Particularly, the nanosized In₂O₃ photocatalysts have the best potential in PFOA decomposition and the decomposition performance is closely related to the specific surface area and the amount of photogenerated holes on the surfaces of In₂O₃ nanostructures. In addition to detailed review of the published studies, future prospects of using nanotechnology for PFAS remediation are also discussed in this article.

The bioavailability of a pollutant is usually evaluated based on its freely dissolved concentration (Cfree), which can be measured by negligible-depletion equilibrium extraction that is commonly suffered from long equilibration time. Herein, metal-organic framework (MOF) composites (Fe3O4@MIL-101), consists of a magnetic Fe3O4 core and a MIL-101 (Cr) MOF shell, is developed as sorbents for negligible-depletion magnetic solid-phase extraction (nd-MSPE) of freely dissolved polyaromatic hydrocarbons (PAHs) in environmental waters. The freely dissolved PAHs in 1000 mL water samples are extracted with 1.5 mg MOF composites, and desorbed with 0.9 mL of acetonitrile under sonication for 5 min. The MOF composites exclude the extraction of dissolved organic matter (DOM) and DOM-associated PAHs by size exclusion. Additionally, the combined interactions (hydrophobic, π-π and π-complexation) between PAHs and composites markedly reduced the extraction equilibration time to < 60 min for all the studied PAHs with logKOW up to 5.74. Moreover, the porous coordination polymers property of the MOFs makes the proposed nd-MSPE based on the partitioning of PAHs and thus excludes the competitive adsorption of coexisting substances. The developed nd-MSPE approach provides low detection limits (0.08–0.82 ng L−1), wide linear range (1–1000 ng L−1) and high precision (relative standard deviations (RSDs) (3.3–4.8%) in determining Cfree of PAHs. The measured Cfree of PAHs in environmental waters are in good agreement with that of verified method. Given the large diversity in structure and pore size of MOFs, various magnetic MOFs can be fabricated for task-specific nd-MSPE of analytes, presenting a prospective strategy for high-efficiency measuring Cfree of contaminants in environments.

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.

Static environmental exposure assessment models based on material flow analysis (MFA) have previously been used to estimate flows of engineered nanomaterials (ENMs) to the environment. However, such models do not account for changes in the system behavior over time. Dynamic MFA used in this study includes the time-dependent development of the modelling system by considering accumulation of ENMs in stocks and the environment, and the dynamic release of ENMs from nano-products. In addition, this study also included regional variations in population, waste management systems, and environmental compartments, which subsequently influence the environmental release and concentrations of ENMs. We have estimated the flows and release concentrations of nano-SiO₂, nano-iron oxides, nano-CeO₂, nano-Al₂O₃, and quantum dots in the EU and six geographical sub-regions in Europe (Central Europe, Northern Europe, Southern Europe, Eastern Europe, South-eastern Europe, and Switzerland). The model predicts that a large amount of ENMs are accumulated in stocks (not considering further transformation). For example, in the EU 2040 Mt of nano-SiO₂ are stored in the in-use stock, 80,400 tonnes have been accumulated in sediments and 65,600 tonnes in natural and urban soil from 1990 to 2014. The magnitude of flows in waste management processes in different regions varies because of differences in waste handling. For example, concentrations in landfilled waste are lowest in South-eastern Europe due to dilution by the high amount of landfilled waste in the region. The flows predicted in this work can serve as improved input data for mechanistic environmental fate models and risk assessment studies compared to previous estimates using static models.