Nanoplastics (NPs) are becoming emerging pollutants of global concern. Understanding the environmental behavior of NPs is crucial for their environmental and human risk assessment. In this study, the aggregation and stability of polystyrene (PS) NPs were investigated under different hydrochemical conditions such as pH, salt type (NaCl, CaCl₂, Na₂SO₄), ionic strength (IS), and natural organic matter (NOM). The critical coagulation concentrations of PS NPs were determined to be 158.7 mM NaCl, 12.2 mM CaCl₂, and 80.0 mM Na₂SO₄. Ca²⁺ was more effective in destabilizing PS NPs, compared to Na⁺, owing to its stronger charge screening effect. In the presence of monovalent ions, NOM reduced aggregation through steric repulsion, whereas in the case of divalent ions, NOM induced aggregation through cation bridging. Initial and long-term stability studies demonstrated that, in waters with high IS and NOM content, NOM was the most significant factor affecting NPs aggregation. PS NPs would be highly suspended in all freshwaters, and even in wastewater, whereas they would aggregate rapidly and deposit in seawater. Finally, a statistical model was established to evaluate the hydrodynamic diameter of NPs in different waters. The results indicated the stability of PS NPs in natural aquatic environments and their potential for long-term transport.

Because of environmental and societal concerns, new strategies are being developed to mitigate the effects of road salt. These include new deicers that are alternatives to or mixtures with the most common road salt, sodium chloride (NaCl), improved techniques and equipment, and biotic mitigation methods. Using outdoor mesocosms, we investigated the impacts of NaCl and two common alternatives, magnesium chloride (MgCl₂) and calcium chloride (CaCl₂) on freshwater communities. We also investigated the mitigation ability of a common macrophyte, Elodea. We hypothesized that road salt exposure reduces filamentous algae, zooplankton, and macrocrustaceans, but results in increases in phytoplankton and gastropods. We also hypothesized that MgCl₂ is the most toxic salt to communities, followed by CaCl₂, and then NaCl. Lastly, we hypothesized that macrophytes mitigate some of the effects of road salt, specifically the effects on primary producers. We found that all three salts reduced filamentous algal biomass and amphipod abundance, but only MgCl₂ reduced Elodea biomass. MgCl₂ had the largest and longest lasting effects on zooplankton, specifically cladocerans and copepods, which resulted in a significant increase in phytoplankton and rotifers. CaCl₂ increased ostracods and decreased snail abundance, but NaCl increased snail abundance. Lastly, while we did not find many interactions between road salt and macrophyte treatments, macrophytes did counteract many of the salt effects on producers, leading to decreased phytoplankton, increased filamentous algae, and altered abiotic responses. Thus, at similar chloride concentrations, NaCl alternatives, specifically MgCl₂, are not safer for aquatic ecosystems and more research is needed to find safer road management strategies to protect freshwater ecosystems.

Measurement of solute-transport parameters through soils for a wide range of solute- and soil-types is time-consuming, laborious, expensive and practically impossible. So, indirect methods for estimating the transport parameters by pedo-transfer functions are now advancing. This study developed and evaluated an Artificial Neural Network (ANN) model for estimating the transport velocity (V), dispersion coefficient (D) and retardation factor (R) of NaAsO₂, Pb(NO₃)₂, Cd(NO₃)₂, C₉H₉N₃O₂ and CaCl₂ from the basic soil properties. Breakthrough data of the solutes were measured in 14 agricultural soils of Bangladesh by time-domain reflectometry (TDR) in repacked soil columns under unsaturated steady-state water-flow conditions. The transport parameters of the chemicals were determined by analyzing the solute breakthrough data. Bulk density (γ), organic carbon (OC), clay (C) content, pH, median grain diameter (D₅₀) and uniformity coefficient (Cᵤ) of the soils were determined. An ANN model for V, D and R was developed by using data of eight soils, validated/tested with the data of five soils and verified with the data of one soil. Clay content and bulk density of the soils were the most sensitive input variables to the ANN model followed by other soil properties (OC, C, pH, D₅₀ and Cᵤ). The model reliably predicted V, D and R with relative root-mean-square error (RRMSE) of 0.028–0.363, mean error (ME) of – 0.00004 to 0.0005, bias error (BOE%) of 0–0.003 and modeling efficiency (EF) of >0.99. Thus, the ANN model can significantly enhance prediction of pollution transport through soils in terms of cost and effort.

Graphene oxide (GO), used in a wide variety of applications, is increasingly being introduced into aquatic environments; this situation calls for research on GO aggregation and sedimentation to regulate the environmental behaviors and risks. Many studies have investigated the aggregation and the mechanism of GO in water with a single background salt (monosalt system); however, this may not reflect real water environments where multiple salts coexist (multisalt system). A typical synthetic surface water (soft water) with representative multisalts was therefore used to study the aggregation and sedimentation of GO. The GO concentration-dependent aggregation (low concentration aggregation, high concentration stability) was observed in the soft water, and this concentration-dependent aggregation is opposite to the aggregation in monosalt systems (NaCl or CaCl2 solutions). The presence of GO sheets induced the formation of amorphous CaMg(CO3)2 nanoparticles on the GO surfaces in the soft water, and the formed nanoparticles promoted the aggregation and sedimentation of low concentrations of GO through bridging action. Neutral and alkaline conditions were favorable for the formation of CaMg(CO3)2 nanoparticles and the induced GO aggregation. These findings show a new mechanism of GO aggregation in environmentally relevant waters and help us to better evaluate the environmental fate of GO.

Land application of biochar has been increasingly recommended as a powerful strategy for carbon sequestration and soil remediation. However, the biochar particles, especially those in the nanoscale range, may migrate or carry the inherent contaminants along the soil profile, posing a potential risk to the groundwater. This study investigated the transport and retention of wood chip-derived biochar nanoparticles (NPs) in water-saturated columns packed with a paddy soil. The environmentally-relevant soil solution chemistry including ionic strength (0.10–50 mM), electrolyte type (NaCl and CaCl2), and natural organic matter (0–10 mg L−1 humic acid) were tested to elucidate their effects on the biochar NPs transport. Higher mobility of biochar NPs was observed in the soil at lower ionic strengths, with CaCl2 electrolyte being more effective than NaCl in decreasing biochar NPs transport. The retained biochar NPs in NaCl was re-entrained (∼57.7%) upon lowering transient pore-water ionic strength, indicating that biochar NPs were reversibly retained in the secondary minimum. In contrast, negligible re-entrainment of biochar NPs occurred in CaCl2 due to the primary minimum and/or particle aggregation. Humic acid increased the mobility of biochar NPs, likely due to enhanced electrosteric repulsive interactions. The transport behaviors of biochar NPs can be well interpreted by a two-site kinetic retention model that assumes reversible retention for one site, and irreversible retention for the other site. Our findings indicated that the transport of wood chip biochar NPs is significant in the paddy soil, highlighting the importance of understanding the mobility of biochar NPs in natural soils for accurately assessing their environmental impacts.

Mining and smelting activities have contaminated the environment with trace metals (TMs) at a worldwide scale for at least two millennia. A combination of chemical approaches and active biomonitoring was performed to analyse the environmental availability and bioavailability of TM palaeo-pollution in a former PbAg mining district in the Vosges Mountains, France. Along a soil TM contamination gradient that covered eight stations, including two archaeological mining sites, the toxicokinetics of six TMs (Pb, Cd, As, Ag, Co, Sb) in the snail Cantareus aspersus revealed that palaeo-pollution from the studied sites remains bioavailable. This study provides the first data on the accumulation kinetics of Ag and Co for C. aspersus. The environmental availability of the TMs was estimated with three chemical extraction methods (aqua regia, EDTA 50 mM, CaCl2 10 mM). Univariate regression analyses showed that EDTA extraction is the best method for estimating the bioavailability of Pb, As, Ag, Co and Sb to snails. None of the three extractants was efficient for Cd. A multivariate analysis of bioaccumulation data revealed that TM bioavailability and transfer were modulated by exposure sources (soil, humus and vegetation) rather than by soil physico-chemical characteristics. Hence, although the deposition of mining wastes dates back several centuries, these wastes still represent a source of contamination that must be considered to develop relevant site management and environmental risk assessment.

Phytoextraction is one of the most promising technologies for the remediation of metal contaminated soils. Changes in soil metal availability during phytoremediation have direct effects on removal efficiency and can also illustrate the interactive mechanisms between hyperaccumulators and metal contaminated soils. In the present study the changes in metal availability, desorption kinetics and speciation in four metal-contaminated soils during repeated phytoextraction by the zinc/cadmium hyperaccumulator Sedum plumbizincicola (S. plumbizincicola) over three years were investigated by chemical extraction and the DGT-induced fluxes in soils (DIFS) model. The available metal fractions (i.e. metal in the soil solution extracted by CaCl2 and by EDTA) decreased greatly by >84% after phytoextraction in acid soils and the deceases were dramatic at the initial stages of phytoextraction. However, the decreases in metal extractable by CaCl2 and EDTA in calcareous soils were not significant or quite low. Large decreases in metal desorption rate constants evaluated by DIFS were found in calcareous soils. Sequential extraction indicated that the acid-soluble metal fraction was easily removed by S. plumbizincicola from acid soils but not from calcareous soils. Reducible and oxidisable metal fractions showed discernible decreases in acid and calcareous soils, indicating that S. plumbizincicola can mobilize non-labile metal for uptake but the residual metal cannot be removed. The results indicate that phytoextraction significantly decreases metal availability by reducing metal pool sizes and/or desorption rates and that S. plumbizincicola plays an important role in the mobilization of less active metal fractions during repeated phytoextraction.

Generic biomarkers are needed to assess environmental risks in metal polluted soils. We assessed the strength of the relationship between earthworm energy reserves and metal availability under conditions of cocktail of metals at low doses and large range of soil parameters. Aporrectodea caliginosa was exposed in laboratory to a panel of soils differing in Cd, Pb and Zn total and available (CaCl2 and EDTA-extractable) concentrations, and in soil texture, pH, CEC and organic-C. Glycogen, protein and lipid contents were recorded in exposed worms. Glycogen contents were not linked to the explaining variables considered. Variable selection identified CaCl2 extractable metals concentrations and soil texture as the main factors affecting protein and lipid contents. The results showed opposite effects of Pb and Zn, high inter-individual variability of biomarkers and weak relationships with easily extractable metals. Our results support the lack of genericity of energy reserves in earthworms exposed to field-contaminated soils.

The present study investigated the impact of solar UV radiation on ZnO nanoparticle toxicity through photocatalytic ROS generation and photo-induced dissolution. Toxicity of ZnO nanoparticles to Daphnia magna was examined under laboratory light versus simulated solar UV radiation (SSR). Photocatalytic ROS generation and particle dissolution were measured on a time-course basis. Two toxicity mitigation assays using CaCl2 and N-acetylcysteine were performed to differentiate the relative importance of these two modes of action. Enhanced ZnO nanoparticle toxicity under SSR was in parallel with photocatalytic ROS generation and enhanced particle dissolution. Toxicity mitigation by CaCl2 to a less extent under SSR than under lab light demonstrates the role of ROS generation in ZnO toxicity. Toxicity mitigation by N-acetylcysteine under both irradiation conditions confirms the role of particle dissolution and ROS generation. These findings demonstrate the importance of considering environmental solar UV radiation when assessing ZnO nanoparticle toxicity and risk in aquatic systems.

This study aimed at assessing the bioavailability and toxicity of lead to Eisenia andrei in shooting range soils representing different land uses (forest, grassland, bullet plot). Soils contained 47–2398 mg Pb/kg dry weight (dw), but also had different pH-CaCl2 (3.2–6.8) and organic matter contents (3.8–13%). Therefore artificial soils with different pH and organic matter contents and two natural soils were included as control soils. Earthworms were exposed for 28 days and toxicity and uptake of Pb were related to total, water and 0.01 M CaCl2 extractable and porewater Pb concentrations as well as to soil characteristics. Pb uptake in the earthworms linearly increased with increasing soil concentrations. At >2000 mg Pb/kg dw and pH 3.3–3.5, high earthworm mortality with significant weight loss and complete inhibition of reproduction were recorded. At <1000 mg/kg dw, earthworm reproduction was more related to differences in pH and other soil characteristics than to Pb.