Elucidating the mechanisms of heavy metal (HM) adsorption on clay minerals is key to solving HM pollution in soil. In this study, the adsorption of four HM atoms (As, Cd, Cr, and Hg) on the illite(001) surface was investigated using density functional theory calculations. Different adsorption configurations were investigated and the electronic properties (i.e., adsorption energy (Eₐd) and electron transfer) were analyzed. The Eₐd values of the four HM atoms on the illite(001) surface were found to be As > Cr > Cd > Hg. The Eₐd values for the most stable adsorption configurations of As, Cr, Cd, and Hg were −1.8554, −0.7982, −0.3358, and −0.2678 eV, respectively. The As atoms show effective chemisorption at all six adsorption sites, while Cd, Cr, and Hg atoms mainly exhibited physisorption. The hollow and top (O) sites were more favorable than the top (K) sites for the adsorption of HM atoms. The Gibbs free energy results show that the illite(001) surface was energetically favorable for the adsorption of As and Cr atoms under the influence of 298 K and 1 atm. After adsorption, there was a redistribution of positions and reconfiguration of the chemical bonding of the surface atoms, with a non-negligible influence around the upper surface atoms. Bader charge analysis shows electrons were transferred from the surface to the HM atoms, and a strong correlation between the valence electron variations and the adsorption energy was observed. HM atoms had a high electronic state overlap with the surface O atoms near the Fermi energy level, indicating that the surface O atoms, though not the topmost atoms around the surface, significantly influence HM adsorption. The above results show illite(001) preferentially adsorbed As among all four investigated HM atoms, indicating that soils containing a high proportion of illite might be more prone to As pollution.

The cationic degradable polymer poly(lactic acid) choline iodide ester methacrylate, poly(PLA₄ChMA), can be used to flocculate particles and dewater sediments from tailings ponds and wastewater. A suitable bioaccessibility method is required to characterize the interactions of this novel flocculant in the human gastrointestinal system. To this end, a physiologically based extraction test (PBET) was modified to evaluate the bioaccessibility of flocculants. Bioaccessibility (bioaccessible fraction) is a measure of the solubility of a contaminant in gastrointestinal fluids and that may be available for systemic absorption. The flocculants poly(PLA₄ChMA), SNF C3276, and FLOPAM A3338 were tested at a solid-to-liquid ratio of 1:200 in the absence and presence of kaolin clay, which is used as a model sediment compound. Bioaccessible fractions were characterized by proton nuclear magnetic resonance spectroscopy and estimated by gravimetry. The bioaccessibility of poly(PLA₄ChMA) in gastric and intestinal PBET solutions decreases from 78% and 100%, respectively, in the absence of kaolin to approximately 0% with kaolin, indicating that poly(PLA₄ChMA) remains adsorbed onto the clay surface throughout the PBET, a result confirmed by thermogravimetric analysis. The bioaccessibility of cationic SNF C3276 and anionic FLOPAM A3338 in gastric solution is approximately 76% and 26%, respectively, and is not affected by the presence of kaolin. However, in intestinal solutions, the bioaccessibility of SNF C3276 and FLOPAM A3338 (60–85% in the absence of kaolin) changes to 0% and 100%, respectively, in the presence of kaolin. These results, interpreted in terms of solution pH and surface charge, demonstrate that interactions with kaolin influence the solubility of flocculants and must be considered in the evaluation of bioaccessibility. In future works, such bioaccessibility methods can be applied to assess the human-health safety of using flocculants in wastewater treatments.

Source apportionment can be an effective tool in mitigating soil pollution but its efficacy is often limited by a lack of information on the factors that influence the accumulation of pollutants at a site. In response to this limitation and focusing on a suite of heavy metals identified as priorities for pollution control, the study established a comprehensive pollution control framework using factor identification coupled with spatial agglomeration for agricultural soils in an industrialized part of Zhejiang Province, China. In addition to elucidating the key role of industrial and traffic activities on heavy metal accumulation through implementing a receptor model, specific influencing factors were identified using a random forest model. The distance from the soil sample location to the nearest likely industrial source was the most important factor in determining cadmium and copper concentrations, while distance to the nearest road was more important for lead and zinc pollution. Soil parent materials, pH, organic matter, and clay particle size were the key factors influencing accumulation of arsenic, chromium, and nickel. Spatial auto-correlation between levels of soil metal pollution and industrial agglomeration can enable a more targeted approach to pollution control measures. Overall, the approach and results provide a basis for improved accuracy in source apportionment, and thus improved soil pollution control, at the regional scale.

Widespread soil contamination threatens living standards and weakens global efforts towards the Sustainable Development Goals (SDGs). Detailed soil mapping is needed to guide effective countermeasures and sustainable remediation operations. Here, we review visible and infrared reflectance spectroscopy (VIRS) based detection methods in combination with machine learning. To date, proximal, airborne and spaceborne carrier devices have been employed for soil contamination detection, allowing large areas to be covered at low cost and with minimal secondary environmental impact. In this way, soil contaminants can be monitored remotely, either directly or through correlation with soil components (e.g. Fe-oxides, soil organic matter, clay minerals). Observed vegetation reflectance spectra has also been proven an effective indicator for mapping soil pollution. Calibration models based on machine learning are used to interpret spectral data and predict soil contamination levels. The algorithms used for this include partial least squares regression, neural networks, and random forest. The processes underlying each of these approaches are outlined in this review. Finally, current challenges and future research directions are explored and discussed.

Precise prediction of uranium adsorption at water-mineral interface is of great significance for the safe disposal of radionuclides in geologic environments. Surface complexation modeling (SCM) as a very useful tool has been extensively investigated for simulating adsorption behavior of metals/metalloids at water-mineral interface. Numerous studies concerning the fitting of uranium adsorption on various adsorbents using SCM are well documented, but the systematic and comprehensive review of uranium adsorption using various SCM is not available. In this review, we briefly summarized the rationale of SCM, including constant-capacitance-model (CCM), diffuse-layer-model (DLM), triple-layer-model (TLM); The recent progress in the application of SCM on the fitting of uranium adsorption towards metal (hydr)oxides, clay minerals and soil/sediments was reviewed in details. This review hopefully provides the beneficial guidelines for predicting the transport and fate of uranium in geologic environments beyond laboratory timescales.

Fungicide application for controlling fungal diseases can increase copper (Cu) accumulation in soil. More urgently, Cu released from fungicides can associate with soil clay and favour the mutual aggregation of Cu and soil clay, thereby potentially intensifying the accumulation of Cu. We investigated the effects of Cu salt and six common Cu-based fungicides on colloidal dynamics of a clay fraction from citrus cultivated soil. Batch experiments were carried out to provide the loading capacity of the clay fraction for Cu. The colloidal dynamic experiments were performed over a pH range from 3 to 8 following a test tube method, while surface charge, the key electrochemical factor of the solid-liquid interface, was quantified by a particle charge detector. It was found that all the studied fungicides, via releasing Cu²⁺, acted to effectively favour clay aggregation. The dissolved organic matter obtained from the dissolution of polymers in fungicides can theoretically stimulate clay dispersion. However, their effects were obscured due to the overwhelming effect of Cu²⁺. Therefore, Cu²⁺ appears as the most active agent in the fungicides that intensifies clay aggregation. These findings imply that the intensive application of fungicides for plant protection purposes can inadvertently reduce clay mobility, favour the co-aggregation of clay and fungicides, and hence potentially exacerbate the contamination of the citrus soil.

This work has been conducted as an integrated approach to study the behavior of soils to the metals from sludge amendment. Bureau Commun Reference (BCR) methodology was used as an appropriate tool to harvest precious information about heavy metals evolution versus depth before and after sludge treatments. This three-step extraction procedure (i.e., BCR) may clarify the leaching or retention of heavy metals from the amended soils, as well as their risk level. Our results indicated that sludge applications has shown an increasing flux of heavy metals towards amended soils, of which Pb was the most abundant. Heavy metals mobility in control and amended soils showed that main influencing factors are pH and total organic carbon, especially for copper mobility. Almost all of the metals decreased with soil depth, except for Ni. Speciation of heavy metals in sludges showed that about 45% of Pb, Cu and Ni were associated with residual fraction; Cd was mainly bound to reducible fraction. Speciation forms in the control soil indicated that short term application of sludge has remobilized a fraction of heavy metals into their most labile forms (i.e., exchangeable and reducible fraction). Multivariate statistical analysis suggested that Cd, Zn, Pb and Cu preferentially accumulated in organic-rich surface horizons and clay layers where adsorption played an important role as a determining mechanism. Nevertheless, adsorption did not appear to be directly controlled by high pH values (pH > 7). From Cluster Analysis (CA), one can easily recognize that Pb, Zn and Cu movement in soil profiles were significantly affected by pH, especially residual fraction, labile fraction and reducible fraction.

Natural media such as soil and sediment contain mineralogical and organic components with distinct chemical, surface, and electrostatic properties. To better understand the role of various soil and sediment components on particle transport, columns were packed with quartz sand and natural sediment with added Fe oxyhydroxide coating, illite clay, and peat moss to investigate how these added components influence nTiO₂ retention and transport in geochemically heterogeneous medium. Results showed that nTiO₂ transport was low at pH 5, attributable to the electrostatic attraction between positively-charged nTiO₂ and negatively-charged medium. While illite did not notably affect nTiO₂ transport at pH 5, Fe oxyhydroxide coating increased nTiO₂ transport due to electrostatic repulsion between Fe oxyhydroxide and nTiO₂. Peat moss also increased nTiO₂ transport at pH 5, attributable to the increased DOC concentration, which resulted in higher DOC adsorption to nTiO₂ and intensified electrostatic repulsion between nTiO₂ and the medium. At pH 9, nTiO₂ transport was high due to the electrostatic repulsion between negatively-charged nTiO₂ and medium surfaces. Fe oxyhydroxide coating at pH 9 slightly delayed nTiO₂ transport due to electrostatic attraction, while illite clay and peat moss substantially inhibited nTiO₂ transport via straining/entrapment or electrostatic attraction. Overall, this study demonstrated that pH has a considerable effect on how minerals and organic components of a medium influence nTiO₂ transport. At low pH, electrostatic attraction was the dominant mechanism, therefore, nTiO₂ mobility was low regardless of the differences in mineralogical and organic components. Conversely, nTiO₂ mobility was high at high pH and nTiO₂ retention was dominated by straining/entrapment and sensitive to the mineralogical and organic composition of the medium.

The wide utilization of plastic related products leads to the ubiquitous presence of plastic particles in natural environments. Plastic particles could interact with kaolinite (one type of typical clay particles abundant in environments) and form plastic-kaolinite heteroaggregates. The fate and transport of both plastic particles and kaolinite particles thus might be altered. The cotransport and deposition behaviors of micron-sized plastic particles (MPs) with different surface charge (both negative and positive surface charge) with kaolinite in porous media in both 5 and 25 mM NaCl solutions were investigated in present study. Both types of MPs (negatively charged carboxylate-modified MPs (CMPs) and positively charged amine-modified MPs (AMPs)) formed heteroaggregates with kaolinite particles under both solution conditions examined, however, CMPs and AMPs exhibited different cotransport behaviors with kaolinite. Specifically, the transport of both CMPs and kaolinite was increased under both ionic strength conditions when kaolinite and CMPs were copresent in suspensions. While, when kaolinite and positively charged AMPs were copresent in suspensions, negligible transport of both kaolinite and AMPs were observed under examined salt solution conditions. The competition deposition sites by kaolinite (the portion suspending in solution) with CMPs-kaolinite heteroaggregates led to the increased transport both CMPs and kaolinite when both types of colloids were copresent. In contrast, the formation of larger sized AMPs-kaolinite heteroaggregates with surface charge heterogeneity led to the negligible transport of both kaolinite and AMPs when they were copresent in suspensions. The results of this study show that when plastic particles and kaolinite particles are copresent in natural environments, their interaction with each other will affect their transport behaviors in porous media. The alteration in the transport of MPs or kaolinite (either increased or decreased transport) is highly correlated with the surface charge of MPs.

Copper oxide nanoparticles (CuO NPs) is one of the most commonly used metal oxide nanoparticles for commercial and industrial products. An increase in the manufacturing and use of the CuO NPs based products has increased the likelihood of their release into the aquatic environment. This has attracted major attention among researchers to explore their impact in human as well as environmental systems. CuO NPs, once released into the environment interact with the biotic and abiotic constituents of the ecosystem. Hence the objective of the study was to provide a holistic understanding of the effect of abiotic factors on the stability and aggregation of CuO NPs and its correlation with their effect on the development of zebrafish embryo. It has been observed that the bioavailability of CuO NPs decrease in presence of humic acid (HA) and heteroagglomeration of CuO NPs occurs with clay minerals. CuO NPs, CuO NPs + HA and CuO NPs + Clay significantly altered the expression of genes involved in development of dorsoventral axis and neural network of zebrafish embryos. However, the presence of HA with clay showed protective effect on zebrafish embryo development. These findings provide new insights into the interaction of NPs with abiotic factors and combined effects of such complexes on developing zebrafish embryos genetic markers.