Packed column experiments were conducted to investigate the transport and blocking behavior of surfactant- and polymer-stabilized engineered silver nanoparticles (Ag-ENPs) in saturated natural aquifer media with varying content of material < 0.063 mm in diameter (silt and clay fraction), background solution chemistry, and flow velocity. Breakthrough curves for Ag-ENPs exhibited blocking behavior that frequently produced a delay in arrival time in comparison to a conservative tracer that was dependent on the physicochemical conditions, and then a rapid increase in the effluent concentration of Ag-ENPs. This breakthrough behavior was accurately described using one or two irreversible retention sites that accounted for Langmuirian blocking on one site. Simulated values for the total retention rate coefficient and the maximum solid phase concentration of Ag-ENPs increased with increasing solution ionic strength, cation valence, clay and silt content, decreasing flow velocity, and for polymer-instead of surfactant-stabilized Ag-ENPs. Increased Ag-ENP retention with ionic strength occurred because of compression of the double layer and lower magnitudes in the zeta potential, whereas lower velocities increased the residence time and decreased the hydrodynamics forces. Enhanced Ag-ENP interactions with cation valence and clay were attributed to the creation of cation bridging in the presence of Ca2+. The delay in breakthrough was always more pronounced for polymer-than surfactant-stabilized Ag-ENPs, because of differences in the properties of the stabilizing agents and the magnitude of their zeta-potential was lower. Our results clearly indicate that the long-term transport behavior of Ag-ENPs in natural, silicate dominated aquifer material will be strongly dependent on blocking behavior that changes with the physicochemical conditions and enhanced Ag-ENP transport may occur when retention sites are filled.

Bacteria–phyllosilicate complexes are commonly found in natural environments and are capable of immobilizing trace metals. However, the molecular binding mechanisms of heavy metals to these complex aggregates still remain poorly understood. This study investigated Cd adsorption on Gram-positive Bacillus subtilis, Gram-negative Pseudomonas putida and their binary mixtures with montmorillonite using surface complexation model, Cd K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and isothermal titration calorimetry (ITC). We have shown that larger amounts of Cd are adsorbed by B. subtilis than by P. putida at pH<∼6, and Cd sorption that binding to phosphate groups plays a more important role in P. putida than in B. subtilis. This remind us that we should consider the microbe species when predict the biochemical behavior of trace metals in microbe-bearing environments. The observed Cd adsorption on the binary bacteria–clay composites was more than that predicted based on the component additivity approach. When taking bacteria–clay (1:1 mass ratio) as a representative example, an approximately 68%:32% metal distribution between the bacterial and mineral fraction was found. Both the EXAFS and ITC fits showed that the binding stoichiometry for Cd-carboxyl/phosphate was smaller in the binary mixtures than that in pure bacteria. We proposed that the significant deviations were possibly due to the physical-chemical interaction between the composite fractions that might reduce the agglomeration of the clay grains, increase the negative surface charges, and provide additional bridging of metals ions between bacterial cells and clays.

Bioremediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils requires a higher microbial viability and an increased PAH bioavailability. The clay/modified clay-modulated bacterial degradation could deliver a more efficient removal of PAHs in soils depending on the bioavailability of the compounds. In this study, we modified clay minerals (smectite and palygorskite) with mild acid (HCl) and alkali (NaOH) treatments (0.5–3 M), which increased the surface area and pore volume of the products, and removed the impurities without collapsing the crystalline structure of clay minerals. In soil incubation studies, supplements with the clay products increased bacterial growth in the order: 0.5 M HCl ≥ unmodified ≥0.5 M NaOH ≥3 M NaOH ≥3 M HCl for smectite, and 0.5 M HCl ≥3 M NaOH ≥0.5 M NaOH ≥3 M HCl ≥ unmodified for palygorskite. A14C-tracing study showed that the mild acid/alkali-treated clay products increased the PAH biodegradation (5–8%) in the order of 0.5 M HCl ≥ unmodified > 3 M NaOH ≥ 0.5 M NaOH for smectite, and 0.5 M HCl > 0.5 M NaOH ≥ unmodified ≥ 3 M NaOH for palygorskite. The biodegradation was correlated (r = 0.81) with the bioavailable fraction of PAHs and microbial growth as affected particularly by the 0.5 M HCl and 0.5 M NaOH-treated clay minerals. These results could be pivotal in developing a clay-modulated bioremediation technology for cleaning up PAH-contaminated soils and sediments in the field.

Perennial plant communities in the proximity of metal smelters and refineries may receive substantial inputs of base metal particulate as well as sulphate from the co-emission of sulphur dioxide. The Ni refinery at Port Colborne (Canada) operated by Inco (now Vale Canada Ltd.) emitted Ni, Co and Cu, along with sulphur dioxide, between 1918 and 1984. The objectives were to determine if vascular plant community composition, including standing litter, in twenty-one woodlots on clay or organic soil, were related to soil Ni concentration which decreased in concentration with distance from the Ni refinery. The soil Ni concentration in the clay woodlots ranged from 16 to 4130 mg Ni/kg, and in the organic woodlots, ranged from 98 to 22,700 mg Ni/kg. The concentrations of Co and Cu in the soils were also elevated, and highly correlated with soil Ni concentration. In consequence, each series of woodlots constituted a ‘fixed ratio ray’ of metal mixture exposure. For each of the woodlots, there were 16 independent measurements of ‘woodlot status’ which were correlated with elevated soil Ni concentration. Of the 32 combinations, there were eight linear correlations with soil Ni concentration, considerably more than would be expected by chance alone at a p-value of 0.05. With the exception of mean crown rating for shrubs at the clay sites, the correlations were consistent with the hypothesis that increased soil metal concentrations would be correlated with decreased diversity, plant community health or fitness, and increased accumulation of litter. Only five of the eight linear correlations were from the organic woodlots, suggesting that the observations were not confounded with soil type nor range in soil metal concentrations.

Here we evaluate the performance and limitations of two frequently used model-types to predict trace element solubility in soils: regression based “partition-relations” and thermodynamically based “multisurface models”, for a large set of elements. For this purpose partition-relations were derived for As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sb, Se, V, Zn. The multi-surface model included aqueous speciation, mineral equilibria, sorption to organic matter, Fe/Al-(hydr)oxides and clay. Both approaches were evaluated by their application to independent data for a wide variety of conditions. We conclude that Freundlich-based partition-relations are robust predictors for most cations and can be used for independent soils, but within the environmental conditions of the data used for their derivation. The multisurface model is shown to be able to successfully predict solution concentrations over a wide range of conditions. Predicted trends for oxy-anions agree well for both approaches but with larger (random) deviations than for cations.

The dichlobenil metabolite BAM (2,6-dichlorobenzamide) is frequently detected in aquifers e.g. in Denmark despite the mother compound dichlobenil was banned here since 1997. BAM mineralization was investigated at environmentally relevant concentrations in sediment samples. Undisturbed sediment cores with known dichlobenil application were collected from topsoil to 8.5 m below surface resulting in 57 samples hereof 4 aquifer samples. Mineralization was only substantial (>10%) in the uppermost meter of the unsaturated zone. Microbial adaptation, observed as faster mineralization in pre-exposed than in pristine sediments from the same location, was only evident in sandy sediment where dichlobenil was still present, but not in clayey sediments. Higher initial concentrations (1–5000 μg/kg) did not stimulate mineralization in pristine clayey or sandy sediments, or in pre-exposed sand. However, in pre-exposed clay mineralization was stimulated at high concentrations. Furthermore BAM was for the first time mineralized in aerobic aquifer sediments from different BAM-contaminated groundwater locations.

The bioavailability of chromium (Cr) in soils is highly dependent on Cr fractions and soil physicochemical properties, but it is still unclear how the Cr fractions change in different soils. In this study, phytotoxicity to wheat root elongation was evaluated in different soils across China, and the kinetics of the biogeochemical processes of the added Cr(VI) were examined. After 105 days of soil Cr(VI) spiking, the added Cr(VI) causing 10% inhibition (EC₁₀) of wheat root elongation varied greatly in soils (0.92–151.12 mg kg⁻¹). The results of correlation analysis between EC₁₀ and soil properties showed that the toxicity of Cr was affected by pH, organic matter (OM), clay, cation exchange capacity (CEC), and amorphous Fe oxides. Moreover, the correlation analysis showed that wheat root elongation was more sensitive to extracted Cr(VI) than Cr(III) after 105 days of incubation. A kinetic model was established to evaluate the redox and aging-activating reactions of Cr(VI)/(III) over 105 days. The correlation analysis between the soil properties and rate constants of the model showed that the pH, clay, and amorphous Fe/Al oxides might be the key factors controlling the aging and reduction processes of Cr(VI), and the OM and CEC might greatly affect the aging process of Cr(III). This modeling study is helpful in understanding which soil properties control the transformation and toxicity of Cr in soils.

Marine invertebrates inhabiting estuaries and coastal areas are exposed to natural suspended particulate matter (SPM) like clay or diatom shells but also to anthropogenic particles like microplastics. SPM concentrations may reach 1 g per liter and more, comprising hundreds of millions of items in the size range of less than 100 μm. Suspension feeders and deposit feeders involuntarily ingest these particles along with their food. We investigated whether natural and anthropogenic microparticles at concentrations of 20 mg L⁻¹, which correspond to natural environmental SPM concentrations in coastal marine waters, are ingested by the brown shrimp Crangon crangon and whether these particles induce an oxidative stress response in digestive gland tissue. Shrimp were exposed to clay, silica, TiO₂, polyvinyl chloride (PVC), or polylactide microplastics (PLA) for 6, 12, 24, and 48 h, respectively. The activities of the anti-oxidative enzymes superoxide dismutase (SOD), glutathione peroxidase (GPx), and glutathione reductase (GR) were measured. All five particle types were ingested by the shrimp along with food. The presence of the particles in the shrimp stomach was verified by scanning electron microscopy. The activities of the anti-oxidative enzymes did not vary between animals exposed to different types of microparticles and control animals that did not receive particles. The temporal activity differed between the three enzymes. The lack of a specific biochemical response may reflect an adaptation of C. crangon to life in an environment where frequent ingestion of non-digestible microparticles is unavoidable and continuous maintenance of inducible biochemical defense would be energetically costly. Habitat characteristics as well as natural feeding habits may be important factors to consider in the interpretation of hazard and species-specific risk assessment.

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.

Herbicide application is a practice commonly used in agricultural systems because it is an efficient method of weed control. An inherent characteristic of some herbicides used in mountain agriculture, such as oxyfluorfen, is high adsorption to soil organic matter (SOM). Thus, intensive management that changes the quantity and quality of SOM, such as soil tillage and the massive application of organic fertilizers such as poultry litter, may favor soil contamination by this herbicide and alter its dynamics in the environment. Therefore, this study aimed to characterize the structures of humic substances (HSs) in the soil of forest areas and areas with intensive production of vegetables, relating them to the accumulation of the herbicide oxyfluorfen in tropical mountain agroecosystems. Organic carbon content was quantified in HSs, humic acid (HAs) were structurally characterized by CP/MAS ¹³C-NMR spectroscopy, and the oxyfluorfen molecule was detected and quantified using the QuEChERS residue detection method with subsequent analysis by LC-MS/MS. Oxyfluorfen was not detected in the forest areas, but it was detected in the vegetable growing areas at points with the lowest slope and high contents of organic matter and clay, with values of up to 0.13 mg kg⁻¹. The intensification in the SOM mineralization process, promoted by the intensive management adopted in the vegetable growing areas, resulted in a 16.46% reduction in COT, a 58.84% reduction in the carbon content in the form of SH and a reduction in the structures that give recalcitrance to the HA molecule (CAₗₖyₗ-H,R, CCOO–H,R, CAᵣₒₘₐₜᵢc-H,R, and CAᵣₒₘₐₜᵢc-O) when compared to those values in the forest area, presenting HAs with more aliphatic and labile properties. Thus, due to the structural characteristics of the HAs in the vegetable production areas, the herbicide oxyfluorfen showed a close relationship with the more aliphatic oxygenated structures, namely, CAₗₖyₗ-O,N, CAₗₖyₗ-O and CAₗₖyₗ-di-O.