Concentrations as high as thousands of milligrams per kilogram (dry weight) of nonylphenol (NP), an endocrine-disrupting chemical of great concern, have been reported in soil. Soil is considered one of the primary pathways for exposure of crop plants to NP. However, there have been few studies on the toxicity of soil NP to crop plants, especially with comprehensive consideration of the application of organic fertiliser which is a common agricultural practice. In this study, tomato plants were grown in soils treated with NP in the presence and/or absence of earthworm casts (EWCs). After four weeks, we tested the physiological and biochemical responses (accumulative levels of hydrogen peroxide (H₂O₂) and superoxide anion radicals (O₂-·), total chlorophyll content, degree of membrane lipid peroxidation, activities of defence-related enzymes, and level of DNA damage) and the changes in plant growth (elongation and biomass). The growth inhibition, reactive oxygen species (H₂O₂ and O₂-·) accumulation, decrease in chlorophyll content, increase in activity of defence-related enzymes (including superoxide dismutase, peroxidase, catalase, ascorbate peroxidase, glutathione S-transferase and glutathione reductase), enhancement of membrane lipid peroxidation, and DNA damage in NP-treated seedlings were clearly reversed by the intervention of EWCs. In particular, the suppressed elongation, biomass, and chlorophyll content in tomato plants exposed to NP alone were significantly restored by EWCs to even greater levels than those of the undisturbed control. In other words, EWCs could efficiently invigorate the photosynthesis of crops via up-regulating the chlorophyll content, thereby overwhelming the NP stress on plant growth. Accordingly, except for reducing the bioavailability of soil NP as reported in our previous study, EWCs could also help crop plants to cope with NP stress by strengthening their stress resistance ability. Our findings are of practical significance for the formulation of strategies to relieve the negative effects of soil NP on crop growth.

Biochar has a wide range of feedstocks, and different feedstocks often resulted in different properties, such as element distribution and heavy metal immobilization performance. In this work, batch experiments were conducted to assess the effectiveness of biochar pyrolyzed from kitchen waste (KWB), corn straw (CSB), and peanut hulls (PHB) on immobilization of Cd and Pb in contaminated soil by planting swamp cabbage (Ipomoea aquatica Forsk.) with a combination of toxicological and physiological tests. The results showed that biochar could all enhance the soil pH, and reduce extractable Pb and Cd in soil by 22.61%–71.01% (KWB), 18.54%–64.35% (CSB), and 3.28%–60.25% (PHB), respectively. The biochar led to a drop in Cd and Pb accumulation in roots, stems, and leaves by 45.43%–97.68%, 59.13%–96.64%, and 63.90%–99.28% at the dosage of 60.00 mg/kg, respectively. The root length and fresh weight of swamp cabbage were promoted, while superoxide dismutase (SOD) and peroxidase (POD) decreased after biochar treatment. The distribution of heavy metal fractions before and after biochar treatment indicated that biochar could transform Cd and Pb into a state of lower bioavailability, thus inhibiting Cd and Pb uptake by swamp cabbage. Biochar with different feedstocks could be ranked by the following order according to immobilization performance: KWB > CSB > PHB.

Cadmium (Cd) concentration was investigated in parent rocks, surrounding soil of black shales outcrop, stream water, stream sediments, paddy soil as well as rice plants. Leaching test and sequential extraction procedure were applied to evaluate Cd mobility and bioavailability in soil samples. This study aims to emphasize ecological risk of Cd induced by black shales by combining various natural medias in black shales area and control area. The black shales parent rocks have elevated Cd concentration and act as a source of Cd. The liberated Cd from black shales outcrop temporarily accumulated in the acidized surrounding soil and could arise potential adverse impacts on environment due to rainfall. Although high concentration of Cd was not detected in stream water, Cd concentrated stream sediment was a hidden toxin for surface water system. Cd in paddy soil was primarily from geogenic source and effected little by anthropogenic source. The concentration as well as mobility and bioavailability of Cd were high in paddy soil in black shales area, which lead to elevated Cd concentration in roots, shoots and grains of rice. As a result, residents in black shales area suffer increased non-carcinogenic risk of Cd via food chain.

This study describes the development of a sequential extraction procedure for the evaluation of metal nanoparticle mobility and bioaccessibility in soils. The procedure, that was developed using gold nanoparticles (AuNPs) as model species, relies on the fractionation of nanoparticles by sequentially dissolving soil matrix components (carbonates, metal oxides, organic matter and mineral phases) in order to release the entrapped nanoparticle species in the extract solution. By summing up the concentration of AuNPs recovered in each fraction it was found that 93.5% of the spiked AuNP concentration could be recovered which satisfactorily represents the nominal AuNP concentration in the soil. The efficiency of the procedure was found to depend on several procedural artifacts related to the separation of AuNPs from soil colloids and the reactivity of the extraction reagents with AuNPs and their precursor metal ions. Based on the results obtained a protocol for the speciation of the AuNPs and Au ions in the soil sample was also developed. The results of the study show that both AuNPs and Au ions are mainly associated with soil organic matter, which significantly reduces their mobility, while a small amount (<10%) is associated with metal oxides which are more mobile and potentially bioaccessible. The developed procedure provides a springboard for further development of sequential extraction procedures of metal nanoparticles in soils that could be used to assess both the exposure and release of metal nanoparticles and their precursor metal ions in the environment (as total extractable concentration) as well as provide evidence regarding their bioaccessibility and potential bioavailability by determining the concentration of nanoparticles in each specific soil fraction.

Naphthalene sulfonic acids (NSAs) are used extensively in industrial applications as dispersants in dyes, rubbers, and pesticides, and as anti-corrosive agents in coatings, gels, and sealants. This study examined the toxicity of three NSA congeners, barium dinonylnaphthalene sulfonate (BaDNS), calcium dinonylnaphthalene sulfonate (CaDNS), and dinonylnaphthalene disulfonic acid (DNDS), to two benthic species, Tubifex tubifex and Hyalella azteca. Two substrates with different levels of organic carbon (sediment [2%] and sand [0%]) were used in toxicity tests. Juvenile production was the most sensitive endpoint for T. tubifex: the 28-d EC50s were <18.2, 22.2, and 64.0 μg/g dw in sand and 281.3, 361.6, and 218.9 μg/g dw in sediment for BaDNS, CaDNS, and DNDS, respectively. The 28-d LC50s for H. azteca were similar among compounds: 115.3, 82.1, and 49.0 μg/g dry weight (dw) in sand, and 627.3, 757.9, and >188.5 μg/g dw in sediment, for BaDNS, CaDNS, and DNDS, respectively. However, when LC50s were estimated based on concentrations of NSAs measured in overlying water (which can be an important route of exposure for H. azteca), BaDNS and CaDNS were 3–4 orders of magnitude more toxic than DNDS. The NSAs examined were >3-fold more toxic when present in substrates with no organic carbon (e.g., sand) for all H. azteca endpoints where LC/EC50s could be calculated and for sublethal endpoints for T. tubifex. The organic carbon content of the sediment appears to have acted as a sink and reduced NSA toxicity by decreasing bioavailability. Environmental sediment samples were collected from 12 river sites across southern Ontario. The maximum concentration of CaDNS observed in sediment collected from this region was 2.8 μg/g dw in sediment with 2% organic carbon; 100-fold lower than the lowest EC10 in the current study.

Polycyclic aromatic compounds (PACs) are ubiquitous in the environment. Wildlife (including fish) are chronically exposed to PACs through air, water, sediment, soil, and/or dietary routes. Exposures are highest near industrial or urban sites, such as aluminum smelters and oil sands mines, or near natural sources such as forest fires. This review assesses the exposure and toxicity of PACs to wildlife, with a focus on the Canadian environment. Most published field studies measured PAC concentrations in tissues of invertebrates, fish, and birds, with fewer studies of amphibians and mammals. In general, PAC concentrations measured in Canadian wildlife tissues were under the benzo[a]pyrene (BaP) guideline for human consumption. Health effects of PAC exposure include embryotoxicity, deformities, cardiotoxicity, DNA damage, changes to DNA methylation, oxidative stress, endocrine disruption, and impaired reproduction. Much of the toxicity of PACs can be attributed to their bioavailability, and the extent to which certain PACs are transformed into more toxic metabolites by cytochrome P450 enzymes. As most mechanistic studies are limited to individual polycyclic aromatic hydrocarbons (PAHs), particularly BaP, research on other PACs and PAC-containing complex mixtures is required to understand the environmental significance of PAC exposure and toxicity. Additional work on responses to PACs in amphibians, reptiles, and semi-aquatic mammals, and development of molecular markers for early detection of biological responses to PACs would provide a stronger biological and ecological justification for regulating PAC emissions to protect Canadian wildlife.

Devon Great Consols (DGC) is a region in south west England where extensive mining for Cu, Sn and As took place in the nineteenth century. Because of its historical and geological significance, DGC has protected status and is part of the Cornwall and West Devon Mining Landscape UNESCO World Heritage Site. Recently, the region was opened up to the public with the construction or redevelopment of various trails, tracks and facilities for walking, cycling and field visits. We used portable x-ray fluorescence spectrometry to measure, in situ, the concentrations of As in soils and dusts in areas that are accessible to the public. Concentrations ranged from about 140 to 75,000 μg g⁻¹ (n = 98), and in all but one case exceeded a Category 4 Screening Level for park-type soil of 179 μg g⁻¹. Samples returned to the laboratory and fractionated to <63 μm were subjected to an in vitro assessment of both oral and inhalable bioaccessibility, with concentrations ranging from <10 to 25,500 μg g⁻¹ and dependent on the precise nature and origin of the sample and the physiological fluid applied. Concentrations of As in PM₁₀ collected along various transects of the region averaged over 30 ng m⁻³ compared with a typical concentration in UK air of <1 ng m⁻³. Calculations using default EPA and CLEA estimates and that factor in for bioaccessibility suggest a 6-h visit to the region results in exposure to As well in excess of that of minimum risk. The overall risk is exacerbated for frequent visitors to the region and for workers employed at the site. Based on our observations, we recommend that the remodelling or repurposing of historical mine sites require more stringent management and mitigation measures.

Whereas the adverse effects of vanadium released from smelting activities on soil microbial ecology have been widely recognized, little is known about spatiotemporal vanadium distribution and microbial community dynamics in typical contaminated sites. This study describes vanadium contents associated with health risk and microbial responses in both topsoil and subsoil during four consecutive seasons around an ongoing-production smelter in Panzhihua, China. Higher levels of vanadium concentration exceeding soil background value in China (82 mg/kg) were found close to the smelter. Vanadium concentrations decreased generally with the increase in distance to the smelter and depth below surface, as soil vanadium pollution is induced mainly by atmospheric deposition of vanadium bearing dust during smelting. Residual fraction was the predominated vanadium form in soils, with pronounced increase in bioavailable vanadium during rainfall period due to frequent drought-rewetting process. Topsoil close to the smelter exhibited significant contamination, inducing high probability of adverse health effects. Spatiotemporal vanadium distribution creates filtering effects on soil microorganisms, promoting metal tolerant genera in topsoil (e.g. Microvirga) and subsoil (e.g. Bacillus, Geobacter), which is the key in maintaining the community structure by promoting cooperative relation with other taxa. Our results reveal spatiotemporal vanadium distribution in soils at site scale with potential health risk and microbial responses, which is helpful in identifying severe contamination and implementing bioremediation.

Coal-Gas replacement project has been implemented to decrease haze pollution in China in recent years. Airborne arsenic (As) mostly originates from coal burning processes. It is noteworthy to compare the distribution of arsenic fraction in PM₂.₅ before and after coal-gas replacement. Eighty PM₂.₅ samples were collected in Baoding in December 2016 (coal dominated year) and December 2017 (gas dominated year) at different functional areas including residential area (RA), industrial area (IA), suburb (SB), roadside (ST) and Botanical Garden Park (BG). The fraction, bioavailability and health risk of As in the PM₂.₅ samples were investigated and compared between these two years. Arsenic was mainly distributed in the non-specifically sorbed fraction (F1) and the residual fraction (F5). However, the proportion of F1 to the total As in 2017 was higher than that in 2016, while the proportion of As in the amorphous and poorly-crystalline hydrous oxides of Fe and Al fraction (F3) in 2017 was lower. The distributions of fraction and bioavailability showed temporal and spatial characteristics. The total concentration and bioavailability of As in SB and IA were significantly higher than those in RA, ST and BG. The BF (Bioavailability Factor) values of As ranged from 0.30 to 0.61. Health risk assessment indicated that the hazard quotient (HQ) and carcinogenic risk (CR) of As in PM₂.₅ significantly decreased after coal-gas replacement.

Fulvic acid (FA) significantly influences the bioavailability and fate of heavy metals in environments, while its acid-base characters and metal binding processes are still unclear. Here, spectroscopic techniques combined with multiple models (e.g., NICA-Donnan model) and two-dimensional correlation spectroscopy (2D COS) were applied to explore the proton and copper binding properties of FA sub-fractions (FA3-FA13). The charge densities, average contents of carboxylic and phenolic groups, average dissociation constants pKa1 and pKa2 of sub-fractions ranged 0–16 meq∙g∙C−1, 5.03–9.58 meq∙g∙C−1, 2.52–4.67 meq∙g∙C−1, 4.15–4.33 and 8.52–9.72, respectively. FA sub-fractions had a relatively narrow distribution of carboxyl group and a broad distribution of phenolic group. FA sub-fractions also exhibited roughly two phenolic hydroxyl groups per every 1–3 phenyl rings. Differential absorbance spectra (DAS) derived Gaussian bands were associated to the inter-chromophore interactions, the changes of molecular conformations and functional groups with copper addition. Differential spectra slopes (DSlope275-295&325-375) were more significant with higher copper concentration and copper amounts bonded to carboxylic groups. UV–Vis and fluorescence spectra with 2D heterospectral COS revealed the copper binding heterogeneities and sequential orders of chromophores and fluorophores, quantitatively confirming by the order of conditional stability constants (log KCu: 4.64–5.56). Salicylic-/polyhydroxyphenolic, hydroxyl and amino groups were strongly associated to the basic units for fluorophores. Sequential changes followed the order of humic-like→fulvic-like materials for FA3/FA5, humic-like→fulvic-like→tryptophan-like materials for FA7, and humic-like→tryptophan-like→fulvic-like→tyrosine-like materials for FA9/FA13. Spectroscopic techniques combined with various models (especially for 2D COS) are beneficial to elucidate the binding heterogeneity and sensitivity for metal-organic matters at the functional group level.