Shooting ranges polluted by antimony (Sb), lead (Pb), copper (Cu) and zinc (Zn) are used for animal grazing, thus pose a risk of contaminants entering the food chain. Many of these sites are subject to waterlogging of poorly drained soils. Using field lysimeter experiments, we compared Sb, Pb, Cu and Zn uptake by four common pasture plant species (Lolium perenne, Trifolium repens, Plantago lanceolata and Rumex obtusifolius) growing on a calcareous shooting range soil under waterlogged and drained conditions. To monitor seasonal trends, the same plants were collected at three times over the growing season. Additionally, variations in soil solution concentrations were monitored at three depths over the experiment. Under reducing conditions, soluble Sb concentrations dropped from ∼50 μg L−1 to ∼10 μg L−1, which was attributed to the reduction of Sb(V) to Sb(III) and the higher retention of the trivalent species by the soil matrix. Shoot Sb concentrations differed by a factor of 60 between plant species, but remained at levels <0.3 μg g−1. Despite the difference in soil solution concentrations between treatments, total Sb accumulation in shoots for plants collected on the waterlogged soil did not change, suggesting that Sb(III) was much more available for plant uptake than Sb(V), as only 10% of the total Sb was present as Sb(III). In contrast to Sb, Pb, Cu and Zn soil solution concentrations remained unaffected by waterlogging, and shoot concentrations were significantly higher in the drained treatment for many plant species. Although showing an increasing trend over the season, shoot metal concentrations generally remained below regulatory values for fodder plants (40 μg g−1 Pb, 150 μg g−1 Zn, 15–35 μg g−1 Cu), indicating a low risk of contaminant transfer into the food chain under both oxic and anoxic conditions for the type of shooting range soil investigated in this study.

Rapid development of industrial production has stimulated the growth of consumption of raw and auxiliary materials including organic paints, among which volatile organic compounds (VOCs) are proved harmful to the population who inhale the polluted air based on epidemiologic studies. Therefore, new types of environment-friendly paints were developed to replace solvent-based paints (SBPs). Nevertheless, new types of paints containing VOCs failed to replace SBPs entirely due to certain disadvantages. Hence, five kinds of paints were employed in simulation experiments to assess the health risk of primary receptor including three kinds of water-based paints (WBPs) and two kinds of SBPs. Conclusions showed that mean TVOC concentration in breathing zone of primary receptor ranged from 9.5 to 13.6 mg/m³ and 3.4 × 10³ to 1.4 × 10⁴ mg/m³ for WBPs and SBPs, respectively. Assessments of non-cancer risk concluded that nearly one third quantified compounds exceeded corresponding thresholds for WBPs, and the maximum risk value was 101.33; for SBPs, the maximum risk value reached 50760.20, and twenty-two compounds exceeded the reference limits. The calculation of cancer risk values showed that seventeen compounds were higher than acceptable limit amongst which 1,2-dibromoethane had maximum values of 1.27 × 10⁻² to 3.24 × 10⁻² for WBPs; for SBPs, all quantified compounds exceeded the acceptable limit, and 82.61% VOCs were distributed in a scope larger than 1 × 10⁻³. Additionally, a removal efficiency of 60% was considered for primary receptor with personal protective equipment, and subsequent results confirmed its inability of lowering the risk resulted from hazardous VOCs. The calculated potential health risk could be applied to estimate the total health risk for both primary and secondary receptor based on consumed materials. The finding suggested that WBPs could improve VOCs exposure condition and reduce the direct and potential health risk significantly for primary receptor, although they might dissatisfy acceptable limit.

Mercury (Hg) and lead (Pb) are widespread contaminants that pose risks to avian scavengers. In fact, Pb exposure is the primary factor limiting population recovery in the endangered California condor (Gymnogyps californianus) and Hg can impair avian reproduction at environmentally relevant exposures. The Pacific Northwest region of the US was historically part of the condor's native range, and efforts are underway to expand recovery into this area. To identify potential threats to reintroduced condors we assessed foraging habitats, Hg and Pb exposure, and physiological responses in two surrogate avian scavenger species (common ravens [Corvus corax] and turkey vultures [Cathartes aura] across the region between 2012 and 2016. Mercury exposure near the Pacific coast was 17–27-fold higher than in inland areas, and stable carbon and sulfur isotopes ratios indicated that coastal scavengers were highly reliant on marine prey. In contrast, Pb concentrations were uniformly elevated across the region, with 18% of the birds exposed to subclinical poisoning levels. Elevated Pb concentrations were associated with lower delta-aminolevulinic acid dehydratase (δ-ALAD) activity, and in ravens there was an interactive effect between Hg and Pb on fecal corticosterone concentrations. This interaction indicated that the effects of Hg and Pb exposure on the stress axis are bidirectional, and depend on the magnitude of simultaneous exposure to the other contaminant. Our results suggest that condors released to the Pacific Northwest may be exposed to both elevated Hg and Pb, posing challenges to management of future condor populations in the Pacific Northwest. Developing a robust monitoring program for reintroduced condors and surrogate scavengers will help both better understand the drivers of exposure and predict the likelihood of impaired health. These findings provide a strong foundation for such an effort, providing resource managers with valuable information to help mitigate potential risks.

Polyhalogenated carbazoles (PHCs) are a class of emerging organic contaminants that have received increasing concern due to their widespread distribution and dioxin-like toxicity. Although previous studies have suggested possible natural sources of PHCs in the environment, the formation pathways are poorly understood. Here we explored the production of PHCs from halogenation of carbazole in the presence of Br⁻ and/or Cl⁻ under the catalysis of chloroperoxidase (CPO) isolated from the marine fungus Caldariomyces fumago. Overall, a total of 25 congeners including mono-to tetra-substituted chlorinated, brominated, and mixed halogenated carbazoles (with substitution patterns of –BrCl, –BrCl2, –BrCl3, –Br2Cl, –Br2Cl2, and –Br3Cl) were produced from the reactions under various conditions. The PHC product profiles were apparently dependent on the halide concentrations. In the CPO-mediated chlorination of carbazole, 3-mono- and 3,6-dichlorocarbazoles predominated in the formation products. In addition to the less abundant mixed halogenated carbazoles (-Br2Cl), 1,3,6-tri- and 1,3,6,8-tetrabromocarbazoles were the dominant products in reactions containing both Br⁻ and Cl⁻. The CPO-catalyzed halogenation of carbazole could take place in pH 3–7, but the formation products were pH dependent. Results of this study suggest that CPO-catalyzed halogenation of carbazole may play an important role in the natural formation of PHCs.

Bromoxynil is a widely used nitrile herbicide applied to maize and other cereals in many countries. To date, still little is known about bromoxynil turnover and the structural identity of bromoxynil non-extractable residues (NER) which are reported to occur in high amounts. Therefore, we investigated the microbial turnover of ¹³C-labeled bromoxynil for 32 days. A focus was laid on the estimation of biogenic NER based on the turnover of ¹³C into amino acids (AA). At the end, 25% of ¹³C₆-bromoxynil equivalents were mineralized, 2% assigned to extractable residues and 72.5% to NER. Based on 12% in the ¹³C-total AA and an assumed share of AA of 50% in microbial biomass we arrived at 24% of total ¹³C-biogenic NER. About 33% of the total ¹³C-NER could thus be explained by ¹³C-biogenic NER; 67% was unknown and by definition xenobiotic NER with potential for toxicity. The ¹³C label from ¹³C₆-bromoxynil was mainly detected in the humic acids (28.5%), but significant amounts were also found in non-humics (17.6%), fulvic acids (13.2%) and humins (12.7%). The ¹³C-total amino acids hydrolyzed from humic acids, humins and fulvic acids amounted to 5.2%, 6.1% and 1.2% of ¹³C₆-bromoxynil equivalents, respectively, corresponding to total ¹³C-biogenic NER amounts of 10.4%, 12.2% and 2.4%. The humins contained mostly ¹³C-biogenic NER, whereas the humic and fulvic acids may be dominated by the xenobiotic NER. Due to the high proportion of unknown ¹³C-NER and particularly in the humic and fulvic acids, future studies should focus on the detailed characterization of these fractions.

The environment is one of the main reservoirs of antibiotic resistance genes (ARGs) but multidrug resistant (MDR) environmental isolates are barely characterised. As suggested by the name, Pedobacter species have been predominantly isolated from soils, but are also recovered from water (including drinking water), chilled food, fish, compost, sludge, glaciers and other extreme environments. The susceptibility phenotype of Pedobacter lusitanus NL19 (isolated from a deactivated uranium mine), its closely related species and the genus type strain were investigated. All strains are MDR bacteria, resistant to β-lactams, colistin, aminoglycosides and ciprofloxacin. Therefore, Pedobacter spp. are likely intrinsically resistant to β-lactams (including ertapenem) and to other three classes of antibiotics. 6%–8% of their total protein-encoding genes encode a diverse collection of putative ARGs, including β-lactamases. These enzymes are highly abundant in all the other Pedobacter strains with sequenced genomes, especially class C, class B3 and class A. LUS-1 and PLN-1 were further characterised in E. coli. LUS-1 is a class A β-lactamase and it conferred an increase in the MIC of cefotaxime, albeit very low. PLN-1 is a class B3 β-lactamase with carbapenemase activity, conferring resistance to ertapenem and a 66x and 16x increase in the MIC of imipenem and meropenem, respectively. PLN-1 also hydrolyses ampicillin, 1st and 3rd generation cephalosporins, and at a lower extent cephamycins and 4th generation cephalosporins. Therefore, Pedobacter spp. encode a large and diverse arsenal of resistance mechanisms that make them environmental superbugs.

Phosphorus (P) limitation has been demonstrated for micro-polluted surface water denitrification treatment in previous study. In this paper, a lab-scale comparative study of autotrophic denitrification (ADN) and heterotrophic denitrification (HDN) in phosphorus-limited surface water was investigated, aiming to find out the optimal nitrogen/phosphorus (N/P) ratio and the mechanism of the effect of P limitation on ADN and HDN. Furthermore, the optimal denitrification process was applied to the West Lake denitrification project, aiming to improve the water quality of the West Lake from worse than grade V to grade IV (GB3838-2006). The lab-scale study showed that the lack of P indeed inhibited HDN more greatly than ADN. The optimal N/P ratio for ADN and HDN was 25 and a 0.15 mg PO43--P L−1 of microbial available phosphorus (MAP) was observed. P additions could greatly enhance the resistance of ADN and HDN to hydraulic loading shock. Besides, The P addition could effectively stimulate the HDN performance via enriching the heterotrophic denitrifiers and the denitrifying phosphate-accumulating organisms (DNPAOs). Additionally, HDN was more effective and cost-effective than ADN for treating P-limited surface water. The study of the full-scale HDBF (heterotrophic denitrification biofilter) indicated that the denitrification performance was periodically impacted by P limitation, particularly at low water temperatures.

Ionizing γ-irradiation and solvent-assisted spiking are frequently applied to eliminate microbial activity and to induce hydrophobic organic compounds (HOCs) into soil, respectively, when studying the accumulation of chemicals in terrestrial organisms. However, the side-effects that may arise from these treatments on soil-HOC interaction and, subsequently, the kinetics and extents of bioaccumulation are not thoroughly understood. To this end, the accumulation of 1,1-dichloro-2,2-bis(p-chlorophenyl)etylene (p,p’-DDE) by Eisenia andrei was studied in sterilized or unsterilized and freshly spiked (FS) or historically contaminated (HC) soils in parallel with an analysis of aliphatic and hydrophilic soil organic matter (SOM) moieties using mid-infrared diffuse reflectance spectroscopy (DRIFT-S). Irradiation did not impart significant changes on spectral SOM descriptors. In contrast, earthworm inhabitation increased the relative presence of aliphatic moieties to a greater extent than hydrophilic ones, reaching or exceeding pre-treatment levels. Overall, effects on SOM chemistry can be ranked as earthworms > spiking > irradiation. Corresponding changes at the bioaccumulation level were observed for the FS soil (i.e., a 27% reduction in bioaccumulation upon sterilization) but not for the HC soil. This implies that in contrast to the interactions between aged p,p’-DDE and sterilized HC soil, the interactions established between freshly added p,p’-DDE and sterilized FS soil were altered by γ-irradiation-induced secondary effects alone or in combination with earthworm inhabitation. Thus, although the soil treatment processes studied here should not drastically impact compound bioaccumulation, they should be considered in mechanistic studies where the qualitative and quantitative aspects of compound-soil (organic matter)-earthworm interactions are at the centre of attention.

The water level fluctuation zone (WLFZ) of the Three Gorges Reservoir (TGR) in China is a unique geomorphological unit that undergoes annual flooding and drying alternation cycle. The alternating redox conditions within the WLFZ are expected to result in dynamic cycling of reduced sulfur species, which could affect mercury (Hg) methylation due to the high affinity of reduced sulfur species to both inorganic divalent mercury (Hg(II)i) and methylmercury (MeHg). Variations of inorganic sulfur species (measured as acid volatile sulfide, chromium reductive sulfur, elemental sulfur, and water-soluble sulfate), total mercury (THg) and MeHg were studied at two typical WLFZ sites in the TGR from July 2015 to June 2016. Whereas the water-soluble sulfate contents stayed essentially constant, the reduced inorganic sulfur contents varied greatly as the water level changed. Compared with the control soils, the MeHg contents in the WLFZ soils increased, suggesting that water level fluctuations accelerated the methylation process of Hg(II)i. In situ Hg(II)i-methylation also appeared to occur in the sub-layer of the drained sediment during the draw-down season. The significant correlation between MeHg and elemental sulfur (S(0)) further suggests that polysulfides may have played a role in Hg(II)i-methylation by increasing the bioavailable Hg(II)i content in the WLFZ of the TGR.

The work was conducted to establish contamination from improper disposal of hazardous wastes containing lead (Pb) and antimony (Sb) into nearby soils. Besides other elements in the affected area, the biological role of Sb, its behaviour in the pedosphere and uptake by plants and the food chain was considered. Wastes contained 139532 ± 9601 mg kg−1 (≈14%) Pb and 3645 ± 194 mg kg−1 (≈0.4%) Sb respectively and variability was extremely high at a decimetre scale. Dramatically high concentrations were also found for As, Cd, Cu, Mn, Ni, Sn and Zn. In adjacent natural soils metal(oid)s amounts decreased considerably (Pb 5034 ± 678 mg kg−1, Sb 112 mg kg−1) though largely exceeded the directives for a given soil use. Metal(oid)s potential mobility was assessed by using H2O→KNO3→EDTA sequential extractions, and EDTA extracts showed the highest concentration suggesting stable humus-metal complexes formation. Nevertheless, selected plants showed high absorption potential of the investigated elements. Pb and Sb values for Dittrichia viscosa grown in wastes was 899 ± 627 mg kg−1 and 37 ± 33 mg kg−1 respectively. The same plant showed 154 ± 99 mg kg−1 Pb and 8 ± 4 mg kg−1 Sb in natural soils. Helichrysum stoechas had 323 ± 305 mg kg−1 Pb, and 8 ± 3 mg kg−1 Sb. Vitis vinifera from alongside vineyards contained 129 ± 88 mg kg−1 Pb and 18 ± 9 mg kg−1 Sb, indicating ability for metal uptake and warning on metal diffusion through the food chain. The biological absorption coefficient (BAC) and the translocation factor (TF) assigned phytoextraction potential to Dittrichia viscosa and Foeniculum vulgare and phytostabilization potential to Helichrysum stoechas. Dissolved metal (oid)s in the analysed water strongly exceeded the current directive being a direct threat for livings. Data warned against the high contamination of the affected area in all its compartments. Even though native plants growing in metal-contaminated sites may have phytoremediation potential, high risk of metal diffusion may threat the whole ecosystem.