Urban stormwater is a major source of chemical pollution to receiving waters. Anthropogenic materials in the built environment can be an important source of chemicals to stormwater runoff. Roofing materials can leach significant amounts of metals, which vary over the life of the roof. We report concentrations of three metals (As, Cu, Zn) leaching into runoff from experimental panels of 14 roofing materials over 4.5 years of weathering. Ten roofing materials leached metals. Several leached >10 ppb during one or more study periods. The most common correlate with metal concentration was panel age, followed by precipitation amount. Extrapolating from these observations, we estimated the loading of metals from each roofing material during the first 10 years following installation. Eight materials were predicted to leach metals above background at the end of the 10 years. In combination with information on the prevalence of different roofing materials in the Puget Sound region of the Pacific Northwest, we estimated the relative amount of metals contributed from roofing materials in this basin. Most arsenic and copper was estimated to be contributed by residential roofing; nearly all arsenic from wood shakes manufactured with copper chromated arsenic, and copper contributed mainly from treated wood shakes followed by copper granule-containing asphalt shingles. Most zinc was estimated to be contributed by commercial roofs, including Zincalume and painted metal roofs. Overall our data shows that roofing materials can be an important long-term source of As, Cu, and Zn to stormwater runoff. Compared with atmospheric deposition, roof materials were a significant source, particularly of As and Cu. To get a complete picture of metals sourced from buildings, there is a need to study whole roof systems, including gutters, downspouts, and HVAC systems, as well as metals contributed from homeowner-applied treatments to their roofs.

This study aims to summarize results on potential phytomanagement of two metal(loid)-polluted military soils using Miscanthus x giganteus. Such an option was tested during 2-year pot experiments with soils taken from former military sites in Sliač, Slovakia and Kamenetz-Podilsky, Ukraine. The following elements were considered: As, Cu, Fe, Mn, Pb, Sr, Ti, Zn and Zr. M. x giganteus showed good growth at both military soils with slightly higher maximum shoot lengths in the second year of vegetation. Based on Principal Component Analysis similarities of metal(loid) uptake by roots, stems and leaves were summarized. Major part of the elements remained in M. x giganteus roots and rather limited amounts moved to the aerial parts. Levels taken up decreased in the second vegetation year. Dynamics of foliar metal(loid) concentrations divided the elements in two groups: essential elements required for metabolism (Fe, Mn, Cu, and Zn) and non-essential elements without any known metabolic need (As, Sr, Ti, and Zr). Fe, Mn, Ti and Sr showed similar S-shaped uptake curve in terms of foliar concentrations (likely due to dilution in growing biomass), while Cu exhibited a clear peak mid-season. Behavior of Zn was in between. Foliar Zr and As concentrations were below detection limit. The results illustrated a good potential of M. x giganteus for safely growing on metal-polluted soils taken from both military localities.

Abandoned nonferrous metal(loid) tailings sites are anthropogenic, and represent unique and extreme ecological niches for microbial communities. Tailings contain elevated and toxic content of metal(loid)s that had negative effects on local human health and regional ecosystems. Microbial communities in these typical tailings undergoing natural attenuation are often very poorly examined. The diversity and inferred functions of bacterial communities were examined at seven nonferrous metal(loid) tailings sites in Guangxi (China), which were abandoned between 3 and 31 years ago. The acidity of the tailings sites rose over 31 years of site inactivity. Desulfurivibrio, which were always coupled with sulfur/sulfide oxidation to dissimilate the reduction of nitrate/nitrite, were specific in tailings with 3 years abandonment. However, genus beneficial to plant growth (Rhizobium), and iron/sulfur-oxidizing bacteria and metal(loid)-related genera (Acidiferrobacter and Acidithiobacillus) were specific within tailings abandoned for 23 years or more. The increased abundance of acid-generating iron/sulfur-oxidizing and metal(loid)-related bacteria and specific bacterial communities during the natural attenuation could provide new insights for understanding microbial ecosystem functioning in mine tailings. OTUs related to Sulfuriferula, Bacillus, Sulfurifustis, Gaiella, and Thiobacillus genera were the main contributors differentiating the bacterial communities between the different tailing sites. Multiple correlation analyses between bacterial communities and geochemical parameters indicated that pH, TOC, TN, As, Pb, and Cu were the main drivers influencing the bacterial community structures. PICRUSt functional exploration revealed that the main functions were related to DNA repair and recombination, important functions for bacterial adaptation to cope with the multi-contamination of tailings. Such information provides new insights to guide future metagenomic studies for the identification of key functions beyond metal-transformation/resistance. As well, our results offers novel outlooks for the management of bacterial communities during natural attenuation of multi-contaminated nonferrous metal(loid) tailings sites.

Enhancing metals phytoextraction using gentile mobilizing agents might be an appropriate approach to increase the phytoextraction efficiency and to shorten the phytoremediation duration. The effect of sulfur-impregnated organoclay (SIOC) on the redistribution of potentially toxic elements (PTEs) among their geochemical fractions in soils and their plant uptake has not yet been studied. Therefore, our aim is to investigate the role of different SIOC application doses (1%, 3% and 5%) on operationally defined geochemical fractions (soluble + exchangeable; bound to carbonate; manganese oxide; organic matter; sulfide; poorly- and well-crystalline Fe oxide; and residual fraction) of Cd, Cr, Cu, Ni, Pb, and Zn, and their accumulation by pea (Pisum sativum) and corn (Zea mays) in a greenhouse pot experiment using a polluted floodplain soil. The SIOC caused a significant decrease in soil pH, and an increase in organic carbon and total sulfur content in the soil. The addition of SIOC increased significantly the soluble + exchangeable fraction and bioavailability of the metals. The SIOC leads to a transformation of the residual, organic, and Fe-Mn oxide fractions of Cd, Cu, Ni, and Zn to the soluble + exchangeable fraction. The SIOC addition increased the potential mobile (non-residual) fraction of Cr and Pb. The SIOC increased the sulfide fraction of Cr, Ni, and Zn, while it decreased the same fraction for Cd, Cu, and Pb. The effect of SIOC on the redistribution of metal fractions increased with enhancing application dosages. Pea accumulated more metals than corn with greater accumulation in the roots than shoots. Application of the higher dose of SIOC promoted the metals accumulation by roots and their translocation to shoots of pea and corn. Our results suggest the potential suitability of SIOC for enhancing the phytomanagement of PTEs polluted soils and reducing the environmental risk of these pollutants.

CuFeO₂/CeO₂ as a novel catalyst was synthesized and its catalytic performance was evaluated for electro-Fenton degradation of acid orange 7 (AO7). It was demonstrated from the characterization results that the rhombohedral structure of CuFeO₂ and face-centered cubic fluorite structure of CeO₂ remained stable after nanocomposite construction. The impact of such operating parameters as pH, current intensity and, catalyst amount was investigated and the optimum conditions (100 mgL⁻¹ AO7, pH 3, 150 mgL⁻¹ CuFeO₂/CeO₂, I: 150 mA) determination led to 99.3% AO7 removal and 79.1% COD removal in 60 min. The introduction of CeO₂ as non-inert support had a significant impact on H₂O₂ electro-generation as an important step in AO7 removal. CuFeO₂/CeO₂ presented negligible metal leaching (iron 4.13%, copper 2.4%, and cerium 0.33%) which could be due to the strong interaction between active species and support. The nanocomposite performed efficiently in salty systems and two samples of real wastewaters due to Brønsted acidity character of ceria, which makes it a potential choice in industrial applications. The good performance of nanocomposite could be the result of the synergistic effect between Fe, Cu, and Ce. Regarding scavenging measurements results, the electro-Fenton process followed the Haber-Weiss mechanism. The by-products detection was performed using GC-MS analysis to propose an acceptable pathway for EF degradation of AO7. The BMG kinetics model (1/b = 0.969 (min) and 1/m = 0.269 (min⁻¹)) was matched with the experimental data and described the kinetics of reaction very well. The catalytic activity of CuFeO₂/CeO₂ almost remained after six cycles. Based on the obtained results, CuFeO₂/CeO₂ using the benefit of the synergistic effect of Ce³⁺ with Fe²⁺ and Cu⁺can be introduced as a promising novel catalyst for the electro-Fenton reaction in wastewater treatment.

Reduced graphene oxide (rGO) is one of the most widely used carbon nanomaterials. When it is released into the environment, rGO can markedly affect the transformation of many pollutants, and change their fate and risk. In this work, the synergetic effects of rGO and Cu(II) on the oxidation of 2-naphthol were examined in water in the dark. It was found that the coexistence of rGO and Cu(II) significantly promoted the oxidation of 2-naphthol. Corresponding products were identified as the coupling oligomers of 2-naphthol (dimer, trimer and tetramer) and hydroxylated compounds (OH-2-naphthol, OH-dimer, di–OH–dimer and naphthoquinone derivatives). In the oxidation reaction, rGO played dual roles, i.e. adsorbent and electron-transfer mediator. rGO firstly adsorbed Cu(II) and 2-naphthol on its surface, and then transferred electrons from 2-naphthol to Cu(II) to yield 2-naphthol radicals and Cu(I). 2-Naphthol radicals coupled to each other to form different oligomers of 2-naphthol. Cu(I) was re-oxidized back to Cu(II) by dissolved oxygen, which sustained the continuous oxidation of 2-naphthol. During the autoxidation of Cu(I), reactive oxygen species were generated, which further reacted with 2-naphthol to form hydroxylated products. These findings provide new insights into the risk assessment of rGO and 2-naphthol in aquatic environments.

Stressors associated with climate change and contaminants, resulting from the activities of humans, are affecting organisms and ecosystems globally. Previous studies suggest that the unique characteristics of polar biota, such as slower metabolisms and growth, and the generally stable conditions in their natural environment, cause higher susceptibility to contamination and climate change than those in temperate and tropical areas. We investigated the effects of increased temperature and decreased salinity on copper toxicity in four subantarctic marine invertebrates using realistic projected conditions under a future climatic change scenario for this region. We hypothesised that these relatively subtle shifts in environmental stressors would impact the sensitivity of cold-adapted species to copper. The four test species were: a copepod Harpacticus sp.; isopod Limnoria stephenseni; flatworm Obrimoposthia ohlini; and bivalve Gaimardia trapesina. These species occupy a range of ecological niches, spanning intertidal and subtidal nearshore zones. We predicted that species would differ in their tolerance to stressors, depending on where they occurred within this ecological gradient. Organisms were exposed to the multiple stressors in a factorial design in laboratory based toxicity tests. Sensitivity estimates for copper (LC50) were calculated using a novel statistical approach which directly assessed the impacts of the multiple stressors. In three of the four species tested, sensitivity to copper was amplified by small increases in temperature (2-4 °C). The effects of salinity were more variable but a decrease of as little as 2 ppt caused a significant effect in one species. This study provides some of the first evidence that high latitude species may be at increased risk from contaminants under projected future climate conditions. This interaction, between contaminants and the abiotic environment, highlights a potential pathway to biodiversity loss under a changing climate.

Microalgae are widely used as representative primary producers in ecotoxicology, while macrophytes are much less studied. Here we compared the bioavailability and cellular toxicity pathways of 2 h-exposure to 10−6 mol L−1 Cu in the macrophyte Elodea nuttallii and the green microalga Chlamydomonas reinhardtii.Uptake rate was similar but faster in the algae than in the macrophyte, while RNA-Sequencing revealed a similar number of regulated genes. Early-regulated genes were congruent with expected adverse outcome pathways for Cu with Gene Ontology terms including gene regulation, energy metabolism, transport, cell processes, stress, antioxidant metabolism and development. However, the gene regulation level was higher in E. nuttallii than in C. reinhardtii and several categories were more represented in the macrophyte than in the microalga. Moreover, several categories including oxidative pentose phosphate pathway (OPP), nitrate metabolism and metal handling were only found for E. nuttallii, whereas categories such as cell motility, polyamine metabolism, mitochondrial electron transport and tricarboxylic acid cycle (TCA) were unique to C. reinhardtii. These differences were attributed to morphological and metabolic differences and highlighted dissimilarities between a sessile and a mobile species. Our results highlight the efficiency of transcriptomics to assess early molecular responses in biota, and the importance of studying more aquatic plants for a better understanding on the impact and fate of environmental contaminants.

The binding of metal ions with humic acid (HA) plays an important role in the aggregation of HA and the migration of metal ions in the environments. The effects of common cations (Na⁺, Mg²⁺, Ca²⁺ and Al³⁺) and heavy metal ions (Ag⁺, Cd²⁺, Cu²⁺, Cr³⁺ and Eu³⁺) on the aggregation of HA were investigated systematically by aggregation kinetics, spectroscopic techniques and molecular dynamic (MD) simulations. The critical coagulation concentration (CCC) of mono-, di- and trivalent cations could be predicted by the Schulze-Hardy rule. The aggregation of HA in the presence of Na⁺ and Ag⁺ was mainly due to the reduction of repulsive force and the hydrogen bonds between HA molecules. While the complexation of di- and trivalent cations with carboxylic/phenolic groups, or the cation-π interactions enhanced the intra- or inter-molecular bridges in HA and then contributed greatly to the aggregation of HA. Heavy metal ions could easily pass through the electric double-layer of HA compared with common cations. MD simulations further signified the strong aggregation ability of HA molecules in solutions containing high valence metal ions. These findings are important for understanding not only how the influence of metal ions on the aggregation of HA, but also the conditions which ions more efficient for aggregation.

Metal contamination in aquatic environments is a severe global concern to human health and aquatic ecosystems. This study used several risk assessment indices, to evaluate metal (Cu, Zn, Pb, Cd and Cr) environmental risk of riverine surface sediments across the rural-urban interface of the rapidly developing Wen-Rui Tang River watershed in eastern China. Risk assessments were determined for 38 sites based on the potential ecological risk index (RI), consensus-based sediment quality guidelines (SQGs) and risk assessment code (RAC). Land-use cluster analysis showed that sediments were severely contaminated, especially for Cd, whose concentrations were ∼100 times higher than background levels and had a high proportion in the bioaccessible fraction. According to RI, ErCd was identified with extremely high risk potential, resulting in the highest ecological risk of Cluster 4 (industrial). Similarly, risk within Cluster 4 (industrial) was also ranked highest by SQGs assessment due to the high proportion of industrial land use. Zinc was determined with high risk due to its high concentration compared to its effect range medium (ERM) value. Discrepancies in predicting environmental risks from metals among the three indices were mainly attributed to the contrasting definitions of these metrics. Environmental risk uncertainty derived from spatial variation was further estimated by Monte Carlo simulation and ranked as: Zn > Cd > Cr > Pb > Cu. This comprehensive environmental risk assessment provides important information to guide remediation strategies for management of metal contamination at the watershed scale.