Antifouling paint particles (APPs) of between 500 μm and >2 mm in diameter have been identified in silty, intertidal estuarine sediments through a combination of microscopy and x-ray fluorescence spectrometry. APPs were heterogeneously distributed, with maximal concentrations of 430 particles L−1 (0.2 g L−1) near to a facility where boats are regularly maintained and 400 particles L−1 (4.2 g L−1) at a location where old boats had been abandoned, with the majority of particles encountered in the finest size fraction retrieved. APPs contained variable concentrations of Cu, Zn, Sn and Pb, with respective maxima of 562,000, 269,000, 9,970 and 126,000 mg kg−1. These characteristics are attributed to a multitude of contemporary and historic sources of an assortment of formulations and result in significant but heterogeneous metal contamination of local sediments. APPs were also identified in the guts of the deposit-feeding ragworm, Hediste diversicolor, that inhabited sediments impacted by abandoned boats or boating activities. The tissue of H. diversicolor was particularly enriched in Cu where ingested APPs were observed, with a significant correlation between dry weight Cu concentrations in the two media (r = 0.734) presumably reflecting the inability of the animal to regulate this metal. While the toxicity of APPs requires further investigation, there is clearly a need for stricter regulations on antifouling wastes in boatyards and marinas and a requirement to better manage abandoned boats.

The Deception Island, located in Maritime Antarctica, is a volcanic island with geothermal activity and one of the most visited by tourists. However, the extent of the anthropogenic impact remains largely unknown and the factors shaping the resistance/tolerance mechanisms in the microbiomes from Whalers Bay ecosystems have never been investigated. In this context, this study aimed to reveal the resistome profiles of Whalers Bay sediments and correlate them with environmental factors. Samples were collected at four sites during the summer 2014/2015 along a transect of 27.5 m in the Whalers Bay sediments. DNA isolated from sediment samples was sequenced using the Illumina HiSeq platform. Bioinformatic analyses allowed the assembly of contigs and scaffolds, prediction of ORFs, and taxonomic and functional annotation using NCBI RefSeq database and KEGG orthology, respectively. Microorganisms belonging to the genera Psychrobacter, Flavobacterium and Polaromonas were shown to dominate all sites, representing 60% of taxonomic annotation. Arsenic (As), copper (Cu) and iron (Fe) were the most abundant metal resistance/tolerance types found in the microbiomes. Beta-lactam was the most common class related to antibiotics resistance/tolerance, corroborating with previous environmental resistome studies. The acridine class was the most abundant amongst the biocide resistance/tolerances, related to antiseptic compounds. Results gathered in this study reveal a repertoire of resistance/tolerance classes to antibiotics and biocides unusually found in Antarctica. However, given the volcanic nature (heavy metals-rich region) of Deception Island soils, this putative impact must be viewed with caution.

In the present study, the competitive adsorption of Cu²⁺, Pb²⁺, and Cd²⁺ by a novel natural adsorbent (i.e., argillaceous limestone) modified with chitosan (C-AL) was investigated. The results demonstrated that both intraparticle diffusion and chemisorption marked significant contributions to the Cu²⁺ adsorption process by both raw argillaceous limestone (R-AL) and C-AL in mono-metal adsorption systems. Antagonism was found to be the predominant competitive effect for Cu²⁺, Pb²⁺ and Cd²⁺ adsorptions by C-AL in the multi-metal adsorption system. The three-dimensional simulation and FTIR analysis revealed that the presence of Cu²⁺ suppressed Pb²⁺ and Cd²⁺ adsorptions, while the effect of Cd²⁺ on Cu²⁺ and Pb²⁺ adsorptions was insignificant. The spectroscopic analyses evidenced that amide groups in C-AL played a crucial role in metal adsorption. The preferential adsorptions of Pb²⁺ > Cu²⁺ > Cd²⁺ were likely due to the different affinities of the metals to the lone pair of electrons on the N atom from the amide groups and/or the O atoms from the –OH and -COO⁻ groups on C-AL. The interactions between C-AL and metal ions and between various metal species influenced their competitive adsorption behaviors. C-AL exhibited a superior metal adsorption capacity in comparison with that the capacities of other natural adsorbents reported during the last decade, suggesting its potential practical applications.

Huelva is a highly industrialized city in SW Spain hosting, among others, a Cu smelter, a phosphate fertilizer plant, a power plant, and oil refineries. This study aims to evaluate metal concentrations in lichens as bioindicators of atmospheric pollution in the impacted urban areas. Xanthoria parietina species from Huelva and nearby villages, as well as reference samples from remote, non-contaminated urban areas, were analyzed for trace elements (V, Cr, Mn, Co, Ni, Cu, Zn, Sr, As, Cd, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Er, Tm, Yb, Lu, Pb, Th, U) using Inductively Coupled Plasma-Mass Spectrometry; and for major elements (Ca, K, Mg, P, and S) by Inductively Coupled Plasma-Optical Emission Spectrometry after acid digestion.The metal composition of X. parietina exhibits spatial distribution patterns with extremely elevated concentrations (Co, Ni, Cu, Zn, As, Cd, Sb, Ba, Pb, U, and S) in the surroundings of the industrial estates to <1 km distance. Mean concentrations were significantly lower in the urban areas >1 km from the pollution sources. However, air pollution persists in the urban areas up to 4 km away, as the mean concentrations of Cu, Zn, As, Cd, Sb and S remained considerably elevated in comparison to the reference samples. Though rigorous source apportionment analysis was not the aim of this study, a good positive correlation of our results with metal abundances in ambient particulate matter and in pollution sources points to the Cu smelter as the main source of pollution. Hence, the severe air pollution affecting Huelva and nearby urban areas may be considered a serious health risk to local residents.

Previous studies have shown the effect of surface coatings on biofouling; however, they did not take into account the interaction of the micro and macrofouling communities, the effect of substrate orientation and the zooplankton-zoobenthic coupling together. Therefore, the aim of this study was to evaluate the effect of Zn- and Cu₂O-based coatings on micro and macrofouling on steel surfaces, while also observing the role of substrate orientation and zooplankton supply. An experiment was carried out in the Patos Lagoon Estuary in southern Brazil for three months between spring and summer, where ASTM-36 steel plates represented different coatings (Zn- and/or Cu₂O-based) and orientations (vertical and horizontal). To assess the zooplankton supply, sampling was carried out weekly using a 200 μm plankton net. Zn-based coating positively affected microfouling density compared to uncoated surfaces. The same pattern was observed with macrofouling, associated with vagile fauna preference, which represented 70% of the settled macrofoulers. Cu₂O-based antifouling painted surfaces showed the highest microfouling density inhibition, while Zn + Cu₂O-based coating did not affect the bacteria adhesion but showed lower density compared to Zn-based coating alone. The coatings combination showed the highest invertebrate inhibition. In this way, the macrofouling community was more sensitive than microfouling was to the antifouling coatings tested. The substrate orientation only affected macrofouling, horizontal surfaces being more attractive than vertical. Meroplankton, tychoplankton and holoplankton were recorded on the surfaces, although their representation in plankton was not proportional to the recruits recorded on the substrates. This was probably due to fast dispersion, the interactions of other factors and/or ecological succession stage. Surface coating, substrate orientation, and zooplankton supply interacted with the biofouling process on steel in different ways depending on the organism evaluated. Therefore, copper oxide- and zinc-based coatings were not suitable as coatings to avoid the total biofouling establishment.

Proper management of waste crop residues has been an environmental concern for years. Yellow mealworms (larvae of Tenebrio molitor Linnaeus, 1758) are major insect protein source. In comparison with normal feed wheat bran (WB), we tested five common lignocellulose-rich crop residues as feedstock to rear mealworms, including wheat straw (WS), rice straw (RS), rice bran (RB), rice husk (RH), and corn straw (CS). We then used egested frass for the production of biochar in order to achieve clean production. Except for WS and RH, the crop residues supported mealworms’ life activity and growth with consumption of the residues by 90% or higher and degraded lignin, hemicellulose and cellulose over 32 day period. The sequence of degradability of the feedstocks is RS > RB > CS > WS > RH. Egested frass was converted to biochar which was tested for metal removal including Pb(II), Cd(II), Cu(II), Zn(II), and Cr(VI). Biochar via pyrolysis at 600 °C from RS fed frass (FRSBC) showed the best adsorption performance. The adsorption isotherm fits the Langmuir model, and kinetic analysis fits the Pseudo-Second Order Reaction. The heavy metal adsorption process was well-described using the Intra-Particle Diffusion model. Complexation, cation exchange, precipitation, reduction, deposition, and chelation dominated the adsorption of the metals onto FRSBC. The results indicated that crop residues (WS, RS, RB, and CS) can be utilized as supplementary feedstock along with biochar generated from egested frass to rear mealworms and achieve clean production while generating high-quality bioadsorbent for environment remediation and soil conditioning.

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.