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.

A biofilm reactor was designed with flat ceramic substrates to remove Co(II), Ni(II) and Zn(II) from industrial wastewater. The ceramics were made of clay and nano-rubber with high mechanical resistance. The surface of the ceramic substrate was modified with neutral fiber and nano-hydroxyapatite. A uniform and stable biofilm mass of 320 g with 2 mm of thickness was produced on the modified ceramic after 3 d. The micro-organisms were identified in the biofilm by polymerase chain reaction (PCR) method. Functional groups of biofilms were identified with a Fourier transform infrared spectrometer (FT-IR). Experiments were designed by central composite design (CCD) using the responsive surface method (RSM). The biosorption process was optimized at pH = 5.8, temperature = 22 °C, feed flux of heavy metal wastewater = 225 ml, substrate flow = 30 ml, and retention time = 7.825 h. The kinetic data was analyzed by pseudo first-order and pseudo second-order kinetic models. Isotherm models and thermodynamic parameters were applied to describe the biosorption equilibrium data of the metal ions on the biofilm-ceramic. The maximum biosorption efficiency and capacity of heavy metal ions were about 72% and 57.21 mg, respectively.

Degrading aquatic organic pollutants efficiently is very important but strongly relied on the design of photocatalysts. Porous graphene could increase photocatalytic performance of ZnO nanoparticles by promoting the effective charge separation of electron-hole pairs if they can be composited. Herein, porous graphene, ZnO nanoparticles and porous graphene/ZnO nanocomposite were prepared by fine tuning of partial combustion, which graphene oxide imperfectly covered by the layered Zn salt was combusted under muffle furnace within few minutes. Resulting ZnO nanoparticles (32–72 nm) are dispersed uniformly on the surface of graphene sheets, the pore sizes of porous graphene are in the range from ∼3 to ∼52 nm. The synthesized porous graphene/ZnO nanocomposite was confirmed to show enhanced efficiency under natural sunlight irradiation compared with pure ZnO nanoparticles. Using porous graphene/ZnO nanocomposite, 100% degradation of methyl orange can be achieved within 150 min. The synergetic effect of photocatalysis and adsorption is main reason for excellent MO degradation of PG/ZnO nanocomposite. This work may offer a new route to accurately prepare porous graphene-based nanocomposite and open a door of their applications.

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.

The imprints of fireworks displays on the adjacent water body were investigated from the perspective of cogeneration of black carbon, metals and perchlorate (ClO₄⁻). In particular, the mixing and dissipation of ClO₄⁻ were studied at Oak Lake, Lincoln, Nebraska, following fireworks displays in 2015 and 2016. Following the display, ClO₄⁻ concentration in the water increased up to 4.3 μg/L and 4.0 μg/L in 2015 and 2016, respectively. A first-order model generally provided a good fit to the measured perchlorate concentrations from which the rate of dissipation was estimated as 0.07 d⁻¹ in 2015 and 0.43 d⁻¹ in 2016. SEM images show imprints of soot and metal particles in aerosol samples. EDS analysis of the lake sediment confirmed the presence of Si, K, Ca, Zn and Ba, most of which are components of fireworks. The δ¹³C range of −7.55‰ to −9.19‰ in the lake water system closely resembles fire-generated carbon. Cogeneration of black carbon and metal with perchlorate was established, indicating that ClO₄⁻ is an excellent marker of fireworks or a burning event over all other analyzed parameters. Future microcosmic, aggregation and column-based transport studies on black carbon in the presence of perchlorate and metals under different environmental conditions will help in developing transport and fate models for perchlorate and black carbon particles.

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.

There is still no consensus over the specific effects of metal-based nanoparticles when compared with the conventional metal salts. Here, the accumulation and toxicity of ZnO-NPs and ZnCl2 in Enchytraeus crypticus over time (1–14 d) were investigated using a sand-solution exposure medium and applying a toxicokinetics and toxicodynamics approach. For both Zn forms, body Zn concentration in the organisms was dependent on both the exposure concentration and exposure time, with equilibrium being reached after 7–14 days of exposure. Generally, the uptake and elimination rate constants (Ku and Ke1) were smaller for ZnO-NPs (5.74–12.6 mg kg−1d−1 and 0.17–0.39 d−1) than for ZnCl2 (8.32–40.1 mg kg−1d−1 and 0.31–2.05 d−1), suggesting that ionic Zn was more accessible for E. crypticus than nanoparticulate Zn. Based on external exposure concentrations, LC50s for ZnO-NPs and ZnCl2 decreased with time from 123 to 67 Zn mg L−1 and from 86 to 62 Zn mg L−1, reaching an almost similar ultimate value within 14 d. LC50s based on body Zn concentrations were almost constant over time (except for 1 d) for both ZnO-NPs and ZnCl2, with overall LC50body of Zn being 1720 and 1306 mg kg−1 dry body weight, respectively. Body Zn concentration, which considers all available pathways, was a good predictor of dynamic toxicity of ZnCl2, but not for ZnO-NPs. This may be attributed to the specific internal distribution and detoxification mechanisms of ZnO-NPs. The particles from ZnO-NPs dominated the accumulation (>75%) and toxicity (∼100%). Our results suggest that dynamic aspects should be taken into account when assessing and comparing NPs and metals uptake and consequent patterns of toxicity.