Although secondary minerals have great potential for heavy metal removal, their impact on chromium biogeochemistry in subsurface environments associated with dissimilatory iron reducing bacteria (DIRB) remains poorly characterized. Here, we have investigated the mechanisms of biogenic secondary minerals on the rate of Cr(VI) bioreduction with shewanella oneidensis MR-1. Batch results showed that the biogenic secondary minerals, schwertmannite and jarosite, appreciably increased the Cr(VI) bioreduction rate. UV–vis diffuse reflection spectra showed that schwertmannite and jarosite are semiconductive minerals, which can be activated by MR-1, followed by transferred conduction electrons toward Cr(VI). Cyclic voltammetry and Tafel analysis suggested that the resistance of secondary minerals is a dominant factor controlling Cr(VI) bioreduction. In addition, Cr(VI) adsorption on secondary minerals through ligand exchange promoted Cr(VI) bioreduction by decreasing the electron transfer distance between MR-1 and chromate. Fe(III)/Fe(II) cycling in schwertmannite and jarosite also contributed to Cr(VI) bioreduction as reflected by X-ray photoelectron spectroscopy and Fourier transform infrared spectrometer. Complementary characterizations further verified the contributions of Fe(III)/Fe(II) cycling, Cr(VI) adsorption, and conduction band electron transfer to enhanced Cr(VI) bioreduction. This study provides new insights on the understanding of Cr(VI) bioreduction by semiconductor minerals containing sulfate in subsurface environments.

House dust is an important medium for exposure to persistent pollutants, such as metals. Detailed characterization of metal composition is needed to identify sources and potential health impacts of exposure. In this study we show that specific metals in dust dominate in different locations within residential homes in a mid-size Canadian city (Fort McMurray, Alberta), up to two years after a major wildfire event in 2016. Dust samples were collected in high-traffic (e.g. bedroom, N = 186), low-traffic (e.g. basement, N = 158), and entranceway areas (N = 171) of residential homes (N = 125), and analyzed for 25 trace metal elements using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The profile of metal concentrations in the entranceway resembled that of outdoor soils, especially for crustal elements. On the other hand, Cu, Zn, and Pb concentrations in dust sampled in indoor living areas were on average three to six times higher than in other indoor locations indicating indoor sources for these elements. In general, Pb concentrations were similar or lower than in an average Canadian residence, but a substantial fraction showed anomalously high concentrations in the low-traffic areas, particularly on concrete surfaces in basements. Notably, the 2016 wildfires showed limited influence on metal concentrations in indoor dust, despite the widespread concerns in the community about long term exposure. Enrichment factor ratio calculations and principal component analysis showed two classes of sources of metals in dust that represent geogenic-outdoor sources and anthropogenic-indoor sources. Overall, we demonstrate that outdoor and indoor sources of dust impact its composition, and these influences are reflected in the different areas of a home.

The presence of chemicals and the destruction of freshwater habitats have been addressed as one of the reasons for the decline in the amphibians’ populations worldwide. Considering the threat that these animals have been suffering in tropical regions, the present study tested if the Brazilian legislation, concerning the permissive levels of lithium and selenium in water bodies and effluents, warrants the protection of aquatic life. To do so, we assessed the metabolic, immunologic, and histopathologic alterations in liver samples of American bullfrog (Lithobates catesbeianus), at the premetamorphic stage, through biomarkers indicative of general energetic status, i.e., glucose, lipid, and protein metabolism using biochemical and histochemical approaches. The immunologic responses were assessed by the quantification of melanomacrophage centres (MMCs); the histopathologic evaluation of the liver sections was also performed. The assay was carried out over 21 days with two periods of sampling (after 7 and 21 days) to assess the effects of exposure over time. The animals were exposed to the considered safe levels of lithium (2.5 mg L⁻¹) and selenium (10 μg L⁻¹), both, isolated and mixed. The exposed animals showed alterations in glucose and lipid metabolism throughout the experiment. The intense presence of MMCs and histopathological responses are compatible with hepatotoxicity. The toxicity expressed by the employed animal model indicates that the Brazilian environmental legislation for the protection of aquatic life needs to be updated. With this study, we intend to provide data for better environmental policies and bring attention to sublethal effects triggered by the presence of contaminants in the aquatic environment.

Based on the concentrations of ten heavy metals (As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, Zn, Fe) in 144 road dust samples collected from 36 sites across 4 seasons from 2016 to 2017 in Beijing, this study systematically analyzed the levels and main sources of health risks in terms of their temporal and spatial variations. A combination of receptor models (positive matrix factorization and multilinear engine-2), human health risk assessment models, and Monte Carlo simulations were used to apportion the seasonal variation of the health risks associated with these heavy metals. While non-carcinogenic risks were generally acceptable, Cr and Ni induced cautionary carcinogenic risks (CR) to children (confidence levels was approximately 80% and 95%, respectively).. Additionally, fuel combustion posed cautionary CR to children in all seasons, while the level of CR from other sources varied, depending on the seasons. Heavy metal concentrations were the most influential variables for uncertainties, followed by ingestion rate and skin adherence factor. The values and spatial patterns of health risks were influenced by the spatial pattern of risks from each source.

The objective of this study was to evaluate the biological and nutritional characteristics of Spodoptera frugiperda (Lepidoptera: Noctuidae), an arthropod pest widely distributed in agricultural regions, after exposure to nano-CeO₂ via an artificial diet and to investigate the presence of cerium in the body of this insect through X-ray fluorescence mapping. Nano-CeO₂, micro-CeO₂, and Ce(NO₃)₃ were incorporated into the diet (0.1, 1, 10, and 100 mg of Ce L⁻¹). Cerium was detected in caterpillars fed with diets containing nano-CeO₂ (1, 10 and 100 mg of Ce L⁻¹), micro-CeO₂ and Ce(NO₃)₃, and in feces of caterpillars from the first generation fed diets with nano-CeO₂ at 100 mg of Ce L⁻¹ as well. The results indicate that nano-CeO₂ caused negative effects on S. frugiperda. After it was consumed by the caterpillars, the nano-CeO₂ reduced up to 4.8% of the pupal weight and 60% of egg viability. Unlike what occurred with micro-CeO₂ and Ce(NO₃)₃, nano-CeO₂ negatively affected nutritional parameters of this insect, as consumption rate two times higher, increase of up to 80.8% of relative metabolic rate, reduction of up to 42.3% efficiency of conversion of ingested and 47.2% of digested food, and increase of up to 1.7% of metabolic cost and 8.7% of apparent digestibility. Cerium caused 6.8–16.9% pupal weight reduction in second generation specimens, even without the caterpillars having contact with the cerium via artificial diet. The results show the importance of new ecotoxicological studies with nano-CeO₂ for S. frugiperda in semi-field and field conditions to confirm the toxicity.

Microplastic pollution is a global concern theme, and there is still the need for less laborious and faster analytical methods aiming at microplastics detection. This article describes a high throughput screening method based on near-infrared hyperspectral imaging (HSI-NIR) to identify microplastics in beach sand automatically with minimum sample preparation. The method operates directly in the entire sample or on its retained fraction (150 μm–5 mm) after sieving. Small colorless microplastics (<600 μm) that would probably be imperceptible as a microplastic by visual inspection, or missed during manual pick up, can be easily detected. No spectroscopic subsampling was performed due to the high-speed analysis of line-scan instrumentation, allowing multiple microplastics to be assessed simultaneously (video available). This characteristic is an advantage over conventional infrared (IR) spectrometers. A 75 cm² scan area was probed in less than 1 min at a pixel size of 156 × 156 μm. An in-house comprehensive spectral dataset, including weathered microplastics, was used to build multivariate supervised soft independent modelling of class analogy (SIMCA) classification models. The chemometric models were validated for hundreds of microplastics (primary and secondary) collected in the environment. The effect of particle size, color and weathering are discussed. Models' sensitivity and specificity for polyethylene (PE), polypropylene (PP), polyamide-6 (PA), polyethylene terephthalate (PET) and polystyrene (PS) were over 99% at the defined statistical threshold. The method was applied to a sand sample, identifying 803 particles without prior visual sorting, showing automatic identification was robust and reliable even for weathered microplastics analyzed together with other matrix constituents. The HSI-NIR-SIMCA described is also applicable for microplastics extracted from other matrices after sample preparation. The HSI-NIR principals were compared to other common techniques used to microplastic chemical characterization. The results show the potential to use HSI-NIR combined with classification models as a comprehensive microplastic-type characterization screening.

Diet, age, and growth rate influences on fish mercury concentrations were investigated for Arctic char (Salvelinus alpinus) and brook trout (Salvelinus fontinalis) in lakes of the eastern Canadian Arctic. We hypothesized that faster-growing fish have lower mercury concentrations because of growth dilution, a process whereby more efficient growth dilutes a fish’s mercury burden. Using datasets of 57 brook trout and 133 Arctic char, linear regression modelling showed fish age and diet indices were the dominant explanatory variables of muscle mercury concentrations for both species. Faster-growing fish (based on length-at-age) fed at a higher trophic position, and as a result, their mercury concentrations were not lower than slower-growing fish. Muscle RNA/DNA ratios were used as a physiological indicator of short-term growth rate (days to weeks). Slower growth of Arctic char, inferred from RNA/DNA ratios, was found in winter versus summer and in polar desert versus tundra lakes, but RNA/DNA ratio was (at best) a weak predictor of fish mercury concentration. Net effects of diet and age on mercury concentration were greater than any potential offset by biomass dilution in faster-growing fish. In these resource-poor Arctic lakes, faster growth was associated with feeding at a higher trophic position, likely due to greater caloric (and mercury) intake, rather than growth efficiency.

Soils containing a large proportion of industrial waste can pose a health risk due to high environmentally available concentrations of toxic metal(loid)s. Nano zero-valent iron (nZVI) and amorphous manganese oxide (AMO) were applied as immobilising amendments (1 wt%) to soils with different industrial origin of As and Sb, and leaching of As, Sb, Pb, and Zn was investigated using a single extraction with deionised water. The different industrial impact was reflected in the mineralogy, chemical composition and pH of these soils. Water-soluble As ratios positively correlated with pH in all experimental treatments. A significant decrease of water-soluble As ratios was observed in all nZVI-amended soils (~65–93% of the control) except for one sample with the lowest solution pH. Nano zero-valent iron was also successful in Sb immobilisation (~76–90% of the control). Highly variable results were obtained for AMO, which only led to a decrease of water-soluble As in soils with solution pH of ≥7 (~70–80% of the control), probably due to lower stability of AMO in acidic conditions. In each case, nZVI was more efficient at decreasing water-soluble As ratios than AMO. Dissolved Pb concentrations remained unchanged after the application of nZVI and AMO, and the decrease of Zn leaching using AMO was controlled mainly by soil pH increase induced by its application. According to the calculated saturation indices, tripuhyite (FeSbO₄) was predicted to be the key mineral controlling Sb solubility in mine soils. Secondary Fe (hydr)oxides either originally present or newly formed due to nZVI oxidation were instrumentally identified at different stages of their transformation and metal(loid) retention. To conclude, nZVI is suitable for application to contaminated soils at a wide pH range, while the use of AMO for decreasing As leaching is limited to soils with pH ≥ 7.

Black carbon (BC), by the combustion of fossil fuels and biomass, has profound effects on climate change and glacier retreat in industrial eras. In the present study, we report refractory BC (rBC) in an ice core spanning 1850–2014, retrieved from the Hariqin Glacier of the Tanggula Mountains in the central Tibetan Plateau, measured using a single particle soot photometer (SP2). The rBC concentration shows a three-fold increase since the 1950s. The mean rBC concentration was 0.71 ± 0.52 ng mL⁻¹ during 1850s–1940s and 2.11 ± 1.60 ng mL⁻¹ during 1950s–2010s. The substantial increase in rBC since the 1950s is consistent with rBC ice core records from the Tibetan Plateau and Eastern Europe. According to the predominant atmospheric circulation patterns over the glacier and timing of changes in regional emissions, the post-1950 amplification of rBC concentration in the central Tibetan Plateau most likely reflects increases in emissions in Eastern Europe, former USSR, the Middle East, and South Asia. Despite the low-level background rBC concentrations in the ice cores from the Tibetan Plateau, the present study highlights a remarkable increase in anthropogenic BC emissions in recent decades and the consequent influence on glaciers in the Tibetan Plateau.

This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/our-business/policies/article-withdrawal).This article has been retracted at the request of the Editors and Corresponding Author.The authors have plagiarized part of a paper that had already appeared in Environmental and Experimental Botany, 179 (2020) 104227, https://doi.org/10.1016/j.envexpbot.2020.104227. One of the conditions of submission of a paper for publication is that authors declare explicitly that their work is original and has not appeared in a publication elsewhere. Re-use of any data should be appropriately cited. As such this article represents a severe abuse of the scientific publishing system. The scientific community takes a very strong view on this matter and apologies are offered to readers of the journal that this was not detected during the submission process.