41 ref. doi:10.1016/j.envpol.2003.12.023 | International audience | Metal distribution patterns in superficial soil horizons of agricultural land affected by metallurgical point-source pollution were studied using optical and electron microscopy, synchrotron radiation and spectroscopy analyses. The site is located in northern France, at the center of a former entry lane to a bunker of World War II, temporarily paved with coarse industrial waste fragments and removed at the end of the war. Thin sections made from undisturbed soil samples from A and B horizons were studied. Optical microscopy revealed the occurrence of yellow micrometer-sized (Ap horizon) and red decamicrometer-sized spherulites (AB, B1g horizons) as well as distinct distribution patterns. The chemical composition of the spherulites was dominated by Fe, Mn, Zn, Pb, Ca, and P. Comparison of calculated Zn stocks, both in the groundmass and in spherulites, showed a quasi-exclusive Zn accumulation in these neoformed features. Their formation was related to several factors: (i) liberation of metal elements due to weathering of waste products, (ii) Ca and P supply from fertilizing practices, (iii) co-precipitation of metal elements and Ca and P in a porous soil environment, after slow exudation of a supersaturated soil solution in more confined mineral media.

This study investigates the incidence of MPs in surface sediment samples, collected from the Anzali Wetland, Gillan province, North of Iran. This natural habitat receives municipal wastewater effluents and hosts industries and recreational activities that could release plastic to the wetland. There is need for studies to understand MPs pollution in wetlands. A total of 40 superficial sediment samples were taken covering potential pollution hotspots in the wetland. The average level of MPs was 362 ± 327.6 MP/kg: the highest MPs levels were near the outlet of a highly urbanized river (Pirbazar River) (1380 MP/kg), which runs through Rasht city. This was followed by 1255 MP/kg where there was intense fishing, boating and tourism activities in the vicinity of Bandar-e Anzali city. Fibers were the most common type of MPs (80% of the total MPs detected). The MPs polluting the wetland were predominantly white/transparent (42%), and about 40% of them were >1000 μm. Polypropylene (PP) and polyethylene (PE) prevailed in MPs found. MPs were characterized with polarized light microscopy, Raman spectroscopy, Scanning Electron Microscopy coupled with Energy-Dispersive X-ray spectroscopy. Microplastics levels were found to correlate significantly (p > 0.7) with electrical conductivity (EC) and sand-size fraction of the sediments. Coarse-grained sediments presented large capacity to lodge the MPs. This study can be used to establish protection policies in wetlands and newly highlights the opportunity of intercepting MPs in the Anzali Wetland, which are generally >250 μm, before they fragment further.

Pollen allergens, widely present in the atmosphere, are the main cause of seasonal respiratory diseases that affect millions of people worldwide. Although previous studies have reported that nitrogen dioxide (NO₂) and ozone (O₃) promote pollen allergy, the specific biological processes and underlying mechanisms remain less understood. In this study, Platanus pollen grains were exposed to gaseous pollutants (NO₂ and O₃). We employed environmental electron microscopy, flow cytometry, western blot assay, enzyme-linked immunoassay, ultraviolet absorption spectrometry, circular dichroism, and protein mass spectrometry to characterise the subpollen particles (SPPs) released from pollen grains. Furthermore, we determined the immunogenicity and pathogenicity induced by Platanus pollen allergen a 3 (Pla a 3). Our results demonstrated that NO₂ and O₃ could damage the pollen cell membranes in SPPs and increase the amount of Pla a 3 allergen released into the atmosphere. Additionally, NO₂ and O₃ altered the structure of Pla a3 protein through nitrification and oxidation, which not only enhanced the immunogenicity of allergens but also increased the stability of the protein. In vivo analysis using an animal model indicated that NO₂ and O₃ greatly aggravated pollen-induced pneumonia. Thus, our study provides guidance for the prevention of pollen allergic diseases.

A massive and dense textured layer (ca. 35–50 cm thick) of hardpan was uncovered at the top layer, which capped the unweathered sulfidic Cu-Pb-Zn tailings in depth and physically supported gravelly soil root zones sustaining native vegetation for more than a decade. For the purpose of understanding functional roles of the hardpan layer in the cover profile, the present study has characterized the microstructures of the hardpan profile at different depth compared with the tailings underneath the hardpans. A suit of microspectroscopic technologies was deployed to examine the hardpan samples, including field emission-scanning electron microscopy coupled with energy dispersive spectroscopy (FE-SEM-EDS), X-ray diffraction (XRD) and synchrotron-based X-ray absorption fine structure spectroscopy (XAFS). The XRD and Fe K-edge XAFS analysis revealed that pyrite in the tailings had been largely oxidised, while goethite and ferrihydrite had extensively accumulated in the hardpan. The percentage of Fe-phyllosilicates (e.g., biotite and illite) decreased within the hardpan profile compared to the unweathered tailings beneath the hardpan. The FE-SEM-EDS analysis showed that the fine-grained Ca-sulfate (possibly gypsum) evaporites appeared as platelet-shaped that deposited around pyrite, dolomite, and crystalline gypsum particles, while Fe-Si gels exhibited a needle-like texture that aggregated minerals together and produced contiguous coating on pyrite surfaces. These microstructural findings suggest that the weathering of pyrite and Fe-phyllosilicates coupled with dolomite dissolution may have contributed to the formation of Ca-sulfate/gypsum evaporites and Fe-Si gels. These findings have among the first to uncover the microstructure of hardpan formed at the top layer of sulfidic Cu-Pb-Zn tailings, which physically capped the unweathered tailings in depth and supported root zones and native vegetation under semi-arid climatic conditions.

Little is known about pollution in urban snow and how aerosol and gaseous air pollutants interact with the urban snowpack. Here we investigate interactions of exhaust pollution with snow at low ambient temperature using fresh snow in a temperature-controlled chamber. A gasoline-powered engine from a modern light duty vehicle generated the exhaust and was operated in homogeneous and stratified engine regimes. We determined that, within a timescale of 30 min, snow takes up from the exhaust a large mass of organic pollutants and aerosol particles, which were observed by electron microscopy, mass spectrometry and aerosol sizers. Specifically, the concentration of total organic carbon in the exposed snow increased from 0.948 ± 0.009 to 1.828 ± 0.001 mg/L (homogeneous engine regime) and from 0.275 ± 0.005 to 0.514 ± 0.008 mg/L (stratified engine regime). The concentrations of benzene, toluene and 13 out of 16 measured polycyclic aromatic hydrocarbons (PAHs), particularly naphthalene, benz[a]anthracene, chrysene and benzo[a]pyrene in snow increased upon exposure from near the detection limit to 0.529 ± 0.058, 1.840 ± 0.200, 0.176 ± 0.020, 0.020 ± 0.005, 0.025 ± 0.005 and 0.028 ± 0.005 ng/kg, respectively, for the homogeneous regime. After contact with snow, 50–400 nm particles were present with higher relative abundance compared to the smaller nanoparticles (<50 nm), for the homogeneous regime. The lowering of temperature from 25 ± 1 °C to (−8) – (−10) ± 1 °C decreased the median mode diameter of the exhaust aerosol particles from 69 nm to 57 nm (p < 0.1) and addition of snow to 51 nm (p < 0.1) for the stratified regime, but increased it from 20 nm to 27 nm (p < 0.1) for the homogeneous regime. Future studies should focus on cycling of exhaust-derived pollutants between the atmosphere and cryosphere. The role of the effects we discovered should be evaluated as part of assessment of pollutant loads and exposures in regions with a defined winter season.

The aim of our study was to investigate how exposure to heavy metal-rich waters from gypsum mining affects the morphology and levels of primary DNA damage in Gammarus balcanicus. Chemical analysis revealed increased concentrations of metals in water and sediment collected at a site impacted by gypsum mine wastewaters. The specimens also showed elevated total tissue metal levels when compared with the organisms collected at the reference site. The most prominent increase was observed for strontium, followed by iron, nickel, vanadium, aluminium, and manganese. The major pathway of entry for these toxic substances was through the degraded exoskeleton as a consequence of excessive strontium input (unbalanced calcium/strontium ratio) and altered permeability. Disturbed exoskeleton integrity was observed only in individuals collected downstream of the gypsum mine, which was confirmed by electron microscopy. Levels of primary DNA damage were evaluated using the alkaline comet assay in the haemolymph of the specimens.

Total suspended particulate (TSP) and PM₁₀ filters collected from two ambient air monitoring stations in Port Pirie were analysed to determine the impact of a lead (Pb) smelter redevelopment on air quality parameters including total elemental concentration, Pb isotopic ratio, Pb bioaccessibility and Pb speciation. Filters from 2009 to 2020 were analysed with a focus on samples from 2017 (immediately prior to smelter redevelopment) and 2020 (post-smelter redevelopment). Lead concentration in 2009–2020 TSP was variable ranging up to 6.94 μg m⁻³ (mean = 0.57 μg m⁻³), however, no significant decrease in Pb concentration was observed at either Port Pirie West (p = 0.56, n = 34) or Oliver Street (p = 0.32, n = 28) monitoring stations when 2017 and 2020 TSP values were compared. Similarly, no significant difference (p = 0.42) in PM₁₀ Pb concentration was observed in 2017 (mean = 0.80 μg m⁻³) and 2020 (0.60 μg m⁻³) Oliver Street filters. Although no change in percentage Pb bioaccessibility was observed when 2017 and 2020 Port Pirie West TSP samples were compared (mean of 88.7% versus 88.0%), Pb bioaccessibility was lower (p < 0.005) in both 2020 TSP (mean of 83.9% versus 62.9%) and PM₁₀ (mean of 70.8% versus 58.3%) Oliver Street filters compared to 2017. While scanning electron microscopy, energy dispersive x-ray spectroscopy identified a number of Pb phases within filters (galena, anglesite, cerussite, conglomerates), differences in Pb speciation between 2017 and 2020 filters could not be identified although it was presumed that this influenced Pb bioaccessibility outcomes at Oliver Street. Data from this study suggests that recent smelter redevelopments have not significantly decreased the concentrations of airborne Pb in Port Pirie although re-entrainment of soil-Pb from historical impact may also be a contributing Pb source.

As a result of the efforts to introduce the principle of the 3Rs (replacement, reduction, and refinement) into animal testing, alternative in vitro skin corrosion test methods have been developed and standardized globally. However, alternative in vitro skin corrosion test methods have some limitations in terms of the use of humanely killed rats or commercial models and kits. The present study focused on the applicability of invertebrates as alternative in vivo skin models. Even though earthworm skin comprises the same biomolecules as human skin, the possibility of using earthworm skin as an alternative for skin testing remains unexplored. In this study, we developed a half-pipe tool for earthworm skin corrosion testing and optimized the test protocol. Subsequently, the applicability of the earthworm half-pipe assay for corrosion testing with six chemicals, including inorganic acids, organic acids, and alkalis, was investigated using stereomicroscopy and electron microscopy. It was observed that the specific concentrations for earthworm skin corrosion were lower than those for animal or in vitro tests. Therefore, the sensitivity of the earthworm half-pipe assay indicates that it could be useful as a screening tool before conducting in vivo animal tests or in vitro skin tests. This new method can contribute to research on alternative skin corrosion tests by reducing ethical issues, time, and cost while achieving effective results.

Arsenic (As) is among the most dangerous metalloids and is harmful to human wellbeing. In this laboratory study, Al(III)-modified kapok fibres (Al-Kapok) were used to remove As(V) from water. The sorbent was characterised using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDX). Batch experiments were performed to observe the performance of Al-Kapok in the removal of As(V) and to examine the effects of pH, temperature, adsorbent dose, and coexisting ions on the adsorption process. The surface of the sorbent changed after aluminium modification, and the results of the batch experiments showed that the adsorption of As(V) occurred mainly via endothermic-spontaneous chemisorption at the solution and solid interface of Al-Kapok. The As(V) removal efficiency was approximately 76%–84%, and it was slightly affected at pH levels below 8.0. Further study showed that the maximum adsorption capacity of Al-Kapok for As(V) was 118 μg/g at 30 °C and pH 6, and notable adverse effects were caused by the presence of SO42−and PO43−. It was also found that the boundary layer and film diffusion contributed more to As(V) adsorption. After five adsorption/desorption cycles, regeneration recovered approximately 92% of the adsorption capacity of Al-Kapok used. Overall, Al-Kapok appears to be a suitable adsorbent material for the purification of As-contaminated water.

To evaluate the influence of surface coatings on nano-fertilizers uptake and their phytotoxicity to crops and its health risk to Chinese adults, trisodium citrate (TC) and polyethylene glycol (PEG) coatings were prepared on the surface of copper oxide nanoparticles (CuO NPs), respectively, with 100 and 500 mg/L of bare CuO NPs, TC-CuO NPs, and PEG-CuO NPs were exposed to soil-grown Ipomoea aquatica Forssk. Combined bio-transmission electron microscopy and micro-CT observed cellular migration of coated CuO NPs in symplastic and apoplastic pathways, as well as nanoparticles transported through vascular tissues to the above-ground parts. Since TC-CuO NPs had less inhibition on vascular phylogeny of I. aquatica roots which was determined by RT-qPCR, their migration in plants was more efficient, thus exhibiting greater phytotoxicity to shoots. Meanwhile, coatings significantly reduced the phytotoxicity of CuO NPs by stimulating plant antioxidant defense. The risk of CuO nano-fertilizers on human dietary safety was evaluated, the HQ > 1 in the 500 mg/L CuO NPs treatment indicated a potential health risk to Chinese adults, which was reduced by the coatings. This work explored for the first time the mechanism of coating effects on nanoparticles migration efficiency and phytotoxicity at the molecular level and demonstrated that the migration of nanoparticles between tissues could have an impact on phytotoxicity. It implied that coating can be tailored to target nanoparticles to specific regions of the plant. In addition, this study highlights the potential health risks associated with the consumption of I. aquatica fertilized with CuO NPs and provides valuable insights into the environmental applications of nano-fertilizers.