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.

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.

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.

Ultrafine (<100 nm) particles related to traffic are of high environmental and human health concern, as they are supposed to be more toxic than larger particles. In the present study transmission electron microscopy (TEM) is applied to obtain a concrete picture on the nature, morphology and chemical composition of non-volatile ultrafine particles in the exhaust of state-of-the-art, Euro 6b, Gasoline and Diesel vehicles. The particles were collected directly on TEM grids, at the tailpipe, downstream of the after-treatment system, during the entire duration of typical driving cycles on the chassis dynamometer. Based on TEM imaging coupled with Energy Dispersive X-ray (EDX) analysis, numerous ultrafine particles could be identified, imaged and analyzed chemically. Particles <10 nm were rarely detected. The ultrafine particles can be distinguished into the following types: soot, ash-bearing soot and ash. Ash consists of Ca, P, Mg, Zn, Fe, S, and minor Sn compounds. Most elements originate from lubricating oil additives; Sn and at least part of Fe are products of engine wear; minor W ± Si-bearing nearly spherical particles in Diesel exhaust derive from catalytic coating material. Ultrafine ash particles predominate over ultrafine soot or are nearly equal in amount, in contrast to emissions of larger sizes where soot is by far the prevalent particle type. This is probably due to the low ash amount per volume fraction in the total emissions, which does not favor formation of large ash agglomerates, opposite to soot, which is abundant and thus easily forms agglomerates of sizes larger than those of the ultrafine range. No significant differences of ultrafine particle characteristics were identified among the tested Gasoline and Diesel vehicles and driving cycles. The present TEM study gives information also on the imaging and chemical composition of the solid fraction of the unregulated sub-23 nm size category particles.

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.

Perfluorooctanesulphonic acid (PFOS) is a ubiquitous contaminant in the aquatic environment and our earlier studies demonstrated that chronic PFOS exposures lead to a female-biased sex ratio and decreased sperm quality in male zebrafish. The underlying mechanism for these reproductive effects is unknown. In the present study, 8 h post-fertilization (hpf) zebrafish were exposed to PFOS at 250 μg/L for 5 months, and the levels of sex hormones, expression of sex determination related genes, and histological and ultrastructural changes of gonads were fully characterized. During the sex differentiation period, we observed elevated estradiol (E2) and decreased testosterone (T) levels in whole tissue homogenates from PFOS exposed juveniles. In fully mature adult male fish, serum E2 levels were slightly increased, however, the estrogen receptor alpha (esr1) was significantly elevated in PFOS treated male gonads. Histological and electron microscopic examinations revealed structural changes in the gonads of PFOS exposed male and female adult zebrafish. In summary, chronic PFOS exposure disrupts sex hormone level and related gene expression and impairs gonadal development, which may contribute to the previously reported PFOS reproductive toxicity.

In the present study, endpoints including in vitro pollen performance (i.e., germination and tube growth) and lethality were used as assessments of nanotoxicity. Pollen was treated with 5–10 nm-sized Pd particles, similar to those released into the environment by catalytic car exhaust converters. Results showed Pd-nanoparticles altered kiwifruit pollen morphology and entered the grains more rapidly and to a greater extent than soluble Pd(II). At particulate Pd concentrations well below those of soluble Pd(II), pollen grains experienced rapid losses in endogenous calcium and pollen plasma membrane damage was induced. This resulted in severe inhibition and subsequent cessation of pollen tube emergence and elongation at particulate Pd concentrations as low as 0.4 mg L−1. Particulate Pd emissions related to automobile traffic have been increasing and are accumulating in the environment. This could seriously jeopardize in vivo pollen function, with impacts at an ecosystem level. Nanoparticulate Pd – which resembles emissions from automobile catalysts – affects pollen to a higher extent than soluble Pd.

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.

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.