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.

Biofilm-mediated bioremediation of xenobiotic pollutants is an environmental friendly biological technique. In this study, 36 out of 55 bacterial isolates developed biofilms in glass test tubes containing salt-optimized broth plus 2% glycerol (SOBG). Scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, and Congo red- and Calcofluor binding results showed biofilm matrices contain proteins, curli, nanocellulose-rich polysaccharides, nucleic acids, lipids, and peptidoglycans. Several functional groups including –OH, N–H, C–H, CO, COO⁻, –NH₂, PO, C–O, and C–C were also predicted. By sequencing, ten novel biofilm-producing bacteria (BPB) were identified, including Exiguobacterium indicum ES31G, Kurthia gibsonii ES43G, Kluyvera cryocrescens ES45G, Cedecea lapagei ES48G, Enterobacter wuhouensis ES49G, Aeromonas caviae ES50G, Lysinibacillus sphaericus ES51G, Acinetobacter haemolyticus ES52G, Enterobacter soli ES53G, and Comamonas aquatica ES54G. The Direct Red (DR) 28 (a carcinogenic and mutagenic dye used in dyeing and biomedical processes) decolorization process was optimized in selected bacterial isolates. Under optimum conditions (SOBG medium, 75 mg L⁻¹ dye, pH 7, 28 °C, microaerophilic condition and within 72 h of incubation), five of the bacteria tested could decolorize 97.8% ± 0.56–99.7% ± 0.45 of DR 28 dye. Azoreductase and laccase enzymes responsible for biodegradation were produced under the optimum condition. UV–Vis spectral analysis revealed that the azo (−NN−) bond peak at 476 nm had almost disappeared in all of the decolorized samples. FTIR data revealed that the foremost characteristic peaks had either partly or entirely vanished or were malformed or stretched. The chemical oxygen demand decreased by 83.3–91.3% in the decolorized samples, while plant probiotic bacterial growth was indistinguishable in the biodegraded metabolites and the original dye. Furthermore, seed germination (%) was higher in the biodegraded metabolites than the parent dye. Thus, examined BPB could provide potential solutions for the bioremediation of industrial dyes in wastewater.

Spirotetramat, a member of tetronic and tetramic acid derivatives, is a unique insecticide and acaricide. Although the effect on zebrafish embryos lipid biosynthesis of spirotetramat has been characterized, the energy metabolism and toxic effect mechanism warrant further investigation. To investigate the toxic mechanism of spirotetramat on energy metabolism, zebrafish embryos were exposed to 100, 500 and 1000 µg/L of spirotetramat for 4 days. Untargeted metabolomics showed the synthesis and degradation of ketone pathway metabolites (R)-3-Hydroxybutyric acid and Acetoacetate significantly decreased, as well as increasing the abundance of Anti-Acetyl Coenzyme A Carboxylase protein (ACC1). Down-regulation of the genes related to ß-oxidation and the tricarboxylic acid cycle in the embryos show decreased energy metabolism. Carnitine palmitoyltransferase 1 (CPT- I) significantly decreased while citrate synthase (CS) significantly increased. Additionally, mitochondrial lesions in embryos were found using electron microscopy. Our study provides novel and robust perspectives, which show that spirotetramat treatment in embryos leads to metabolic disturbances that adversely affect cellular energy homeostasis.

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.

Large amounts of aluminum (Al) are found in wastewater from industrial bauxite mining, which is often responsible for the contamination of drinking water sources in urban and rural communities. Although this metal exhibits broad environmental distribution, its cardiac repercussions are poorly understood, making it difficult to establish diagnostic criteria in cases of Al intoxication. In the absence of clinical data, we used a preclinical model to investigate the impact of Al exposure on heart bioaccumulation, molecular oxidation, micromineral distribution, structural and ultrastructural remodeling of the cardiac tissue. Male Wistar rats were equally randomized into five groups: G1 = distilled water; and G2 to G5 = 0.02, 0.1, 50, and 200 mg/kg aluminum solution, respectively. After 120 days, the hearts were collected and subjected to mineral microanalysis, immunoenzymatic detection of 8-OHdG, as well as bright field, polarizing, scanning and transmission electron microscopy to estimate the extent of the cardiac remodeling and cardiomyocytes ultrastructure. Long-term Al exposure induced dose-dependent bioaccumulation, micromineral imbalance, genomic DNA oxidation, structural and ultrastructural abnormalities of the cardiac tissue, resulting in extensive parenchymal loss, stromal expansion, diffuse inflammatory infiltrate, increased glycoconjugate and collagen deposition, subversion and collapse of the collagen network, reduced myocardial vascularization index, mitochondrial swelling, sarcomere disorganization, myofilament dissociation, and fragmentation in cardiomyocytes. Our findings indicated that the heart was sensitive to Al-mediated toxicity, especially in animals treated with the three highest doses of Al. In response to Al-induced loss of the parenchyma, heart stroma exhibited a reactive and compensatory expansion, which, in combination with the increased distribution of thick myofibrils and degenerated mitochondria in cardiomyocytes, provides morphological evidence that cardiac tissue adaptations are not enough to adjust the relationships between the parenchyma and stroma until a steady state is reached, resulting in continuous pathological remodeling potentially associated with Al-induced proinflammatory and pro-oxidant events.