Proteomics technology is an attractive biomarker candidate discovery tool that can be applied to study large sets of biological molecules. To identify novel biomarkers and molecular targets in arsenic-induced skin lesions, we have determined the protein profile of arsenic-affected human epidermal stratum corneum by shotgun proteomics. Samples of palm and foot sole from healthy subjects were analyzed, demonstrating similar protein patterns in palm and sole. Samples were collected from the palms of subjects with arsenic keratosis (lesional and adjacent non-lesional samples) and arsenic-exposed subjects without lesions (normal). Samples from non-exposed healthy individuals served as controls. We found that three proteins in arsenic-exposed lesional epidermis were consistently distinguishably expressed from the unaffected epidermis. One of these proteins, the cadherin-like transmembrane glycoprotein, desmoglein 1 (DSG1) was suppressed. Down-regulation of DSG1 may lead to reduced cell-cell adhesion, resulting in abnormal epidermal differentiation. The expression of keratin 6c (KRT6C) and fatty acid binding protein 5 (FABP5) were significantly increased. FABP5 is an intracellular lipid chaperone that plays an essential role in fatty acid metabolism in human skin. This raises a possibility that overexpression of FABP5 may affect the proliferation or differentiation of keratinocytes by altering lipid metabolism. KRT6C is a constituent of the cytoskeleton that maintains epidermal integrity and cohesion. Abnormal expression of KRT6C may affect its structural role in the epidermis. Our findings suggest an important approach for future studies of arsenic-mediated toxicity and skin cancer, where certain proteins may represent useful biomarkers of early diagnoses in high-risk populations and hopefully new treatment targets. Further studies are required to understand the biological role of these markers in skin pathogenesis from arsenic exposure.

Fullerenes are carbon based nanoparticles that may enter the environment as a consequence of both natural processes and human activities. Although little is known about the presence of these chemicals in the environment, recent studies suggested that soil may act as a sink. The aim of the present work was to investigate the presence of fullerenes in soils collected in The Netherlands. Samples (n = 91) were taken from 6 locations and analyzed using a new developed LC-QTOF-MS method. The locations included highly trafficked and industrialized as well as urban and natural areas. In general, C60 was the most abundant fullerene found in the environment, detected in almost a half of the samples and at concentrations in the range of ng/kg. Other fullerenes such as C70 and an unknown structure containing a C60 cage were detected to a lower extent. The highest concentrations were found in the proximity of combustion sites such as a coal power plant and an incinerator, suggesting that the nanoparticles were unintentionally produced during combustions processes and reached the soil through atmospheric deposition. Consistent with other recent studies, these results show that fullerenes are widely present in the environment and that the main route for their entrance may be due to human activities. These data will be helpful in the understanding of the distribution of fullerenes in the environment and for the study of their behavior and fate in soil.

Vertical profiles of O3 and SO2 concentrations were monitored at the Borden Forest site in southern Ontario, Canada from May 2008 to April 2013. A modified gradient method (MGM) was applied to estimate O3 and SO2 dry deposition fluxes using concentration gradients between a level above and a level below the canopy top. The calculated five-year mean (median) dry deposition velocity (Vd) were 0.35 (0.27) and 0.59 (0.54) cm s−1, respectively, for O3 and SO2. Vd(O3) exhibited large seasonal variations with the highest monthly mean of 0.68 cm s−1 in August and the lowest of 0.09 cm s−1 in February. In contrast, seasonal variations of Vd(SO2) were smaller with monthly means ranging from 0.48 (May) to 0.81 cm s−1 (December). The different seasonal variations between O3 and SO2 were caused by the enhanced SO2 uptake by snow surfaces in winter. Diurnal variations showed a peak value of Vd in early morning in summer months for both O3 and SO2. Canopy wetness increased the non-stomatal uptake of O3 while decreasing the stomatal uptake. This also applied to SO2, but additional factors such as surface acidity also played an important role on the overall uptake.

Concentrations of persistent organic pollutants (POPs) were measured for an entire year in the region of Tuscany, Italy. Passive air samplers consisting of polyurethane foam (PUF) disks were deployed over four sampling periods of 3–5 months from April 2008 to July 2009 in urban (n = 6) and rural (n = 4) sites. The aim of the study was to characterize the spatial and seasonal variations in selected POPs. The POP concentrations (pg m−3) in the air were dominated by dichlorodiphenyltrichloroethane and metabolites (DDTs) and polychlorinated biphenyls (∑7PCBs). DDTs, and ∑7PCBs showed a clear decreasing urban > rural gradient. The concentrations of DDTs and PCBs were up to 10 and 6 times higher, respectively, in urban sites than in rural sites. ∑7PCBs showed a significant correlation with the urbanized areas located <5 km around the sampling sites. For hexachlorocyclohexanes (HCHs), α-HCH concentrations were similar at both sampling sites and were found to be quite uniform during the four sampling periods. Seasonal fluctuations were observed for DDTs, and ∑7PCBs, with the highest concentrations observed during period 4 (summer–spring); this is most likely due to a temperature-driven re-emission from local sources. These findings were also supported by an air back trajectory analysis in the study area. This study contributes new information about POP levels in the Italian atmosphere and demonstrates the feasibility of using PUF disks to simultaneously assess seasonal concentrations at different sampling sites.

Toxic metalloids including arsenic (As) can neither be eliminated nor destroyed from environment; however, they can be converted from toxic to less/non-toxic forms. The form of As species and their concentration determines its toxicity in plants. Therefore, the microbe mediated biotransformation of As is crucial for its plant uptake and toxicity. In the present study the role of As tolerant Trichoderma in modulating As toxicity in chickpea plants was explored. Chickpea plants grown in arsenate spiked soil under green house conditions were inoculated with two plant growth promoting Trichoderma strains, M-35 (As tolerant) and PPLF-28 (As sensitive). Total As concentration in chickpea tissue was comparable in both the Trichoderma treatments, however, differences in levels of organic and inorganic As (iAs) species were observed. The shift in iAs to organic As species ratio in tolerant Trichoderma treatment correlated with enhanced plant growth and nutrient content. Arsenic stress amelioration in tolerant Trichoderma treatment was also evident through rhizospheric microbial community and anatomical studies of the stem morphology. Down regulation of abiotic stress responsive genes (MIPS, PGIP, CGG) in tolerant Trichoderma + As treatment as compared to As alone and sensitive Trichoderma + As treatment also revealed that tolerant strain enhanced the plant's potential to cope with As stress as compared to sensitive one. Considering the bioremediation and plant growth promotion potential, the tolerant Trichoderma may appear promising for its utilization in As affected fields for enhancing agricultural productivity.

Nanoparticulate mackinawite (FeS) can be an important host-phase for arsenic (As) in sulfidic, subsurface environments. Although not previously investigated, phosphate (PO43−) may compete with As for available sorption sites on FeS, thereby enhancing As mobility in FeS-bearing soils, sediments and groundwater systems. In this study, we examine the effect of PO43− on sorption of arsenate (As(V)) and arsenite (As(III)) to nanoparticulate FeS at pH 6, 7 and 9. Results show that PO43− (at 0.01–1.0 mM P) did not significantly affect sorption of either As(V) or As(III) to nanoparticulate FeS at initial aqueous As concentrations ranging from 0.01 to 1.0 mM. At pH 9 and 7, sorption of both As(III) and As(V) to nanoparticulate FeS was similar, with distribution coefficient (Kd) values spanning 0.76–15 L g−1 (which corresponds to removal of 87–98% of initial aqueous As(III) and As(V) concentrations). Conversely, at pH 6, the sorption of As(III) was characterized by substantially higher Kd values (6.3–93.4 L g−1) than those for As(V) (Kd = 0.21–0.96 L g−1). Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy indicated that up to 52% of the added As(V) was reduced to As(III) in As(V) sorption experiments, as well as the formation of minor amounts of an As2S3-like species. In As(III) sorption experiments, XANES spectroscopy also demonstrated the formation of an As2S3-like species and the partial oxidation of As(III) to As(V) (despite the strictly O2-free experimental conditions). Overall, the XANES data indicate that As sorption to nanoparticulate FeS involves several redox transformations and various sorbed species, which display a complex dependency on pH and As loading but that are not influenced by the co-occurrence of PO43−. This study shows that nanoparticulate FeS can help to immobilize As(III) and As(V) in sulfidic subsurface environments where As co-exists with PO43−.

To explore the mechanisms and influence factors on the production of 2,4,6-trichloroanisole (2,4,6-TCA) in surface waters, the 2,4,6-TCA formation potential (FP) test was conducted by incubating the real lake water with the addition of 2,4,6-trichlorophenol (2,4,6-TCP) precursor. Besides bacteria and fungi, two common cyanobacteria and algae species, i.e., Chlorella vulgaris and Anabaena flos-aquae, have been proved to have strong capabilities to produce 2,4,6-TCA, which may contribute the high 2,4,6-TCA FP (152.2 ng/L) of lake water. The microbial O-methylation of 2,4,6-TCP precursor is catalyzed by chlorophenol O-methyltransferases (CPOMTs), and their characteristics were identified by adding inductive methyl donors or excluding microorganisms via ultrafiltration. The results indicated both S-adenosyl methionine (SAM) dependent and non-SAM dependent CPOMTs played important roles; extracellular CPOMTs also participated in the biosynthesis of 2,4,6-TCA. Moreover, investigating the effects of various environmental factors revealed initial 2,4,6-TCP processor concentration, temperature, pH and some divalent metal cations (i.e., Mn2+, Mg2+ and Zn2+) had obvious effects on the production of 2,4,6-TCA.

The focus of the present study was to find the relationship between concentrations of bisphenol A (BPA), 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in zooplankton and seasonal changes in the composition and biomass of particular zooplankton taxa in the Gulf of Gdansk (Southern Baltic) in the years 2011–2012. Assays of BPA, OP and NP in water and zooplankton samples were performed using the HPLC/FL system. High mean concentrations of the studied compounds, determined in spring (405.9 (BPA); 25.7 (OP); 111.2 (NP) ng g−1 dw), can be linked to the high proportion of meroplankton in that season. Rotifera also had an influence on the rise in concentrations of the studied compounds but to a lesser degree, while the lowest concentrations (determined in summer) can be associated with the high participation of Copepoda and Cladocera in zooplankton biomass. It was also observed that juvenile forms can be more susceptible to accumulating endocrine disrupting compounds (EDCs). This is indicated by the positive correlation between BPA concentration in zooplankton and the proportion of Copepoda nauplii biomass in spring (r = 0.90; p < 0.05). In most cases, greater zooplankton biomass accumulated higher concentrations and loads of the studied compounds. With biomass growth (to 123.32 μg m−3), the bioconcentration factor also rose (to max 46.1·103), demonstrating that unlike typical hydrophobic compounds the studied EDCs do not become “diluted” in zooplankton biomass. The highest BPA concentrations from all compounds may be connected with anthropogenic sources located in the coastal zone.

Addressing the challenge that phosphorus is the key factor and cause for eutrophication, we evaluated the phosphorus release control performance of a new phosphorus inactive clay (PIC) and compared with Phoslock®. Meanwhile, the impacts of PIC and Phoslock® on phytoplankton abundance and community structure in eutrophic water were also discussed. With the dosage of 40 mg/L, PIC effectively removed 97.7% of total phosphorus (TP) and 98.3% of soluble reactive phosphorus (SRP) in eutrophic waters. In sediments, Fe/Al-phosphorus and organic phosphorus remained stable whereas Ca-phosphorus had a significant increase of 13.1%. The results indicated that PIC may form the active overlay at water-sediment interface and decrease the bioavailability of phosphorus. The phytoplankton abundance was significantly reduced by PIC and decreased from (1.0–2.4) × 107 cells/L to (1.3–4.3) × 106 cells/L after 15 d simultaneous experiment. The phytoplankton community structure was also altered, where Cyanobacteria and Bacillariophyceae were the most inhibited and less dominant due to their sensitivity to phosphorus. After PIC treatment, the residual lanthanum concentration in water was 1.44–3.79 μg/L, and the residual aluminium concentration was low as 101.26–103.72 μg/L, which was much less than the recommended concentration of 200 μg/L. This study suggests that PIC is an appropriate material for phosphorus inactivation and algal bloom control, meaning its huge potential application in eutrophication restoration and management.

Concentrations of vehicular emitted heavy metals in roadside soils result in long term environmental damage. This study assessed the relationships between traffic characteristics (traffic density, road age and vehicular speed) and roadside soil heavy metals. Significant levels were recorded for Cd (0.06–0.59 mg/kg), Cr (18–29 mg/kg), Cu (4–12 mg/kg), Ni (7–20 mg/kg), Mn (92–599 mg/kg), Pb (16–144 mg/kg) and Zn (10.36–88.75 mg/kg), with Mn concentrations exceeding the Ecological Investigation Level. Significant correlations were found between roadside soil metal concentration and vehicular speed (R = 0.90), road age (R = 0.82) and traffic density (R = 0.68). Recently introduced metals in automotive technology (e.g. Mn and Sb) were higher in younger roads, while the metals present for many years (e.g. Cd, Cu, Pb, Zn) were higher in medium and old age roads confirming the risk of significant metal deposition and soil metal retention in roadside soils.