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.

Understanding how engineered nanoparticles (ENPs) interact with natural organic acids is important to ecological risk assessment of ENPs, but this interaction remains poorly studied. Here, we investigate the dispersion stability, ion release, and toxicity of yttrium oxide nanoparticles (nY2O3) suspensions after exposure to two low molecular weight natural organic acids (LOAs), namely benzoic acid and gallic acid. We find that in the presence of LOAs the nY2O3 suspensions become more stable with surface zeta potential more positive or negative, accompanied by small agglomerated size. LOA interaction with nY2O3 is shown to promote the release of dissolved yttrium from the nanoparticles, depending on the concentrations of LOAs. Toxic effects of the nY2O3 suspensions incubated with LOAs on Scenedesmus obliquus as a function of their mixture levels show three types of signs: stimulation, inhibition, and alleviation. The mechanism of the effects of LOAs on the nY2O3 toxicity may be mainly associated with the degree of agglomeration, particle-induced oxidative stress, and dissolved yttrium. Our results stressed the importance of LOA impacts on the fate and toxicity of ENPs in the aquatic environment.

The Three Gorges Reservoir (TGR) is one of the world's largest man-made hydropower projects, which has posed great challenges to the aquatic environment of the Yangtze River since the impoundment of water. As a non-essential toxic metalloid, information on the bioavailability of Antimony (Sb) in TGR sediments is lacking. Four sediment cores were collected from a tributary and the mainstream in the TGR to investigate the distribution and remobilization of Sb using the diffusive gradients in thin films (DGT) technique. The results showed that the concentrations of Sb obtained by DGT (CDGT-Sb) at all of the sampling stations were low (below 0.30 μg/L), compared to the relatively high Sb concentrations in the sediments. The lateral and vertical distributions of CDGT-Sb revealed different tendencies in overlying water and sediments at all of the sampling sites in the TGR, which may be attributed to anthropogenic impacts, the heterogeneity of sediments and the unevenness of the sediment-water interface (SWI) during the deployment of DGT probes. In addition, CDGT-Sb in the surface sediments were lower than those in the overlying water, and concentration gradients were found near the SWI, demonstrating that Sb has the potential to diffuse from the overlying water into the sediment. In the sediment cores, different peaks were discovered in the DGT probes and the remobilization of Sb simultaneously appeared in the vicinity of −10 cm. Correlation analysis showed that CDGT-Sb had no or negative correlation with CDGT-Fe and CDGT-Mn in all of the DGT probes, suggesting that the release of Sb was unassociated with Fe and Mn in the sediments in the study area.

Graphene oxide (GO) and reduced graphene oxide (RGO) materials contain a variety of surface O-functional groups that are chemically reactive. When released into the environment these materials may significantly affect the abiotic transformation of organic contaminants, and therefore, may alter their fate and risks. We found that two GO and five RGO materials that varied in C/O ratio, hydrophobicity, and type/distribution of surface O-functionality all had catalytic effects on the dehydrochlorination of 1,1,2,2-tetrachloroethane (TeCA). Even though the catalytic effects of the materials originated from their deprotonated surface O-functional groups, which served as conjugated bases to catalyze the reaction, the catalytic efficiencies of the materials did not correlate strongly with their surface O contents. The spectroscopic evidence (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy), surface charge data, and adsorption experiments demonstrated that the catalytic efficiencies of the GO/RGO materials were controlled by a complex interplay of the type and distribution of surface O-functionality, as well as adsorption affinity of the materials. Both Ca2+ and Mg2+ inhibited the catalytic efficiency of the materials by binding to the surface O-functional groups, and consequently, decreasing the basicity of the functional groups. At an environmentally relevant concentration of 10 mg/L, Suwannee River humic acid (used as a model dissolved organic matter) alone had little effect on the dehydrochlorination of TeCA. However, it could inhibit the catalytic efficiency of the GO/RGO materials by coating on their surface and thus, decreasing the adsorption affinity of these materials for TeCA. The findings further underline the potentially important impacts of nanomaterials on contaminant fate and effects in the environment.