Two microcosm types -sediment-biota and biota-biota- were constructed to simulate different pathways of BDE-47 uptake, metabolism and oxidative stress effects in two key estuarine invertebrates (polychaete Laeonereis acuta and crab Cyrtograpsus angulatus). In the sediment-biota experiment, both species were exposed to spiked sediments; an environmentally reported and a high concentration of BDE-47 for 2 weeks. In the biota-biota experiment, crabs were fed with polychaetes pre-exposed to BDE-47 in the sediment-biota experiment. The sediment-biota experiment first revealed that polychaetes significantly accumulated BDE-47 (biota-sediment accumulation factor >2; p < 0.05) to a much greater extent than the crab organs (muscle, hepatopancreas, gills) at both sediment concentrations. For oxidative stress responses, polychaete and crab tissues exposed to spiked sediment showed a significant increase (p < 0.05) of only glutathione S-transferase (GST) activity with respect to controls in both BDE-47 concentrations. No lipid peroxidation (TBARS) or total antioxidant capacity (ACAP) changes were evident in the species or organs exposed to either BDE-47 sediment concentration. The biota-biota experiment showed that feeding crabs with pre-exposed polychaetes caused BDE-47 accumulation in organs as well as significant amounts of BDE-47 eliminated through feces (p < 0.05). Unlike the sediment-biota exposure, crabs fed with pre-exposed BDE-47 polychaetes showed the most conspicuous oxidative stress responses. Significant changes in GST and ACAP in both hepatopancreas and gills, in addition to enhanced TBARS levels in the hepatopancreas with respect to controls (p < 0.05), revealed that BDE-47 assimilated by invertebrates represents a potential source of toxicity to their predators. No methoxylated metabolites (MeO-PBDEs) were detected during BDE-47 metabolism in the invertebrates in either of the two different exposure types. In contrast, hydroxylated metabolites (OH-PBDEs) were detected in polychaetes and crab organs/feces in both experiments. Our results demonstrate that PBDE hydroxylation is one of the main biotransformation routes of BDE-47 in estuarine animals, which could be associated with the oxidative stress responses found.

Rivers and effluents have been identified as major pathways for microplastics of terrestrial sources. Moreover, lakes of different dimensions and even in remote locations contain microplastics in striking abundances. This study investigates concentrations of microplastic particles at two lakes in central Italy (Lake Bolsena, Lake Chiusi). A total number of six Manta Trawls have been carried out, two of them one day after heavy winds occurred on Lake Bolsena showing effects on particle distribution of fragments and fibers of varying size categories. Additionally, 36 sediment samples from lakeshores were analyzed for microplastic content. In the surface waters 2.68 to 3.36 particles/m3 (Lake Chiusi) and 0.82 to 4.42 particles/m3 (Lake Bolsena) were detected, respectively. Main differences between the lakes are attributed to lake characteristics such as surface and catchment area, depth and the presence of local wind patterns and tide range at Lake Bolsena. An event of heavy winds and moderate rainfall prior to one sampling led to an increase of concentrations at Lake Bolsena which is most probable related to lateral land-based and sewage effluent inputs. The abundances of microplastic particles in sediments vary from mean values of 112 (Lake Bolsena) to 234 particles/kg dry weight (Lake Chiusi). Lake Chiusi results reveal elevated fiber concentrations compared to those of Lake Bolsena what might be a result of higher organic content and a shift in grain size distribution towards the silt and clay fraction at the shallow and highly eutrophic Lake Chiusi. The distribution of particles along different beach levels revealed no significant differences.

It has been known that substitution is not a suitable method to address non-detect (ND) data and can result in significant errors. However, reports of reliable statistical methods for handling ND data of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in fish are rare. This work examines US-EPA's recommended statistical methods and traditional substitution-based methods for handling ND data in PCDD/F and DL-PCB datasets obtained from 240 fish samples. The Kaplan-Meier (KM) method was confirmed as a suitable statistical approach for dealing with our fish datasets. The results of the KM and substitution methods were compared; a significant difference was found in TEQs derived from KM and substitution for PCDD/Fs, suggesting that the handling of ND data is a critical issue for PCDD/Fs. For example, the substitution by ½LOD resulted in 20–25% overestimation of PCDD/F TEQs for fish samples with ND data (60–70%). In conclusion, the use of KM method is preferable for average TEQs, and if the use of KM is not applicable, substitution by zero is preferred. Based on this conclusion, the characteristics of fish contamination by PCDD/Fs and DL-PCBs in Korea were investigated.

In recent years, a trend toward a declining proportion of male births has been noted in several, but not all, industrialized countries. The underlying reason for the drop in the sex ratio is unclear, but one theory states that widespread environmental endocrine disrupting chemicals affecting the male reproductive system in a negative manner could be part of the explanation. The present study was designed to investigate whether the urinary phthalate, pyrethroids and polycyclic aromatic hydrocarbons metabolites concentrations were associated with sperm Y:X ratio.The study population consisted of 194 men aged under 45 years of age who attended infertility clinic in Lodz, Poland for diagnostic purposes with normal semen concentration of 20–300 mln/ml or with slight oligozoospermia (semen concentration of 15–20 mln/ml) (WHO, 1999). The Y:X ratio was assessed by fluorescent in situ hybridization. Urinary concentrations of 1-hydroxypyrene were measured by high performance liquid chromatography, phthalate metabolites were analyzed using a procedure based on the LC-MS/MS methods and metabolites of synthetic pyrethroids were assessed by gas chromatography ion-tap mass spectrometry method.After adjustment for potential confounders (past diseases, age, abstinence, smoking, alcohol consumption, sperm concentration, motility, morphology) 5OH MEHP, CDCCA to TDCCA and 1-OHP was negatively related to Y:X sperm chromosome ratio (p = 0.033, p < 0.001, p = 0.047 respectively).As this is the first study to elucidate the association between the level of metabolites of widespread environmental endocrine disrupting chemicals (phthalates, synthetic pyrethroids, polycyclic aromatic hydrocarbons) on sex chromosome ratio in sperm therefore, these findings require further replication in other populations.

Agricultural soils account for more than 50% of nitrogen leaching (LN) to groundwater in China. When excess levels of nitrogen accumulate in groundwater, it poses a risk of adverse health effects. Despite this recognition, estimation of LN from cropland soils in a broad spatial scale is still quite uncertain in China. The uncertainty of LN primarily stems from the shape of nitrogen leaching response to fertilizer additions (Nrate) and the role of environmental conditions. On the basis of 453 site-years at 51 sites across China, we explored the nonlinearity and variability of the response of LN to Nrate and developed an empirical statistical model to determine how environmental factors regulate the rate of N leaching (LR). The result shows that LN-Nrate relationship is convex for most crop types, and varies by local hydro-climates and soil organic carbon. Variability of air temperature explains a half (∼52%) of the spatial variation of LR. The results of model calibration and validation indicate that incorporating this empirical knowledge into a predictive model could accurately capture the variation in leaching and produce a reasonable upscaling from site to country. The fertilizer-induced LN in 2008 for China's cropland were 0.88 ± 0.23 TgN (1σ), significantly lower than the linear or uniform model, as assumed by Food and Agriculture Organization and MITERRA-EUROPE models. These results also imply that future policy to reduce N leaching from cropland needs to consider environmental variability rather than solely attempt to reduce Nrate.

Cadmium (Cd) availability can be significantly affected by soil properties. The effect of pH value on Cd availability has been confirmed. Paddy soils in South China generally contain high contents of iron (Fe). Thus, it is hypothesized that Fe fractions, in addition to pH value, may play an important role in the Cd bioavailability in paddy soil and this requires further investigation. In this study, 73 paired soil and rice plant samples were collected from paddy fields those were contaminated by acid mine drainage containing Cd. The contents of Fe in the amorphous and DCB-extractable Fe oxides were significantly and negatively correlated with the Cd content in rice grain or straw (excluding DCB-extractable Fe vs Cd in straw). In addition, the concentration of HCl-extractable Fe(II) derived from Fe(III) reduction was positively correlated with the Cd content in rice grain or straw. These results suggest that soil Fe redox could affect the availability of Cd in rice plant. Contribution assessment of soil properties to Cd accumulation in rice grain based on random forest (RF) and stochastic gradient boosting (SGB) showed that pH value should be the most important factor and the content of Fe in the amorphous Fe oxides should be the second most important factor in affecting Cd content in rice grain. Overall, compared with the studies from temperate regions, such as Europe and northern China, Fe oxide exhibited its unique role in the bioavailability of Cd in the reddish paddy soil from our study area. The exploration of practical remediation strategies for Cd from the perspective of Fe oxide may be promising.

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.

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.

Dechlorane compounds, including Dechlorane Plus (DP), mirex, and Dechlorane (Dec) 602, 603 and 604, were measured in 61 serum samples collected from a Korean urban area (Seoul) in 2013. Dechlorane Plus and Dec 602 were dominant in most samples, whereas Dec 604 was not detected in any samples. The median value of DP was 0.75 ng/g lipid, which was comparable with the levels observed in Europe and Canada, but lower than that observed in China. Statistically significant correlations among Dechlorane compounds were observed. The median anti-isomer fractional abundance (fanti) was 0.74, and a negative correlation between fanti and the DP concentration in serum samples was observed. Polybrominated diphenyl ethers (PBDEs) were also measured for comparison with Dechlorane compounds, and BDE-153 was found the most abundant congener with a median value of 1.43 ng/g lipid. A time trend of Dechlorane compounds was investigated in 7 pooled serum samples to cover the period from 2006 to 2013. A distinct trend of Dechlorane compounds was not observed, while PBDEs steadily decreased with time.