Chemical composition and pollutant sorption of biochar-derived organic matter fractions (BDOMs) are critical for understanding the long-term environmental significance of biochar. Phenanthrene (PHE) sorption by the humic acid-like (HAL) fractions isolated from plant straw- (PLABs) and animal manure-based (ANIBs) biochars, and the residue materials (RES) after HAL extraction was investigated. The HAL fraction comprised approximately 50% of organic carbon (OC) of the original biochars. Results of XPS and 13C NMR demonstrated that the biochar-derived HAL fractions mainly consisted of aromatic clusters substituted by carboxylic groups. The CO2 cumulative surface area of BDOMs excluding PLAB-derived RES fractions was obviously lower than that of corresponding biochars. The sorption nonlinearity of PHE by the fresh biochars was significantly stronger than that of the BDOM fractions, implying that the BDOM fractions were more chemically homogeneous. The BDOMs generally exhibited comparable or higher OC-normalized distribution coefficients (Koc) of PHE than the original biochars. The PHE logKoc values of the fresh biochars correlated negatively with the micropore volumes due to steric hindrance effect. In contrast, a positive relationship between the sorption coefficients (Kd) of BDOMs and the micropore volumes was observed in this study, suggesting that pore filling could dominate PHE sorption by the BDOMs. The positive correlation between the PHE logKoc values of the HAL fractions and the aromatic C contents indicates that PHE sorption by the HAL fractions was regulated by aromatic domains. The findings of this study improve our knowledge of the evolution of biochar properties after application and its potential environmental impacts.

Private groundwater sources in the Republic of Ireland provide drinking water to an estimated 750,000 people or 16% of the national population. Consumers of untreated groundwater are at increased risk of infection from pathogenic microorganisms. However, given the volume of private wells in operation, remediation or even quantification of public risk is both costly and time consuming. In this study, a hierarchical logistic regression model was developed to ‘predict’ contamination with E. coli based on the results of groundwater quality analyses of private wells (n = 132) during the period of September 2011 to November 2012. Assessment of potential microbial contamination risk factors were categorised into three groups: Intrinsic (environmental factors), Specific (local features) and Infrastructural (groundwater source characteristics) which included a total of 15 variables. Overall, 51.4% of wells tested positive for E. coli during the study period with univariate analysis indicating that 11 of the 15 assessed risk factors, including local bedrock type, local subsoil type, septic tank reliance, 5 day antecedent precipitation and temperature, along with well type and depth, were all significantly associated with E. coli presence (p < 0.05). Hierarchical logistic regression was used to develop a private well susceptibility model with the final model containing 8 of the 11 associated variables. The model was shown to be highly efficient; correctly classifying the presence of E. coli in 94.2% of cases, and the absence of E. coli in 84.7% of cases. Model validation was performed using an external data set (n = 32) and it was shown that the model has promising accuracy with 90% of positive E. coli cases correctly predicted. The developed model represents a risk assessment and management tool that may be used to develop effective water-quality management strategies to minimize public health risks both in Ireland and abroad.

A mobile pilot plant was set up in a wastewater treatment plant (WWTP) in southwest Spain to address potential adverse effects of effluents as a whole contaminant, which are discharging into marine environments. Ruditapes philippinarum specimens were exposed to different effluent concentrations (50%, 25%, 12.5%, 6.25%, and 3.15%) during seven days. After effluent exposure, lysosomal membrane stability alterations (LMS), changes in the energy status storage (total lipids content (TLP) and in the mitochondrial electron transport (MET), inhibition of inflammatory mechanisms (cyclooxygenase activity (COX)), and neurotoxic effects (acetylcholinesterase (AChE) were determined in exposed organisms. Furthermore, potential toxic reduction in the effluent was analysed by the application of an additional microalgae tertiary treatment called photobiotreatment (PhtBio). Results after PhtBio confirmed the toxic effect reduction in exposed organisms. Neuroendocrine effects, alterations in energy budget and in lipid storage revealed alterations in clam's health status causing stress conditions after effluent exposure.

To examine the mechanism of hexavalent chromium [Cr(VI)]-induced carcinogenesis, a cross-sectional study in workers with or without exposure to Cr(VI) as well as in vitro administration of Cr(VI) in 16HBE cells was conducted. We explored the associations between Cr(VI) exposure, methylation modification of DNA repair genes and their expression levels, and genetic damage. Results showed that hypermethylation of CpG sites were observed in both occupationally exposed workers and 16HBE cells administrated Cr(VI). DNA damage markers including 8-hydroxydeoxyguanosine (8-OHdG) and micronucleus frequency in Cr(VI)-exposed workers were significantly higher than the control group. Among workers, blood Cr concentration was positively correlaed with the methylation level of CpG sites in DNA repair genes including CpG6,7, CpG8, CpG9,10,11 of MGMT, CpG11 of HOGG1; CpG15,16,17, CpG19 of RAD51, and genetic damage markers including 8-OHdG and micronucleus frequency. Significant negative association between methylation levels of CpG sites in DNA repair genes and corresponding mRNA was also observed in 16HBE cells. This indicated that Cr(VI) exposure can down-regulate DNA repair gene expression by hypermethylation, which leads to enhanced genetic damage. The methylation level of these CpG sites of DNA repair genes can be potential epigenetic markers for Cr(VI)-induced DNA damage.

We analyzed the acute toxicity of the 48% glyphosate (GLY)-based Credit®, the 57.71% dicamba (DIC)-based Kamba®, and the 83.5% 2,4-dichlorophenoxyacetic acid (2,4-D)-based Weedar® Full, alone and as mixtures on the fish Cnesterodon decemmaculatus. Mortality revealed the LC50 96h values of 91.73 mg L−1 (range: 86.80–98.00 mg L−1), 1401.57 mg L−1 (range: 1243.78–1527.35) and 678.04 mg L−1 (range: 639.35–718.04 mg L−1) for GLY, DIC and 2,4-D, respectively. Mean values for the toxic unit (TU) that induced 50% mortality (TU50 96h) of fish exposed to equitoxic mixtures were 1.67 (range: 1.65–1.69) for Credit® and Kamba® and 1.28 (range: 1.20–1.36) for Credit® and Weedar® Full suggesting that both mixtures are antagonic. Non-equitoxic combinations demonstrated an antagonistic interaction of herbicides Credit® and Kamba®, whereas a synergistic effect was observed for Credit® and Weedar® Full formulations. GLY and DIC as a mixture demonstrated lower toxicity on non-target species compared to GLY and 2,4-D in combination, at least for C. decemmaculatus, leading to the conclusion that the former combination could be strongly recommended in further agricultural practices.

Environmental exposure of fish to steroid hormones through wastewater and agricultural runoff may pose a health risk. Thus far, ecotoxicological studies have largely been focused on the disruption of the sex hormone system, but additional effects have been poorly investigated. Here we report on the effects of a series of different natural and synthetic steroid hormones on the locomotor behavior and the transcriptional levels of core clock genes in zebrafish eleuthero-embryos (Danio rerio). Of the 20 steroids analyzed, progestins and corticosteroids, including progesterone and cortisol, significantly decreased the locomotor activities of eleuthero-embryos at concentrations as low as 16 ng/L, while estrogens such as 17β-estradiol led to an increase. Consistently, progestins and corticosteroids displayed similar transcriptional effects on core clock genes, which were remarkably different from those of estrogens. Of these genes, per1a and nr1d2a displayed the most pronounced alterations. They were induced upon exposure to various progestins and corticosteroids and could be recovered using the progesterone receptor/glucocorticoid receptor antagonist mifepristone; this, however, was not the case for estrogens and the estrogen receptor antagonist 4-hydroxy-tamoxifen. Our results suggest that steroid hormones can modulate the circadian molecular network in zebrafish and provide novel insights into their mode of actions and potential environmental risks.

Soil particulate organic matter (POM) has rapid turnover and metal enrichment, but the interactions between organic matter (OM) and metals have not been well studied. The present study aimed to investigate changes in the OM concentration and composition of the POM fraction and their corresponding effects on metal distribution and extractability in long-term polluted paddy soils. Soil 2000–53 μm POM size fractions had higher contents of C–H and C=O bonds, C–H/C=O ratios and concentrations of fulvic acid (FA), humic acid (HA), cadmium (Cd) and zinc (Zn) than the bulk soils. Cadmium and Zn stocks in soil POM fractions were 24.5–27.9% and 7.12–16.7%, respectively, and were more readily EDTA-extractable. Compared with the control soil, the 2000–250 μm POM size fractions had higher organic carbon concentrations and C/N ratios in the polluted soils. However, there were no significant differences in the contents in C–H and C=O bonds or C–H/C=O ratios of POM fractions among the control, slightly and highly polluted soils. In accordance with the lower contents of C=O bonds and FA and HA concentrations, the Cd and Zn concentrations in 250–53 μm POM size fractions were lower than those in 2000–250 μm POM size fractions. Enrichment of Cd in POM fractions increased with increasing soil pollution level. These results support the view that changes in the OM concentration and the size and composition of POM fractions play a key role in determining the distribution of Cd and Zn in paddy soils.

Wind induced flow velocity patterns and associated thermal destratification can drive to hypoxia reduction in large shallow lakes. The effects of wind induced hydrodynamic changes on destratification and hypoxia reduction were investigated at the Meiling bay (N 31° 22′ 56.4″, E 120° 9′ 38.3″) of Lake Taihu, China. Vertical flow velocity profile analysis showed surface flow velocities consistency with the wind field and lower flow velocity profiles were also consistent (but with delay response time) when the wind speed was higher than 6.2 m/s. Wind field and temperature found the control parameters for hypoxia reduction and for water quality conditions at the surface and bottom profiles of lake. The critical temperature for hypoxia reduction at the surface and the bottom profile was ≤24.1C° (below which hypoxic conditions were found reduced). Strong prevailing wind field (onshore wind directions ESE, SE, SSE and E, wind speed ranges of 2.4–9.1 m/s) reduced the temperature (22C° to 24.1C°) caused reduction of hypoxia at the near surface with a rise in water levels whereas, low to medium prevailing wind field did not supported destratification which increased temperature resulting in increased hypoxia. Non-prevailing wind directions (offshore) were not found supportive for the reduction of hypoxia in study area due to less variable wind field. Daytime wind field found more variable (as compared to night time) which increased the thermal destratification during daytime and found supportive for destratification and hypoxia reduction. The second order exponential correlation found between surface temperature and Chlorophyll-a (R²: 0.2858, Adjusted R-square: 0.2144 RMSE: 4.395), Dissolved Oxygen (R²: 0.596, Adjusted R-square: 0.5942, RMSE: 0.3042) concentrations. The findings of the present study reveal the driving mechanism of wind induced thermal destratification and hypoxic conditions, which may further help to evaluate the wind role in eutrophication process and algal blooms formation in shallow water environments.Wind field is the key control factor for thermal destratification and hypoxia reduction. 24.1C° is the critical/threshold temperature for hypoxia, Chlorophyll-a and NH3-N concentrations of the shallow freshwater lake.

Pharmaceutically active compounds (PhACs) are excreted by humans and animals and released into the aquatic environment through wastewater, which can have potential negative impacts on ecological systems. To conduct a nationwide investigation of the occurrence of PhACs in water resources in China, an analytical procedure based on solid-phase extraction (SPE) and LC-MS/MS was used to measure 45 PhACs in surface water samples from a network of 29 rivers across 31 provinces in China in 2014 and 2015. PhACs were prevalent in all sampled streams. The concentrations of commonly detected PhACs were comparable to those detected in other countries. High total concentrations (mean > 1 μg L−1) of all tested PhACs were primarily detected in areas under extreme water stress, specifically northern and eastern coastal areas. Source apportionment based on the profiles of the target compounds found that 54% of the PhACs in China originated from freshly discharged untreated sewage. Metformin (MET) and its biodegradation product, guanylurea (GUL), were used as a pair of indicators to predict PhAC contamination levels and differentiate between biotreated and unbiotreated wastewater. High MET/GUL can be used to indicate untreated wastewater, whereas low MET/GUL values are a strong indicator of treated wastewater. Furthermore, wastewater biotreatment ratios were calculated. We estimated that the biotreatment ratios of most of the provinces in China were less than 50%. We conclude that more attention should be paid to untreated sewage water, especially water in rural areas rather than the existing concentration on urban sewage treatment-oriented management.

With the commercialization of transgenic cotton that expresses Bt (Bacillus thuringiensis) insecticidal proteins, mirid bugs have become key pests in cotton and maize fields in China. Genetically engineered (GE) crops for controlling mirids are unavailable owing to a lack of suitable insecticidal genes. In this study, we developed and validated a dietary exposure assay for screening insecticidal compounds and for assessing the potential effects of insecticidal proteins produced by GE plants on Apolygus lucorum, one of the main mirid pests of Bt cotton and Bt maize. Diets containing potassium arsenate (PA) or the cysteine protease inhibitor E-64 were used as positive controls for validating the efficacy of the dietary exposure assay. The results showed that with increasing concentrations of PA or E-64, A. lucorum larval development time was prolonged and adult weight and fecundity were decreased, suggesting that the dietary exposure assay was useful for detecting the toxicity of insecticidal compounds to A. lucorum. This assay was then used to assess the toxicity of Cry1Ab, Cry1Ac, Cry1F, Cry2Aa, and Cry2Ab proteins, which have been transformed into several crops, against A. lucorum. The results showed that A. lucorum did not show a negative effect by feeding on an artificial diet containing any of the purified Cry proteins. No significant changes in the activities of digestive, detoxifying, or antioxidant enzymes were detected in A. lucorum that fed on a diet containing Cry proteins, but A. lucorum fitness was reduced when the insect fed on a diet containing E-64 or PA. These results demonstrate that A. lucorum is not sensitive to the tested Cry proteins and that the dietary exposure assay is useful for evaluating the toxicity of insecticidal compounds to this species.