High-density polyethylene (HDPE) is a known sorbent for non-ionic organic compounds in technical applications. Nevertheless, there is little information available describing sorption to industrial HDPE for a broad range of compounds. With a better understanding of the sorption properties of synthetic polymers, environmental risk assessment would achieve a higher degree of accuracy, especially for microplastic interactions with organic substances. Therefore, a robust methodology for the determination of sorbent properties for non-ionic organic compounds by HDPE is relevant for the understanding of molecular interactions for both technical use and environmental risk assessment.In this work, sorption properties of HDPE material used for water pipes were characterized using a poly-parameter linear free-energy relationship (ppLFER) approach. Sorption batch experiments with selected probe sorbates were carried out in a three-phase system (air/HDPE/water) covering an aqueous concentration range of at least three orders of magnitude. Sorption in the concentration range below 10⁻² of the aqueous solubility was found to be non-linear and the Freundlich model was used to account for this non-linearity. Multiple regression analysis (MRA) using the determined distribution coefficients and literature-tabulated sorbate descriptors was performed to obtain the ppLFER phase descriptors for HDPE. Sorption properties of HDPE were then derived from the ppLFER model and statistical analysis of its robustness was conducted. The derived ppLFER model described sorption more accurately than commonly used single-parameter predictions, based i.e., on log Kₒ/w. The ppLFER predicted distribution data with an error 0.5 log units smaller than the spLFERs. The ppLFER was used for a priori prediction of sorption by the characterized sorbent material. The prediction was then compared to experimental data from literature and this work and demonstrated the strength of the ppLFER, based on the training set over several orders of magnitude.

Fifty-six groundwater samples were taken from the island of Favignana to evaluate the interaction between the groundwater and seawater, as well as the deterioration factors for the aquifers, using the combined hydrogeochemical and multivariate statistical approaches. Results show that the order of the groundwater chemistry in the study area was Na+> Ca2+>Mg2+>K+ and Cl->HCO3−>SO42->NO3−. The groundwater samples were in the moderate saline zone to highly saline zone and indicate that the groundwater of the island of Favignana was recharged with seawater. The spatial distribution maps of Cl− and NO3− show that most of the groundwater samples had high concentrations of Cl− and NO3− in the study area. The ionic ratio diagrams, such as Na+/Cl− versus Cl−, Mg2+/Ca2+ versus Cl− and Ca2+/HCO3− versus Cl−, and other hydrogeochemical plots reveal that the groundwater chemistry of the study was primarily controlled by the seawater intrusion and reverse ion exchange process, with a small contribution from carbonate dissolution. Additionally, the NO3−/Cl− versus Cl− diagram and principal component analysis (PCA) show that the contamination of nitrate in the study area was due to human activities (i.e. agriculture and domestic sewage disposal). The outcome of the present research could be helpful for groundwater resource management in coastal environments.

Endocrine-disrupting chemicals (EDCs) are widely used in various consumer goods. Consequently, humans are constantly exposed to EDCs, which is associated with a variety of endocrine-related diseases. In this study, we demonstrated the effects of bisphenol A (BPA), benzyl butyl phthalate (BBP), and di(2-ethylhexyl) phthalate (DEHP) on estrogen receptor alpha (ERα) expression under normoxia and hypoxia. First, we confirmed the effects of EDCs on ER activity using OECD Test Guideline 455. Compared to the 100% activity induced by 1 nM 17-β-estradiol (positive control), BPA and BBP exhibited 50% ERα activation at concentrations of 1.31 μM and 4.8 μM, respectively. In contrast, and consistent with previous reports, DEHP did not activate ERα. ERα is activated and degraded by hypoxia in breast cancer cells. BPA, BBP, and DEHP enhanced ERα-mediated transcriptional activity under hypoxia. All three EDCs decreased ERα protein levels under hypoxia in MCF-7 cells. The transcriptional activity of hypoxia-inducible factor-1 was decreased and secretion of vascular endothelial growth factor (VEGF) was increased by BPA and BBP under hypoxia in MCF-7 cells, but not by DEHP. All three EDCs decreased the ERα protein expression level in Ishikawa human endometrial adenocarcinoma cells, and DEHP caused a weak decrease in VEGF secretion under hypoxia. These results demonstrate down-regulation of ERα by EDCs may influence the pathological state associated with hypoxia.

Spirocyclic tetramic acids are widely used in controlling phytophagous mite species throughout the world. the data set is incomplete and provides insufficient evidence for drawing the same conclusion for fish. To fill the gap whether these acaricides alter lipid metabolism on vertebrates, zebrafish embryos exposed to a series concentration of pesticides, the developmental effects, enzyme activities and levels of gene expression were assessed, battery of biomarker utilized by the integrated biomarker response (IBRv2) model. The 96 h-LC₅₀ of spirodiclofen, spiromesifen and spirotetramat were 0.14, 0.12 and 5.94 mg/L, respectively. Yolk sac deformity, pericardial edema, spinal curvature and tail malformation were observed. Three spirocyclic acids were unfavouring the lipid accumulation of by inhibited the acetyl-CoA carboxylase (ACC), fatty acid synthesis (FAS), fatty acid binding proteins (FABP2) and lipoprotein lipase (LPL) activity. The total cholesterol (TCHO) level significantly decreased in the 0.072 mg/L spirodiclofen group and 0.015 and 0.030 mg/L in the spiromesifen groups. No expected change in spirotetramat group on the TCHO and triglycerides (TGs) levels for any of the treatments. The mRNA levels of the genes related to lipid metabolism also significantly altered. In both spirodiclofen and spiromesifen, ACC achieved the highest scores among a battery of biomarkers using integrated biomarker response (IBRv2). The results suggest that spiromesifen was the most toxic for embryos development and spirodiclofen was the most toxic for lipid metabolism in embryos. The 0.07 mg/L of spirodiclofen, 0.05 mg/L of spiromesifen and 2.00 mg/L would cause malformation on zebrafish embryos. This study will provide new insight that fatty acid metabolism may be a suitable biomarker for the spirocyclic tetramic acids in fish species.

The use of insecticides based on metabolites found in live organisms, such as the insecticide spinosad, has been an option for the control of agricultural pests because of the allegedly low toxicological risk for nontarget arthropods, such as stingless bees. In the current study, we evaluate the effects of chronic oral exposure to spinosad during the larval phase on survival, developmental time, body mass, midgut epithelial remodeling, and the peritrophic matrix (PM) of Partamona helleri stingless bee workers. Worker larvae that were raised in the laboratory were orally exposed to different concentrations (0, 6.53, 13.06, 32.64, and 3,264 ng. a.i. bee⁻¹) of spinosad (formulation), and the resulting survival, developmental time, and body mass were studied. The concentration of spinosad recommended for use in the field (3,264 ng. a.i. bee⁻¹) reduced the survival of workers during development. Also, sublethal concentrations of spinosad delayed the development and caused morphological changes in the midgut epithelium. Finally, the chronic exposure of larvae to 32.64 ng. a.i. bee⁻¹ spinosad also altered the remodeling of the midgut during metamorphosis and affected the organization of the PM of larvae, pupae, and adults. Our data suggest possible environmental risks for using spinosad in cultures that are naturally pollinated by stingless bees.

Cyanobacterial blooms are of global concern due to the multiple harmful risks they pose towards aquatic ecosystem and human health. However, information on the fate of organic pollutants mediated by cyanobacterial blooms in eutrophic water remains elusive. In the present study, endocrine disruptive potentials of phytoplankton samples were evaluated throughout a year-long surveillance in a large and eutrophic freshwater lake. Severe cyanobacterial blooms persisted during our sampling campaigns. Estrogenic agonistic, anti-estrogenic, anti-androgenic, and anti-glucocorticogenic effects were observed in the phytoplankton samples using in vitro reporter gene bioassays. 27 endocrine disrupting chemicals (EDCs) of different modes of action were detected in the samples via UPLC-MS/MS system. Results from mass balance analysis indicated that the measured estrogenic activities were greater than the predicted estrogenic potencies from chemical analysis, demonstrating that chemical analysis of targeted EDCs is unable to fully explain the compounds responsible for the observed estrogenicities. Results from Spearman's correlation analysis concluded that the concentrations of ten EDCs in phytoplankton samples were negatively correlated with cyanobacterial biomass, suggesting the potential occurrence of biomass bio-dilution effects of EDCs due to the huge biomass of cyanobacteria during bloom seasons. The present study provided complementary information about the potential endocrine disruptive risks of cyanobacterial blooms, which is important for understanding and regulating EDCs in eutrophic lakes.

A novel carbonaceous material (NCM), prepared by the pyrolyzation of the oily sludge of tank bottom, was proposed to remove Cr(VI) from a synthetic solution for the first time. The effects of initial Cr(VI) concentration, NCM dosage and initial solution pH on Cr(VI) removal and the adsorption kinetics, the adsorption isothem were investigated. The removal mechanism was studied by comparing the surface properties of NCM before and after the Cr(VI) removal. The results showed that NCM can effectively remove Cr(Ⅵ) from the synthetic solution with the increase of solution pH at equilibrium. At the initial Cr(Ⅵ) concentrations of 40, 100, 150 and 250 mg/L and NCM dosages of 1, 3, 6 and 8 g/L with initial solution pH of 2, the removal efficiency of Cr(VI) was 95.5, 96.8, 95.2 and 81.2%, and the solution pH at equilibrium reached 2.3, 3.5, 5.8 and 7.5, respectively. NCM was suitable for Cr(Ⅵ) removal while the initial Cr(VI) concentration was less than 100 mg/L and initial solution pH was lower than 2.5. Most of Cr(VI) was removed by the reduction of Fe2+ and S2− in NCM to Cr(III) and with the generation of stable FeCr2O4. Some Cr(VI) may be removed by reacting with Fe2+ and Ca2+ to produce CaCrO4 and FeCrO4 on the NCM surface. The dissolution of CaAl2Si2O8 and CaS in the solution increased the solution pH at equilibrium. NCM has been proved to be a material with dual functions both chemical reduction and adsorption.

We evaluated the short-term effect of mixtures of ambient air pollutants on respiratory and circulatory morbidity in four Colombian cities.Daily Emergency Department (ED) visit records for respiratory and circulatory selected diagnosis and daily concentrations for six criteria air pollutant were obtained in four of the five major cities in Colombia: Bucaramanga, Bogota, Cali, and Medellin during 2011–2014. Using conditional Poisson time series analysis with fixed effects, we assessed the effect of air pollutants on health outcomes using single-pollutant, two-pollutant and specific mixtures-of-pollutant models controlling for meteorology and time trends. The percentages of change in the rate of ED visits and their 95% confidence interval were estimated for the joint effect of pollutants.In single-pollutant models increases in gases concentrations were associated with increases in ED visits for respiratory and circulatory diseases. The two-pollutant models for respiratory diseases showed that the effect of NO₂ alone (% change 2.86 95% CI 1.87–3.85) is higher than the joint effect of any of its combinations except for its combination with SO₂ (% change 3.05 95%CI 1.04–5.05). The two-pollutant models for circulatory diseases showed synergistic effects between NO₂ and PM₂.₅ (% change 2.13 95%CI 0.001–4.26). Specific mixtures models showed that the mixture of “traffic-related pollutants” has the higher joint effect on circulatory morbidity and respiratory morbidity.The results show the dominant effect of NO₂ in air pollution mixtures on respiratory and circulatory morbidity, and the synergistic effect of NO₂ and SO₂ in air pollution mixtures on respiratory morbidity.

Environmentally persistent free radicals (EPFRs) are defined as organic free radicals stabilized on or inside particles. They are persistent because of the protection by the particles and show significant toxicity to organisms. Increasing research interests have been attracted to study the potential environmental implications of EPFRs. Because of their different physical forms from conventional contaminants, it is not applicable to use the commonly used technique and strategy to predict and assess the behavior and risks of EPFRs. Current studies on EPFRs are scattered and not systematic enough to draw clear conclusions. Therefore, this review is organized to critically discuss the current research progress on EPFRs, highlighting their occurrence and transport, generation mechanisms, as well as their environmental implications (including both toxicity and reactivity). EPFR formation and stabilization as affected by the precursors and environmental factors are useful breakthrough to understand their formation mechanisms. To better understand the major differences between EPFRs and common contaminants, we identified the unique processes and/or mechanisms related to EPFRs. The knowledge gaps will be also addressed to highlight the future research while summarizing the research progress. Quantitative analysis of the interactions between organic contaminants and EPFRs will greatly improve the predictive accuracy of the multimedia environmental fate models. In addition, the health risks will be better evaluated when considering the toxicity contributed by EFPRs.

Metabolic uncouplers are widely used for the in-situ reduction of excess sludge from activated sludge systems. However, the interaction mechanism between the metabolic uncouplers and extracellular polymeric substances (EPS) of activated sludge is unknown yet. In this study, the interactions between a typical metabolic uncoupler, o-chlorophenol (oCP), and the EPS extracted from activated sludge were explored using a suite of spectral methods. The binding constants calculated for the four peaks of three-dimensional excitation-emission matrix fluorescence were in a range of 1.24–1.76 × 10³ L/mol, implying that the tyrosine protein-like substances governed the oCP-EPS interactions. Furthermore, the results of Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and ¹H nuclear magnetic resonance indicated that the carboxyl, carbonyl, amine, and hydroxyl groups of EPS were the main functional groups involved in the formation of the oCP-EPS complex. The results of this study are useful for understanding the interactions between metabolic uncouplers and the EPS of activated sludge as well as their fates in biological wastewater treatment systems.