Carbamazepine (CBZ), a widely detected pharmaceutical in wastewaters, cannot currently be treated by conventional activated sludge technologies, as it is highly resistant to biodegradation. In this study, the degradation kinetics and reaction mechanisms of CBZ by hydroxyl radical (OH) and sulfate radical (▪)–based advanced oxidation processes (AOPs) were investigated with a combined experimental/theoretical approach. We first measured the UV absorption spectrum of CBZ and compared it to the theoretical spectrum. The agreement of two spectra reveals an extended π–conjugation system on CBZ molecular structure. The second–order rate constants of OH and ▪ with CBZ, measured by competition kinetics method, were (4.63 ± 0.01) × 10⁹ M⁻¹ s⁻¹ and (8.27 ± 0.01) × 10⁸ M⁻¹ s⁻¹, respectively at pH 3. The energetics of the initial steps of CBZ reaction with OH and ▪ were also calculated by density functional theory (DFT) at SMD/M05–2X/6–311++G**//M05–2X/6–31 + G**level. Our results reveal that radical addition is the dominant pathway for both OH and ▪. Further, compared to the positive ΔGR0 value for the single electron transfer (SET) reaction pathway between CBZ and OH, the ΔGR0 value for SET reaction between CBZ and ▪ is negative, showing that this reaction route is thermodynamically favorable. Our results demonstrated the remarkable advantages of AOPs for the removal of refractory organic contaminants during wastewater treatment processes. The elucidation of the pathways for the reaction of OH and ▪ with CBZ are beneficial to predict byproducts formation and assess associated ecotoxicity, providing an evaluation mean for the feasibility of AOPs application.

In this study, the Songgang River (SR) was selected as a typical tributary that is heavily polluted by rapid urbanization and industrialization. The polycyclic aromatic hydrocarbon (PAH) distribution at five representative sampling sites from different urban functional areas was studied. The chemical and physical properties and spatial and vertical distribution of PAHs in sediments were investigated. PAH source identification and the ecological risks of the sediments were evaluated. The results suggested that the industrial zone and dense residential and commercial areas were the most contaminated areas of the SR, as the chemical and physical properties of total organic carbon content in sediments was the highest at the dense residential and commercial areas (0.1–4.5%); however, the acid volatile sulfide, total nitrogen, and total phosphorus contents were the highest in the industrial zone, with ranges of 700.0–1618.4 mg/kg dw, 22.4–3543.9 mg/kg dw, and 82.3–4550.7 mg/kg dw, respectively. The spatial distribution of residual PAHs in the sediment cores showed a wide variation among different urban functional areas, and the vertical characterization (0–300 cm) depicted a significant decreasing trend with depth and with an abrupt increase at 180 cm. The concentration of ∑16 PAHs ranged from 208.7 to 7709.8 ng/g dw, with the highest concentrations obtained in the industrial zone. The low molecular weight-PAHs (153–6720 ng/g dw) were predominant in the sediments. Furthermore, there were combined sources (biomass burning: 40.3%; fossil fuel combustion: 25.5%; mixed source: 21.5%; oil pollution: 12.7%) and a long term accumulation effect, with anthropogenic activities and industrial pollution as the major contributing sources. The concentrations of Nap, Acy, Ace, Flu, and Ant exceeded the lower limit of the sediment quality criteria, and higher toxic equivalent concentration values of the total carcinogenic PAHs were observed nearby the midstream of the SR, which may cause adverse biological effects and implies a need for regular monitoring.

This study provided a comprehensive characterization on ingestion of different typologies of microplastics in several fish and invertebrate species from the Adriatic Sea, considered as a preferential area of plastic accumulation in the Mediterranean. Almost 500 organisms were sampled in the three sectors of Northern, Central and Southern Adriatic, testing the hypothesis that area of collection, habitat and feeding strategy might influence the occurrence of plastic particles in biota. In this study, the overall characterization considered separately plastic microparticles (MPs) from textile microfibers (MFs) which also included natural and semi-synthetic ones. Ingestion of MPs was a widespread phenomenon, but their number (typically 1 or 2) did not reveal any significant relationship with biometric values, geographical areas or ecological features of the species. Conversely, the frequency of ingestion, ranging from 13 to 35% of organisms containing MPs, appeared a more reliable index to highlight such differences, revealing higher values in species from Central and Southern basins compared to the Northern one, as well as in benthopelagic compared to benthic or pelagic organisms. Geographical differences also occurred in terms of size and typology of ingested particles, suggesting the importance of local river runoffs and surface currents dynamics. Textile microfibers (MFs) were also abundant in Adriatic food webs occurring in all the analyzed species with average numbers (3–10) and frequencies (40–70%) higher than those reported for MPs; further, an elevated percentage of MFs (>80%) was of natural or semi-synthetic origin.Overall, this study provided general insights toward the harmonization of a common biomonitoring strategy, as in the context of MSFD, including the suggestion of a frequency-based index and of a multi-species approach to increase the ecological relevance of assessment, as well as the comparability between different areas and trophic webs.

Hydraulic fracturing of horizontal wells is a cost effective means for extracting oil and gas from low permeability formations. Hydraulic fracturing often produces considerable volumes of flowback and produced water (FPW). FPW associated with hydraulic fracturing has been shown to be a complex, often brackish mixture containing a variety of anthropogenic and geogenic compounds. In the present study, the risk of FPW releases to aquatic systems was studied using the model benthic invertebrate, Lumbriculus variegatus and field-collected FPW from a fractured well in Alberta. Acute, chronic, and pulse toxicity were evaluated to better understand the implications of accidental FPW releases to aquatic environments. Although L.variegatus is thought to have a high tolerance to many stressors, acute toxicity was significant at low concentrations (i.e. high dilutions) of FPW (48 h LC50: 4–5%). Chronic toxicity (28 d)of FPW in this species was even more pronounced with LC50s (survival/reproduction) and EC50s (total mass) at dilutions as low as 0.22% FPW. Investigations evaluating pulse toxicity (6 h and 48 h exposure) showed a significant amount of latent mortality occurring when compared to the acute results. Additionally, causality in acute and chronic bioassays differed as acute toxicity appeared to be primarily driven by salinity, which was not the case for chronic toxicity, as other stressors appear to be important as well. The findings of this study show the importance of evaluating multiple exposure regimes, the complexity of FPW, and also shows the potential aquatic risk posed by FPW releases.

With the increase in population and industrialization, air pollution has become one of the global problems nowadays. Therefore, air pollutant parameters should be measured at regular intervals, and the necessary measures should be taken by evaluating the results of measurements. In order to prevent air pollution, pollutant parameters must be evaluated within the framework of a model. Recently, in order to obtain objective and more sensitive results with regard to air pollution nowadays, studies, which use machine learning algorithms in artificial intelligence technologies, have been carried out. In this study, PM₁₀ concentrations, which are obtained from 7 stations in Ankara province in Turkey, were trained with machine learning algorithms (LASSO, SVR, RF, kNN, xGBoost, ANN). The PM₁₀ concentrations of the years 2009–2017 of 6 stations in Ankara were given as input, and the PM₁₀ concentrations of the seventh station for the year 2018 were predicted. The model development stage was repeated for each station, and the performance and error rates of the algorithms were determined by comparing the results produced by the algorithms with the actual results. The best results were provided with ANN (R² = 0.58, RMSE = 20.8, MAE = 14.4). The spatial distribution of the estimated concentration results was provided through Geographic Information System (GIS), and spatial strategies for improving air pollution over land use were established.

A laboratory bioassay was conducted to investigate the ecotoxicity of a chromium-enriched superfood, Spirulina platensis, on the meiofauna collected from the Ghar El Melh lagoon, Tunisia. After 1 month of exposure, the abundances of meiobenthic taxa and the taxonomic and morpho-functional diversity of nematodes showed significant differences between the Spirulina and Spirulina + chromium groups. The nematodes were more tolerant of all types of stressors compared to harpacticoids, polychaetes, and oligochaetes, and the lowest taxonomic and morpho-functional diversity of nematodes was observed in the highest sedimentary concentration of S. platensis (50% DW). The mixed treatments may have been richer in micro-habitats and subject to low selective pressure, thereby hosting nematodes with a wide range of adaptations. The responses of the nematode species differed depending on their functional traits. Spirulina enriched with chromium induced two responses for the same feeding group: high toxicity for Daptonema fallax and low toxicity for two Theristus species (T. flevensis and T. modicus). The ecotoxicity of the Spirulina/chromium mixtures were lower than that of Spirulina alone, suggesting mutual neutralization between these two elements. The association between functional traits and taxonomic diversity showed that the effects of the mixtures were not additive and that one of the stressors camouflaged the effect of the other. Our findings should encourage the commercialization of chromium-enriched S. platensis owing to its lower ecotoxicity than Spirulina alone.

Although association between polycyclic aromatic hydrocarbons (PAHs) exposure and mitochondrial DNA copy number (mtDNAcn) was researched by traditional linear model extensively, most of these studies analyzed independent effect of each PAHs metabolite and adjust for the confounding other metabolites concomitantly, without considering others interactions. As a complex organic pollutant, a reasonable statistical method is needed to study toxic effects of PAHs.Therefore, we aimed to conduct a novel statistical approach, Bayesian Kernel Machine Regression (BKMR), to explore the effect of PAHs exposure on mtDNAcn among coke oven workers. In this cross-sectional study, the concentrations urinary of PAHs metabolites were measured using high performance liquid chromatography mass spectrometry (HPLC-MS). The mtDNAcn was measured using real-time quantitative polymerase chain reaction (RT-PCR) in peripheral blood of 696 Chinese coke oven workers. The relationship of urinary of PAHs metabolites and mtDNAcn were evaluated by BKMR model. And the results showed a significant negative effect of PAHs metabolites on mtDNAcn when PAHs metabolites concentrations were all above 35th percentile compared to the median and the statistically significant negative single-exposure effect of 2-OHNAP and 2-OHPHE on mtDNAcn when all of the other PAHs are fixed at a particular threshold (25th, 50th, 75th percentile). The changes in log 2-OHNAP and 2-OHPHE from the 25th to the 75th percentile when other PAHs metabolites were at the 50th percentile were associated with change in mtDNAcn of −0.082 (−0.021, −0.124) and −0.048 (−0.021, −0.090) respectively. And evidence of a linear effect of urinary 2-OHNAP and 2-OHPHE were found. Finally, our findings suggested that PAHs cumulative exposures and particularly single-exposure of 2-OHNAP and 2-OHPHE might compromise mitochondrial function by decreasing mtDNAcn in Chinese coke oven workers.

The metabolic syndrome (MetS) is a group of diseases that tend to occur together, including diabetes, hypertension, central obesity, cardiovascular disease and hyperlipidemia. Exposure to persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) has been associated with increased risk of development of several of the components of the MetS. The goal of this study is to determine whether the associations with POPs are identical for each of the components and for the MetS. The subject population was 601 Native Americans (Akwesasne Mohawks) ages 18 to 84 who answered a questionnaire, were measured for height and weight and provided blood samples for clinical chemistries (serum lipids and fasting glucose) and analysis of 101 PCB congeners and three OCPs [dichlorodiphenyldichloroethylene (DDE), hexachlorobenzene (HCB) and mirex]. Associations between concentrations of total PCBs and pesticides, as well as various PCB congener groups with each of the different components of the MetS were determine so as to ask whether there were similar risk factors for all components of the MetS. After adjustment for other contaminants, diabetes and hypertension were strongly associated with lower chlorinated and mono-ortho PCBs, but not other PCB groups or pesticides. Obesity was most closely associated with highly chlorinated PCBs and was negatively associated with mirex. High serum lipids were most strongly associated with higher chlorinated PCBs and PCBs with multiple ortho-substituted chlorines, as well as total pesticides, DDE and HCB. Cardiovascular disease was not closely associated with levels of any of the measured POPs. While exposure to POPs is associated with increased risk of most of the various diseases comprising the MetS, the specific contaminants associated with risk of the component diseases are not the same.