Recently, sulfate radical-based advanced oxidation processes (SR-AOPs) have been studied extensively for the removal of pollutants, however, few researches focused on the activation of bisulfite by nanoscale zerovalent iron (nZVI), especially, surface reaction mechanism and sulfate radical-mediated degradation pathway have not been elucidated in detail. In this study, influencing factors, the kinetics, transformation pathway and mechanism of triphenyl phosphate (TPHP) degradation in the nZVI/bisulfite system were systematically discussed. Compared with Fe²⁺, nZVI was found to be a more efficient and long-lasting activator of bisulfite via gradual generation of iron ions. The optimal degradation efficiency of TPHP (98.2%) and pseudo-first-order kinetics rate constant (kₒbₛ = 0.2784 min⁻¹) were obtained by using 0.5 mM nZVI and 2.0 mM bisulfite at the initial pH 3.0. Both Cl⁻ and NO₃⁻ inhibited the degradation of TPHP and the inhibitory effect of Cl⁻ was stronger than that of NO₃⁻ due to the higher reaction rate of Cl⁻ with •SO₄⁻. Furthermore, SEM, XRD and XPS characterization revealed that a thin passivation layer (Fe₂O₃, Fe₃O₄, FeOOH) deposited on the surface of fresh nZVI and a few iron corrosion products generated and assembled on the surface of reacted nZVI. Radical quenching tests identified that •SO₄⁻ was the dominant reactive oxidative species (ROS) for TPHP removal. Based on HRMS analysis, six degradation products were determined and a sulfate radical-mediated degradation pathway was proposed. In a word, this study revealed that the nZVI/bisulfite system had a great potential for the TPHP elimination in waterbody.

The dissemination of antibiotic resistance (AR) has attracted global attention because of the increasing antibiotic treatment failure it has caused. Through natural transformation, a live bacterium takes up extracellular DNA (exDNA), which facilitates AR dissemination. However, recovery of exDNA from water samples is challenging. In this study, we validated a consecutive ultrafiltration-based protocol to simultaneously recover intracellular DNA (inDNA), dissolved exDNA (Dis_exDNA, dissolved in the bulk water), and adsorbed exDNA (Ads_exDNA, adsorbed to the surfaces of suspended particles). Using hollow fiber ultrafiltration (HFUF), all DNA fractions were concentrated from environmental water samples, after which Dis_exDNA (supernatant) was separated from inDNA and Ads_exDNA (pellets) using centrifugation. Ads_exDNA was washed off from the pellets with proteinase K and sodium phosphate buffer. Dis_exDNA and Ads_exDNA were further concentrated using centrifugal ultrafiltration, from which silica binding was performed. inDNA was extracted from washed pellets with a commercial kit. For inDNA, HFUF showed recovery efficiencies of 96.5 ± 18.5% and 88.0 ± 2.0% for total cells and cultured Escherichia coli, respectively (n = 3). To represent all possible DNA fragments in water environment, exDNA with different lengths (10.0, 4.0, 1.0, and 0.5 kbp) were spiked to test the recovery efficiencies for Dis_exDNA. The whole process achieved 62.2%–62.9% recovery for 10 and 4 kbp exDNA, and 38.8%–44.5% recovery for 1.0 and 0.5 kbp exDNA. Proteinase K treatment enhanced the recovery of Ads_exDNA by 4.0–10.7 times. The protocol was applied to water samples from an urban river in Tokyo, Japan. The abundance of AR genes (ARGs) in inDNA, Dis_exDNA, and Ads_exDNA increased downstream of wastewater treatment plants. ARGs in Ads_exDNA and Dis_exDNA accounted for 1.8%–26.7% and 0.03%–20.9%, respectively, of the total DNA, implying that Ads_exDNA and Dis_exDNA are nonnegligible potential pools for the horizontal transfer of ARGs.

Accurate estimation of historical PM2.5 exposures for epidemiological studies is challenging when extensive monitoring data are limited in duration. Here, we develop a national-scale PM2.5 exposure model for Japan using measurements recorded between 2014 and 2016 to estimate monthly means for 1987 through 2016. Our objective is to obtain accurate PM2.5 estimates for years prior to implementation of extensive PM2.5 monitoring, using observations from a limited period. We utilize a neural network to convey the non-linear relationship between the target pollutant and predictors, while incorporating the associated air pollutants. We obtain high R² values of 0.76 and 0.73 through spatial and temporal cross validation, respectively. We evaluate estimation accuracy using an independent data set and achieve an R² of 0.75. Moreover, monthly variations for 2000–2013 are well reproduced with correlation coefficients of greater than 0.78, obtained through a comparison with observations. We estimate monthly means at 1 × 1 km resolution from 1987 through 2016. The estimates show decreases in the area and population weighted means beginning in the 1990s. We successfully estimate monthly mean PM2.5 concentrations over three decades with outstanding predictive accuracy. Our findings illustrate that the presented approach achieves accurate long-term historical estimations using observations limited in duration.

Environmental chemical exposures have been implicated as risk factors for the development of non-alcoholic fatty liver (NAFLD). Bisphenol S (BPS), widely used in multitudinous consumer products, could disrupt lipid metabolism in the liver. This study aimed at examining the hypothesis that long-term exposure to BPS promotes the development of liver fibrosis and inflammation by means of the application of a semi-static exposure experiment that exposed zebrafish to 1, 10, and 100 μg/L BPS from 3 h post fertilization to 120 day post fertilization. Results showed that the 120-d BPS exposure elevated plasma aspartate aminotransferase and alanine aminotransferase activities, increased triacylglycerol (TAG) and total cholesterol levels in male liver, and even induced hepatic apoptosis and fibrosis. Hepatic lipid accumulation observed in the 30-d BPS-exposed zebrafish was recovered after a 90-d depuration phase, thereby indicating that long-term BPS exposure promotes the progression of simple steatosis to non-alcoholic steatohepatitis. Furthermore, BPS exposure for 120-d promoted the synthesis of TAG and lipotoxic free fatty acids by elevating the transcription of srebp1, acc, fasn, and elovl6, induced endoplasmic reticulum (ER) stress with increasing expression levels of unfolded protein response (UPR) genes (perk, hsp5, atf4a, and ddit3), and then stimulated the expression of two key autophagy genes (atg3 and lc3) and inflammatory genes (il1b and tnfα). It is indicated that BPS can induce the development of steatohepatitis via the activation of the PERK-ATF4a pathway of the UPR. Data gathered suggest that environmental pollutants-induced ER stress with the activation of UPR can potentially trigger the NAFLD development in males. Overall, our study provided new sights into understanding of the adverse health effects of metabolism disrupting chemicals.

Plastic debris has become a major threat to the marine environment and wildlife. Sea turtles are particularly vulnerable, and are known to ingest plastic debris globally; however, information from Greek waters is still absent. In this study, 36 stranded dead loggerhead turtles (Caretta caretta) were collected from the Greek coastline area, and their gastrointestinal content was analysed for ingested plastic debris. Twenty-six individuals (72%) were found to have ingested plastic, with an average of 7.94 ± 3.85 (SE) plastic items per turtle. In total, 286 plastic items were counted and categorised by size, shape, colour, and polymer type. Fourier Transform Infrared Spectrometry revealed that polypropylene and polyethylene were the dominant polymer plastic types found. Results indicated a variation in plastic ingestion amongst life stages of the loggerhead specimens. This study provides evidence of plastic ingestion by loggerhead turtles in Greek waters.

There is limited research on the ingestion of microplastic particles (MPs) by fish from the southern part of the Mediterranean Sea. This study provides the occurrence of small MPs (≤3 μm) in the gastrointestinal tract and muscle of adult benthopelagic fish Serranus scriba (L.1758), caught along Tunisian coasts. MPs were extracted from selected tissues using a potassium hydroxide digestion method (KOH 10%) and then quantified, and their chemical structure was characterized through Raman microspectroscopy. The results highlighted that MPs were present in all samples. The average abundance of MPs per gram of fish tissue identified through successive filters of 3 μm, 1.2 μm, and 0.45 μm differed significantly among the sites. The properties of the MPs extracted indicated that polyethylene-vinyl-acetate (PEVA: 33.45%), high density polyethylene (HD-PE: 17.33%), and fragments were the most abundant plastic types and shape found, respectively. Among those, most MPs were found at a size class of 3–1.2 μm (∼60%), especially in the muscle, suggesting a high transfer of MPs into the human diet. Our field work also aimed to explore the effects observed in the gastrointestinal tract with a battery of biomarkers assessing oxidative stress and neurotoxicity. The preliminary results of this study showed the existence of a link between small MPs, sites, and their associated urban activities and induced oxidative stress. However, more detailed studies are required to evaluate the transfer of MPs into tissues and the potential impacts of this transfer on human health.

Microbial community in wastewater treatment plants (WWTPs) are affected by various environmental factors. The microbial communities from different WWTPs around world were compared by meta-analysis of the published high-throughput sequencing data of 16S rRNA of these WWTPs, the various environmental factors considered. Community richness indexes showed significant difference between altitude groups, and there was no latitudinal diversity gradient in WWTPs’ microbiomes. Climate was the most important influential factor and process was the second factor, and latitude and altitude contributed 5.51% and 4.78% of the overall variance of the data separately. Three significantly enriched bacterial communities in latitude and altitude respectively were showed by ternary plots. Mantel test illustrated that microbial community was strongly correlated with dissolved oxygen, temperature and pollutants concentrations. The prediction of potential functions revealed that microbial function structures were more stable than community structures. Some dominant bacteria in WWTPs have potential pathogenicity may pose serious threat to the environment and human health.

The Tharsis mine is presently abandoned, but the past intense exploitation has left large dumps and other sulphide-rich mining wastes in the area generating acid mine drainages (AMD). The main goal of this work is to study the effect of hydrogeochemical processes, hydrological regime and the waste typology on the physicochemical parameters and dissolved concentrations of pollutants in a deeply AMD-affected zone. Extreme leachates are produced in the area, reaching even negative pH and concentrations of up to 2.2 g/L of As and 194 g/L of Fe. The results of the comparison of ore grades of sulphide deposits with dissolved concentrations in waters shows that Pb is the least mobile element in dissolution probably due to the precipitation of Pb secondary minerals and/or its coprecipitation on Fe oxyhydroxysulphates. Arsenic, Cr, and V are also coprecipitated with Fe minerals. Seasonal patterns in metal contents were identified: elements coming from the host rocks, such as Al, Mn and Ni, show their maximum values in the dry period, when dilution with freshwater is lower and the interaction of water-rock processes and evaporation is higher. On the other hand, As, Cr, Fe, Pb and V show minimum concentrations in the dry period due to intense Fe oxyhydroxysulphate precipitation. In this sense, large sulphide rich waste heaps would be a temporal sink of these elements (i.e. Pb, As, Cr and V) in the dry period, and a significant source upon intense rainfalls.

Ochratoxin A (OTA) is a potent mycotoxin that frequently contaminates agro-products and threatens food safety. A highly efficient OTA degrading strain Lysobacter sp. CW239 was isolated, and the OTA degradation characteristics were investigated. A novel OTA degrading gene carboxypeptidase cp4 was successfully cloned and characterized from CW239. The heterologous recombinant was constructed by gene cp4 and expression vector pET-32a⁽⁺⁾ and overexpressed by E. coli BL21 CodonPlus™ (DE3). The recombinant protein rCP4 was purified, and the OTA-degrading activity was evaluated. Although OTA was efficiently degraded by CW239 (24-h degradation ratio of 86.2%), the 24-h OTA degradation ratio for rCP4 was only 36.8% at fairly high concentration (0.25 mg/mL) protein. The degraded product was obtained by immune affinity column (IAC) and determined by mass spectrometry (MS), and the degraded product was the less toxic ochratoxin α (OTα). Based on the serial investigations of this study, OTA might be simultaneously co-degraded by CP4 and another unknown degrading agent in that degrading strain.

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