A global and systematic theoretical research on the singlet and triplet potential energy surfaces (PESs) of the CH₂ClO₂/CHCl₂O₂ with ClO reactions are done at the CCSD(T)//B3LYP level and accompanied with RRKM computations to forecast the mechanism and distribution of products. The simulation results revealed that, on the singlet PES, products P1 (CHClO + HO₂ + Cl)/P1 (CCl₂O + HO₂ + Cl) from IM1 (CH₂ClOOOCl)/IM1 (CHCl₂OOOCl) are forecasted to the primary products of the CH₂ClO₂/CHCl₂O₂ + ClO reactions, which are initiated by the oxygen atom of ClO radical addition to the terminal-O atom of CH₂ClO₂/CHCl₂O₂ barrierlessly, while other product channels contribute less to the whole reactions owing to higher barriers. Two other isomers, including IM2 (CH₂ClOOClO) and IM3 (CH₂ClOClO₂) for the CH₂ClO₂ + ClO reaction, and three other isomers, including IM2 (CHCl₂OOClO), IM3 (CHCl₂OClO₂), and IM4 (CHCl₂ClO₃) for the CHCl₂O₂ + ClO reaction, could be produced as less significant products. RRKM calculations presented that the initial adducts IM1 (CH₂ClOOOCl)/IM1 (CHCl₂OOOCl) are the primary products at T < 400 K and T < 600 K, respectively, and products P1 (CHClO + HO₂ + Cl)/P1 (CCl₂O + HO₂ + Cl) are dominant the reactions at T ≥ 400 K and T ≥ 600 K, respectively. The atmospheric lifetime of CH₂ClO₂ and CHCl₂O₂ in ClO is around 4.61 and 3.24 h, respectively.

The presence of plastic debris < 5 mm called microplastics (MPs) which results mainly from macroplastic’s fragmentation has been reported in aquatic ecosystems. Several studies have shown that MPs are persistent and their accumulation was observed in various aquatic species. However, the majority of studies focused on marine species, and much less on continental and estuarine biota. The goal of the present study was to investigate the effects of a mixture of two types of MPs (polyethylene and polypropylene), frequently found in natural environments, towards the ragworm Hediste diversicolor to determine their accumulation in organisms exposed through the water phase or sediment. Two concentrations of exposure were selected for medium and heavily contaminated areas reported for water phase (10 and 100 μg/L) and sediment (10 and 50 mg of MPs/kg). To study the potential toxic effect of MPs, immune parameters were selected since they are involved in many defense mechanisms against xenobiotics or infectious agents. An average number of MP items/worm ranging from 0 to 2.5 and from 1 to 36 were identified in animals exposed to the lowest and the highest concentration of MPs through water exposure. In worms exposed through sediment, less than 1 MP/worm was found and a greater number of particles were identified in depurated sediment. For immunotoxic impact, MP exposure induced a decrease in coelomocytes viability, but no alteration of phagocytosis activity, phenoloxydase, and acid phosphatase was measured. This study brings new results on the potential accumulation and immunotoxicity of MPs for the ragworm H. diversicolor who plays a key role in the structure and functioning of estuarine ecosystem.

Metal pollution has been a serious problem facing river systems worldwide, which can adversely affect human health through food chain. The goal of this study was to determine the distribution, sources, and health risk of dissolved metals (Cr, Mn, Ni, Cu, Zn, As, Cd, Pb, Al, Sb, V, Co, Mo) in major rivers located in the hilly area of southeastern China (namely, Jiulongjiang River (JL), Minjiang River (MJ), Oujiang River (OJ), Qiantangjiang River (QT), Raohe River (RR), Fuhe River (FR), Xinjiang River (XR), Ganjiang River (GR), Xiushui River (XS), Xiangjiang River (XJ), Zishui River (ZR), Yuanjiang River (YR), Lishui River (LR)) during dry and wet seasons. Results indicated that metal concentrations were spatially and temporally distinct. Metals of Mn, Ni, Cu, Cd, Sb were significantly higher in specific rivers than other metals. And metals of Cr, Ni, As, and Al concentrations were obviously higher in dry season than in wet season. The comparison with drinking water guidelines of China and other countries indicated that waterbodies were polluted higher by Al than other metals at most sites. Metals in JL and XJ may have health risk to local adults with hazard index (HI) > 1. While special attention should be paid to As, which had a potential carcinogenic risk to adults in study area with CR higher than the critical value. Source analysis with statistical method indicated that point and non-point pollutants from anthropogenic activities are the main sources of metals, with the exception of Al, Ni, V, Cr, and Mo that were mainly from natural processes. This study could be useful for the management and protection of the China’s Southern hilly area river systems.

This study was conducted to verify a hypothesis that immune cells are a target for the action of endocrine disrupting chemicals (EDCs) by investigating whether methylparaben (MeP) modulates human neutrophil functions. Neutrophils isolated from 15 donor samples were studied. Cells were incubated in the presence of increasing MeP concentrations (0.06, 0.8, 10, and 20 μM). The cytotoxic effect of MeP on neutrophils was evaluated by the MTT test. The ability of the neutrophils for chemotaxis, phagocytosis, NADPH oxidase activity, and superoxide anion generation was assessed in Boyden’s chamber, Park’s method with latex, the NBT test, and the cytochrome C reduction test, respectively. The total nitric oxide (NO) concentration was measured by the Griess reaction. There was no observable cytotoxic effect of MeP on human neutrophils. MeP (10 and 20 μM) exposure decreased neutrophilic ability for the tested functions, except for NO production. In neutrophils incubated with MeP (0.8 μM as well as 0.06 and 0.8 μM, respectively), we observed a decreased activity of NADPH oxidase as well as decreased generation of superoxide anion. Our results suggest a suppressive effect of MeP on the tested functions of human neutrophils, which confirms that immune cells are vulnerable to EDC action. Therefore, the disturbance of neutrophils’ oxygen-dependent phagocytic function as a result of exposure to environmental doses of MeP action could lead to impairment of innate immune responses in humans exposed to xenoestrogens.

Water level (a vital indicator for flood warnings and water management in floodplains) has been changed notably due to climatic and anthropogenic forces; however, very little is known about the relative effects of these agents. In this study, we take the Taihu Plain as an example to investigate potential factors driving changes in water level components through quantiles from 1954 to 2014. To quantify the extent of water level component changes attributable to climate variability and human activity, several non-stationary models considering rainfall, tide, evaporation, and hydraulic regulation as covariates are established based on generalized additive models for location, scale, and shape. The results indicate that most water level components increased over time and changed abruptly around the mid-1980s. As for climatic factors, the variability of rainfall, tide and evaporation significantly affected water level variation based on most quantiles from 1954 to 2014. Among several kinds of human activities, hydraulic regulation was a key factor influencing water level based on a high correlation coefficient. Positive effects were identified from hydraulic regulation regarding the association between rainfall and water level components; these effects depend on water level quantiles and the amount of rainfall occurrence. Our study has broad implications, providing a better understanding of water level variation and regional flood management.

Water supplies in coastal aquifers throughout the world are often threatened by salinization due to seawater intrusion and anthropogenic activities. In the Kalpitiya Peninsula in Sri Lanka, agricultural and domestic water supplies entirely depend on groundwater resources extracted from unconfined Holocene sandy aquifers. To differentiate the effects of seawater intrusion and agriculture on the coastal aquifers of this 160 km² peninsula, 43 groundwater samples were collected. These samples were analyzed for major ions, trace elements, and stable isotopes of water (δ¹⁸O and δ²H). The solute compositions were dominated by Cl⁻, [Formula: see text], and [Formula: see text], which were mostly balanced by Ca²⁺, Na⁺, and Mg²⁺. Among the four main water types, Na⁺-Cl⁻ and Ca²⁺-[Formula: see text] classifications were predominant in the investigated aquifers. Modifications of the groundwater due to evaporation during irrigation activities, but also due to seawater intrusion seem most plausible as indicated by the correlation of δ¹⁸O with δ²H (δ²H = 5.51 * δ¹⁸O-3.08, r = 0.93) deviating from the local meteoric water line. Particularly in the southern part of the peninsula, Mg²⁺/Ca²⁺ ratios and stable isotopes of water attributed salinization of groundwater to agricultural activities. However, especially in the north, seawater intrusions were also evident. Established mass balance calculations revealed that local groundwater had seawater admixtures of up to 12%. Our results indicate that integrated water management is essential and water resources should critically monitor in the Kalpitiya Peninsula in order to avoid over-exploitation and further seawater inflows.

Dechlorane plus (DP) is a chlorinated flame retardant with high production volume (HPV) and is widely used in our daily necessities. In the present study, a laboratory-scale microcosm was built up to simulate the uptake, depuration, bioaccumulation, and stereoselective enrichment of DP in a lower concentration and equilibration condition. Common carp (Cyprinus carpio) were used for 32 days exposure and 32 days depuration. The concentration ratios of syn-DP to total DP (fₛyₙ values) in fish examined were lower than that in commercial products. Rate constants of uptake (kS) and elimination (kₑ) for the syn- and anti-DP were calculated using a first-order kinetic model. The uptake rate constants of syn- and anti-DP were 0.63 and 0.89 day⁻¹, respectively. The depuration rate constants of syn-DP (0.11 day⁻¹) were similar to anti-DP (0.096 day⁻¹), suggesting that anti-DP is absorbed faster than syn-DP by common carp. The estimated bioconcentration factors for both syn-DP (5700 L/kg) and anti-DP (9300 L/kg) were higher than the bioconcentration hazard criteria outlined in the Stockholm Convention, suggesting the bioconcentration potential to aquatic organisms for DP.

This research was aimed to investigate the leaching behavior of zinc and copper from a porcelain stone tailings sample using RSM-CCD modeling. The synergetic and individual effects of five main factors including liquid/solid ratio, sulfuric acid concentration, agitation speed, leaching time, and temperature were examined on the recoveries of zinc and copper. For this purpose, two 2F1 models with R² values of 0.9341 and 0.8693 were developed for the relationship between the leaching efficiencies of copper and zinc and effective terms, respectively. The results indicated that the leaching process was significantly influenced by the interactive effects between factors. The leaching recoveries increased by increasing all factors in the range studied. However, the recoveries were nearly independent of the agitation rate, indicating surface chemical reaction as the leaching kinetics controlling step. It was also found that the linear effect of temperature, the interaction effect of leaching time with liquid/solid ratio, and the interactive effect between sulfuric acid concentration and agitation rate had the greatest impact on the leaching rate of copper. Additionally, the linear effect of temperature and the interactive effect of temperature with agitation speed and liquid/solid ratio were distinguished to be the most effective factors on the recoveries of zinc. Moreover, the optimization was performed using desirability function approach, and the highest recoveries of copper (73.95%) and zinc (81.02%) were obtained at an acid concentration of 10%, 300 rpm agitation rate, 10 mL/g liquid/solid ratio, 35 °C temperature, and 75 min leaching time.

In this study, a laboratory scale experiment for the treatment of synthetic molasses wastewater using a combination of an anaerobic baffled reactor (ABR) and a two-stage down-flow hanging sponge (TSDHS) reactor (ABR–TSDHS system) was conducted. The TSDHS comprised a closed-type first-stage down-flow hanging sponge (first DHS) for desulfurization and an open-type second-stage DHS (second DHS) for post-treatment of effluent from the ABR and first DHS. Effluent from the second DHS was sprinkled on top of the first DHS, whereas biogas produced from the ABR was supplied to its bottom. A chemical oxygen demand (COD) removal efficiency of 88.3% was found for the ABR–TSDHS system during the final treatment phase. The ABR achieved a maximum organic loading rate (OLR) of 3.70 kg COD/(m³ day). Most of the organic matter was degraded in the first compartment of the ABR, with methane-producing archaea as its main consumer. The biogas generated by the ABR contained high concentrations of hydrogen sulfide (up to 4,500 ppm). In the TSDHS, the first DHS achieved 87.3% hydrogen sulfide removal via dissolution into sprinkled effluent water. Dissolved sulfide in the first DHS effluent was oxidized to sulfate in the second DHS in the absence of aeration. In addition, 85.0% of the ammonia and 57.7% of the total nitrogen were removed in the second DHS via biological reactions, including sulfur-based autotrophic denitrification. Therefore, the ABR–TSDHS system can be applied to not only molasses wastewater treatment but also the desulfurization of the produced biogas.

Corbicula fluminea (C. fluminea) is one of the mollusc species commonly eaten as a popular snack in Kelantan, Malaysia. This species contributes to the local economic activity. However, the handling process of C. fluminea at different processing stages (raw, smoke and selling stages) is believed to have affected the nutritional value in their soft tissue. Hence, this study aims to provide information about the chemical content (moisture, crude fat, ash, crude protein and carbohydrate) of C. fluminea and fatty acid of smoked C. fluminea at different processing stages. Samples were collected from Pasir Mas and Tumpat, Kelantan, Malaysia. The chemical content analysis was carried out based on the Association of Official Analytical Chemists (AOAC) standard procedures. The results have indicated that moisture (80.93 ± 0.37%) and crude fat (10.82 ± 0.21%) in C. fluminea were significantly higher (p < 0.05) at the raw stage. On the other hand, the ash (2.09 ± 0.03%) and crude protein (9.45 ± 0.42%) were significantly higher (p < 0.05) at smoked stage. Meanwhile, carbohydrate (3.39 ± 0.49%) was significantly higher (p < 0.05) at the selling stage. The fatty acid percentage of smoked C. fluminea indicates that the total saturated fatty acid (SFA) content was higher than the total of both monounsaturated fatty acids (MUFA) and polyunsaturated fatty acids (PUFA). The obtained data indicates that the composition percentage of omega-6 (n-6) in PUFA is significantly greater than omega-3 (n-3). The n-6/n-3 ratio of smoked C. fluminea is 2.95–3.11 and therefore can be considered as a healthy diet. The findings of this study can improve consumers’ health through sufficient nutrient consumption and also provide economic benefits by increasing sellers’ income in Kelantan.