Industrial effluents and N-nitrosamines in karst aquatic systems: a study on distribution and ecological implications.

The discharge of electroplating wastewater, containing high concentrations of N-nitrosamines, poses significant risks to human health and aquatic ecosystems. Karst aquatic environment is easily impacted by N-nitrosamines due to the fragile surface ecosystem. However, it's still unclear in understanding N-nitrosamine transformation in karst water systems. To explore the response and transport of nine N-nitrosamines in electroplating effluent within both karst surface water and groundwater, different river and groundwater samples were collected from both the upper and lower reaches of the effluent discharge areas in a typical karst industrial catchment in Southwest China. Results showed that the total average concentrations of N-nitrosamines (∑NAs) in electroplating effluent (1800 ng/L) was significantly higher than that in the receiving river water (130 ng/L) and groundwater (70 ng/L). The dynamic nature of karst aquifers resulted in comparable average concentrations of ∑NAs in groundwater (70 ng/L) and river water (79 ng/L) at this catchment. Based on the principal component analysis and multiple linear regression analysis, the electroplating effluent contributed 89% and 53% of N-nitrosamines to the river water and groundwater, respectively. The results based on the species sensitivity distribution model revealed N-nitrosodibutylamine as a particularly toxic compound to aquatic organisms. Furthermore, the average N-nitrosamine carcinogenic risk was significantly higher in lower groundwater reaches compared to upper reaches. This study represents a pioneering effort in considering specific N-nitrosamine properties in evaluating their toxicity and constructing species sensitivity curves. It underscores the significance of electroplating effluent as a primary N-nitrosamine source in aquatic environments, emphasizing their swift dissemination and significant accumulation in karst groundwater.

Controlled solvothermal synthesis of self-assembled SrTiO3 microstructures for expeditious solar-driven photocatalysis dye effluents degradation.

In this work, the self-assembled SrTiO3 (STO) microstructures were synthesized via a facile one-step solvothermal method. As the solvothermal temperature increased from 140 °C to 200 °C, the STO changed from a flower-like architecture to finally an irregularly aggregated flake-like morphology. The photocatalytic performance of as-synthesized samples was assessed through the degradation of rhodamine B (RhB) and malachite green (MG) under simulated solar irradiation. The results indicated that the photocatalytic performance of STO samples depended on their morphology, in which the hierarchical flower-like STO synthesized at 160 °C demonstrated the highest photoactivities. The photocatalytic enhancement of STO-160 was benefited from its large surface area and mesoporous configuration, hence facilitating the presence of more reactive species and accelerating the charge separation. Moreover, the real-world practicality of STO-160 photocatalysis was examined via the real printed ink wastewater-containing RhB and MG treatment. The phytotoxicity analyses demonstrated that the photocatalytically treated wastewater increased the germination of mung bean seeds, and the good reusability of synthesized STO-160 in photodegradation reaction also promoted its application in practical scenarios. This work highlights the promising potential of tailored STO microstructures for effective environmental remediation applications.

Mechanism of the Synergistic Toxicity of Ampicillin and Cefazoline on Selenastrum capricornutum.

Ampicillin (AMP) and cefazolin (CZO) are commonly used ß-lactam antibiotics which are extensively globally produced. Additionally, AMP and CZO are known to have relatively high ecotoxicity. Notably, the mix of AMP and CZO creates a synergistic effect that is more harmful to the environment, and how exposure to AMP-CZO can induce synergism in algae remains virtually unknown. To yield comprehensive mechanistic insights into chemical toxicity, including dose-response relationships and variations in species sensitivity, the integration of multiple endpoints with de novo transcriptomics analyses were used in this study. We employed Selenastrum capricornutum to investigate its toxicological responses to AMP and CZO at various biological levels, with the aim of elucidating the underlying mechanisms. Our assessment of multiple endpoints revealed a significant growth inhibition in response to AMP at the relevant concentrations. This inhibition was associated with increased levels of reactive oxygen species (ROS) and perturbations in nitrogen metabolism, carbohydrate metabolism, and energy metabolism. Growth inhibition in the presence of CZO and the AMP-CZO combination was linked to reduced viability levels, elevated ROS production, decreased total soluble protein content, inhibited photosynthesis, and disruptions in the key signaling pathways related to starch and sucrose metabolism, ribosome function, amino acid biosynthesis, and the production of secondary metabolites. It was concluded from the physiological level that the synergistic effect of Chlorophyll a (Chla) and Superoxide dismutase (SOD) activity strengthened the growth inhibition of S. capricornutum in the AMP-CZO synergistic group. According to the results of transcriptomic analysis, the simultaneous down-regulation of LHCA4, LHCA1, LHCA5, and sodA destroyed the functions of the photosynthetic system and the antioxidant system, respectively. Such information is invaluable for environmental risk assessments. The results provided critical knowledge for a better understanding of the potential ecological impacts of these antibiotics on non-target organisms.

Analysing N-nitrosamine occurrence and sources in karst reservoirs, Southwest China.

N-nitrosamines in reservoir water have drawn significant attention because of their carcinogenic properties. Karst reservoirs containing dissolved organic matter (DOM) are important drinking water sources and are susceptible to contamination because of the fast flow of various contaminants. However, it remains unclear whether N-nitrosamines and their precursor, DOM, spread in karst reservoirs. Therefore, this study quantitatively investigated the occurrence and sources of N-nitrosamines based on DOM properties in three typical karst reservoirs and their corresponding tap water. The results showed that N-nitrosamines were widely spread, with detection frequencies > 85%. Similar dominant compounds, including N-nitrosodimethylamine, N-nitrosomethylethylamine, N-nitrosopyrrolidine, and N-nitrosodibutylamine, were observed in reservoirs and tap water, with average concentrations of 4.7-8.9 and 2.8-6.7 ng/L, respectively. The average carcinogenic risks caused by these N-nitrosamines were higher than the risk level of 10-6. Three-dimensional fluorescence excitation-emission matrix modeling revealed that DOM was composed of humus-like component 1 (C1) and protein-like component 2 (C2). Fluorescence indicators showed that DOM in reservoir water was mainly affected by exogenous pollution and algal growth, whereas in tap water, DOM was mainly affected by microbial growth with strong autopoietic properties. In the reservoir water, N-nitrosodiethylamine and N-nitrosopiperidine were significantly correlated with C2 and biological indicators, indicating their endogenously generated sources. Based on the principal component analysis and multiple linear regression methods, five sources of N-nitrosamines were identified: agricultural pollution, microbial sources, humus sources, degradation processes, and other factors, accounting for 46.8%, 36.1%, 7.82%, 8.26%, and 0.96%, respectively. For tap water, two sources, biological reaction processes, and water distribution systems, were identified, accounting for 75.7% and 24.3%, respectively. Overall, this study presents quantitative information on N-nitrosamines' sources based on DOM properties in typical karst reservoirs and tap water, providing a basis for the safety of drinking water for consumers.

N-nitrosamines in electroplating and printing/dyeing industrial wastewater treatment plants: Removal efficiency, environmental emission, and the influence on drinking water.

The discharge of industrial wastewater containing high concentrations of N-nitrosamines to the aquatic environment can impair downstream source waters and pose potential risks to human health. However, the transport and fate of N-nitrosamines in typical industrial wastewater treatment plants (IWWTPs) and the influence of these effluents on source water and drinking water are still unclear. This study investigated nine N-nitrosamines in four full-scale electroplating (E-) and printing/dyeing (PD-) IWWTPs, two drinking water treatment plants (DWTPs) in the lower reaches of these IWWTPs, and the corresponding tap water in South China. The total concentrations of N-nitrosamines (∑NAs) were 382-10,600, 480-1920, 494-789, and 27.9-427 ng/L in influents, effluents, source water, and tap water, respectively. The compositions of N-nitrosamine species in different influents varied a lot, while N-nitrosodi-n-butylamine (NDBA) and N-nitrosodimethylamine (NDMA) dominated in most of the effluents, source water, and tap water. More than 70 % N-nitrosamines were removed by wastewater treatment processes used in E-IWWTPs such as ferric-carbon micro-electrolysis (Fe/C-ME), while only about 50 % of N-nitrosamines were removed in PD-IWWTPs due to the use of chlorine reagent or other inefficient conventional processes such as flocculation by cationic amine-based polymers or bio-contact oxidation. Therefore, the mass fluxes of N-nitrosamines discharged from these industrial wastewaters to the environment in the selected two industrial towns were up to 14,700 mg/day. The results based on correlation and principal component analysis significantly demonstrated correlations between E-and PD-effluents and source water and tap water, suggesting that these effluents can serve as sources of N-nitrosamines to local drinking water systems. This study suggests that N-nitrosamines are prevalent in typical IWWTPs, which may infect drinking water systems. The findings of this study provide a basis data for the scientific evaluation of environmental processes of N-nitrosamines.

Toxic interactions at the physiological and biochemical levels of green algae under stress of mixtures of three azole fungicides.

Assessing the interactions between environmental pollutants and these mixtures is of paramount significance in understanding their negative effects on aquatic ecosystems. However, existing research often lacks comprehensive investigations into the physiological and biochemical mechanisms underlying these interactions. This study aimed to reveal the toxic mechanisms of cyproconazole (CYP), imazalil (IMA), and prochloraz (PRO) and corresponding these mixtures on Auxenochlorella pyrenoidosa by analyzing the interactions at physiological and biochemical levels. Higher concentrations of CYP, IMA, and PRO and these mixtures resulted in a reduction in chlorophyll (Chl) content and increased total protein (TP) suppression, and malondialdehyde (MDA) content exhibited a negative correlation with algal growth. The activity of catalase (CAT) and superoxide dismutase (SOD) decreased with increasing azole fungicides and their mixture concentrations, correlating positively with growth inhibition. Azole fungicides induced dose-dependent apoptosis in A. pyrenoidosa, with higher apoptosis rates indicative of greater pollutant toxicity. The results revealed concentration-dependent toxicity effects, with antagonistic interactions at low concentrations and synergistic effects at high concentrations within the CYP-IMA mixtures. These interactions were closely linked to the interactions observed in Chl-a, carotenoid (Car), CAT, and cellular apoptosis. The antagonistic effects of CYP-PRO mixtures on A. pyrenoidosa growth inhibition can be attributed to the antagonism observed in Chl-a, Chl-b, Car, TP, CAT, SOD, and cellular apoptosis. This study emphasized the importance of gaining a comprehensive understanding of the physiological and biochemical interactions within algal cells, which may help understand the potential mechanism of toxic interaction.

Carbide lime as substrates to boost energy recuperation and dyestuff removal in constructed wetland-microbial fuel cell integrated with copper oxide/carbon cloth cathode.

Methylene blue (MB) was regarded as a highly toxic and hazardous substance owing to its irreparable hazard and deplorable damage on the ecosystem and the human body. The treatment of this colorant wastewater appeared to be one of the towering challenges in wastewater treatment. In this study, a microbial fuel cell coupled with constructed wetland (CW-MFC) with effective MB elimination and its energy recuperation concurrently based on the incorporation of carbide lime as a substrate in a new copper oxide-loaded on carbon cloth (CuO/CC) cathode system was studied. The crucial influencing parameters were also delved, and the MB degradation and chemical oxygen demand (COD) removal efficiencies were correspondingly incremented by 97.3% and 89.1% with maximum power output up to 74.1 mW m-2 at optimal conditions (0.2 g L-1 carbide lime loading and 500 Ω external resistance). The carbide lime with high calcium ion content was greatly conducive for the enrichment of critical microorganism and metabolic activities. The relative abundances of functional bacteria including Proteobacteria and Actinobacteriota were vividly increased. Moreover, the impressive results obtained in printed ink wastewater treatment with a COD removal efficiency of 81.3% and a maximum power density of 58.2 mW m-2, which showcased the potential application of CW-MFC.

Occurrence and fate of N-nitrosamines in full-scale domestic wastewater treatment plants and their impact on receiving waters along the Lijiang River, China.

Domestic wastewaters contaminated with N-nitrosamines pose a significant threat to river ecosystems worldwide, particularly in urban areas with riparian cities. Despite widespread concern, the precise impact of these contaminants on receiving river waters remains uncertain. This study investigated eight N-nitrosamines in wastewater treatment plants (WWTPs) and their adjacent receiving river, the Lijiang River in Guilin City, Southwest China. By analyzing thirty wastewater samples from five full-scale WWTPs and twenty-three river water samples from Guilin, we quantified the mass loads of N-nitrosamines discharged into the surrounding watershed via domestic effluents. The results revealed that N-nitrosodimethylamine (10-60 ng/L), N-nitrosodiethylamine (3.4-22 ng/L), and N-nitrosopyrrolidine (not detected-4.5 ng/g) were predominant in influents, effluents, and sludge, respectively, with the overall removal efficiencies ranging from 17.7 to 65.6% during wastewater treatment. Cyclic activated sludge system and ultraviolet disinfection were effective in removing N-nitrosamines (rates of 59.6% and 24.3%), while chlorine dioxide disinfection promoted their formation. A total of 30.4 g/day of N-nitrosamine mass loads were observed in the Lijiang River water, with domestic effluents contributing about 31.3% (19.4 g/day), followed by livestock breeding wastewater (34.5%, 12.0 g/day), and unknown sources (24.7%, 7.5 g/day). These findings highlight the critical role of WWTPs in transporting N-nitrosamines to watersheds and emphasize the urgent need for further investigation into other potential sources of N-nitrosamine pollution within watersheds.

Monitoring of Medical Wastewater by Sensitive, Convenient, and Low-Cost Determination of Small Extracellular Vesicles Using a Glycosyl-Imprinted Sensor.

The monitoring of small extracellular vesicles (sEVs) in medical waste is of great significance for the prevention of the spread of infectious diseases and the treatment of environmental pollutants in medical waste. Highly sensitive and selective detection methods are urgently needed due to the low content of sEVs in waste samples and the complex sample composition. Herein, a glycosyl-imprinted electrochemical sensor was constructed and a novel strategy for rapid, sensitive, and selective sEVs detection was proposed. The characteristic trisaccharide at the end of the glycosyl chain of the glycoprotein carried on the surface of the sEVs was used as the template molecule. The glycosyl-imprinted polymer films was then prepared by electropolymerization with o-phenylenediamine (o-PD) and 3-aminophenylboronic acid (m-APBA) as functional monomers. sEVs were captured by the imprinted cavities through the recognition and adsorption of glycosyl chains of glycoproteins on sEVs. The m-APBA molecule also acted as a signal probe and was then attached on the immobilized glycoprotein on the surface of sEVs by boric acid affinity. The electrochemical signal of m-APBA was amplificated due to the abundant glycoproteins on the surface of sEVs. The detection range of the sensor was 2.1 × 104 to 8.7 × 107 particles/mL, and the limit of detection was 1.7 × 104 particles/mL. The sensor was then applied to the determination of sEVs in medical wastewater and urine, which showed good selectivity, low detection cost, and good sensitivity.

Synergistic removal performance and mechanism of Cd(II) and As(III) from irrigation water by iron sulfide-based porous biochar.

Since Cd(II) and As(III) have extremely opposite chemical characteristics, it is a huge challenging to simultaneously remove these two ions from aqueous solutions. Therefore, a novel iron sulfide-based porous biochar (FSB) was synthesized and used to evaluate its Cd(II) and As(III) removal performance and mechanisms. The characterization and batch experiments results indicated that FeS was successfully loaded on the surface of biochar and increased its adsorption sites. The iron sulfide-based porous biochar was very favorable for the removal of Cd(II) and As(III) in the weakly acidic environment. The maximum adsorption of Cd(II) and As(III) by FSB was 108.8 mg g-1 and 76.3 mg g-1, respectively, according to the Langmuir and Freundlich isothermal adsorption model, and the adsorption equilibrium time was 12 h and 4 h, respectively, according to the pseudo-second-order kinetic model. In the coexisting ion system, Cd(II) adsorption was suppressed by Ca2+, Mg2+, and humic acid, but enhanced by PO43- and As(III). As(III) adsorption was inhibited by PO43- and humic acid. Precipitation and complexation are the predominant adsorption mechanisms of Cd(II) and As(III), which contribute to the formation of Cd-O, Fe-O-Cd, As-O, Fe-O-As, ternary complex Cd-Fe-As, and stable compounds FeAsO4·2H2O and CdS. Therefore, The iron sulfide-based porous biochar can be an efficient and environmentally friendly candidate for the treatment of Cd(II) and As(III) co-polluted irrigation water.

Impact of agricultural activities on the occurrence of N-nitrosamines in an aquatic environment.

N-Nitrosamines, nitroso compounds with strong carcinogenic effects on humans, have been frequently detected in natural waters. In agricultural areas, there is typically a lack of drinking water treatment processes and distribution systems. As a result, residents often consume groundwater as drinking water which may contain N-nitrosamines, necessitating the investigation of the occurrence, sources, and carcinogenic risk of N-nitrosamines within the groundwater of agricultural areas. This study identified eight N-nitrosamines in groundwater and river water in the Jianghan Plain, a famous agricultural region in central China. N-Nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosomorpholine (NMOR), N-nitrosopyrrolidine (NPYR), and N-nitrosodi-n-butylamine (NDBA) were detected in groundwater, with NDMA being the main compound detected (up to 52 ng L-1). Comparable concentrations of these N-nitrosamines were also found in river water. From laboratory experiments, we found a tremendous potential for the formation of N-nitrosamines in groundwater. Principal component analysis and multiple linear regression analysis results showed that the primary sources of N-nitrosamines in groundwater were the uses of nitrogen fertilizers and pesticides carrying specific N-nitrosamines such as NPYR. The average total carcinogenic risk values of detected N-nitrosamines were higher than the acceptable risk level (10-5), suggesting a potential carcinogenic risk of groundwater. Further research is urgently needed to minimize N-nitrosamine levels in the groundwater of agricultural areas, particularly in those where pesticides and fertilizers are heavily used.

Eminent destruction of organics and pathogens concomitant with power generation in a visible light-responsive photocatalytic fuel cell with NiFe2O4/ZnO pine tree-like photoanode and CuO/Cu2O nanorod cathode.

Environmental conservation and energy scarcity have become two core challenges with the ever-increasing advancement of industry, particularly chemical energy rich wastewater comprising refractory organics and pathogenic microbes. Here, a multifunctional photocatalytic fuel cell (PFC) was devised using NiFe2O4 nanoparticle-loaded on pine tree-like ZnO/Zn (NiFe2O4/ZnO/Zn) photoanode and CuO/Cu2O nanorods-loaded on Cu (CuO/Cu2O/Cu) cathode for extracting electricity upon wastewater treatment. When fed with Rhodamine B (RhB) dyestuff, the NiFe2O4/ZnO/Zn-PFC provided the maximum power density (Pmax) of 0.539 mW cm-2 upon visible light irradiation with an average RhB degradation of 85.2%, which were 2.8 and 2.7 times higher than ZnO/Zn, respectively. The remarkable enhanced NiFe2O4/ZnO/Zn-PFC performance was owing to the synergistic effect of pine tree-like structure and Z-scheme heterostructure. The pine tree-like with high surface area was not only for effective harnessing photon energies but also provided more directional routes for rapid segregation and transport of carriers and higher interface contacting areas with electrolyte. Through a series of systematic characterizations, the Z-scheme heterostructure mechanism of the system and organics degradation pathway were also speculated. Additionally, the performance of the NiFe2O4/ZnO/Zn-PFC in industry printing wastewater showed Pmax of 0.600 mW cm-2, which was considerably impressive as real wastewater was challenging to accomplish. The phytotoxicity outcome also manifested that the comprehensive toxicity of RhB was eradicated after PFC treatment. Lastly, the excellent recyclability and the pronounced bactericidal effect towards Escherichia coli and Staphylococcus aureus were other attributions which enabled the NiFe2O4/ZnO/Zn-PFC for possible practical application.

Biodegradation of nitrate and p-bromophenol using hydrogen-based membrane biofilm reactors in parallel.

ABSTRACTP-bromophenol (4-BP) is a toxic halogenated phenolic organic compound. The conventional treatment processes for 4-BP elimination are costly and inefficient, with complete mineralization remaining a challenge for water treatment. To overcome these limitations, we investigated the treatment of 4-BP in a membrane biofilm reactor (MBfR) using hydrogen as an electron donor. The pathway of 4-BP degradation within the H2-MBfR was investigated through long-term operational experiments by considering the effect of nitrate and 4-BP concentrations, hydrogen partial pressure, static experiments, and microbial community diversity, which was studied using 16S rRNA. The results showed that H2-MBfR could quickly remove approximately 100% of 4-BP (up to 20 mg/L), with minimal intermediate product accumulation and 10 mg/L of nitrate continuously reduced. The microbial community structure showed that the presence of H2 created an anaerobic environment, and Thauera was the dominant functional genus involved in the degradation of 4-BP. The genes encoding related enzymes were further enhanced. This study provides an economically viable and environmentally friendly bioremediation technique for water bodies that contain 4-BP and nitrates.

Treatment of diluted palm oil mill effluent (POME) synchronous with electricity production in a persulfate oxidant-promoted photocatalytic fuel cell.

Attributable to the prosperous production growth of palm oil in Malaysia, the generated palm oil mill effluent (POME) poses a high threat owing to its highly polluted characteristic. Urged by the escalating concern of environmental conservation, POME pollution abatement and potential energy recovery from the effluent are flagged up as a research topic of interest. In this study, a cutting-edge photocatalytic fuel cell (PFC) system with employment of ZnO/Zn nanorod array (NRA) photoanode, CuO/Cu cathode, and persulfate (PS) oxidant was successfully designed to improve the treatment of POME and simultaneous energy production. The photoelectrodes were fabricated and characterized by field emission scanning electron microscopy with energy (FESEM), X-ray diffraction (XRD), energy-dispersive X-ray (EDX), and Brunauer, Emmett, and Teller analysis (BET). Owing to the properties of strong oxidant of PS, the proposed PFC/PS system has exhibited exceptional performance, attaining chemical oxygen demand (COD) removal efficiency of 96.2%, open circuit voltage (Voc) of 740.0 mV, short circuit current density (Jsc) of 146.7 µA cm-2, and power density (Pmax) of 35.6 µW cm-2. The pre-eminent PFC/PS system performance was yielded under optimal conditions of 2.5 mM of persulfate oxidant, POME dilution factor of 1:20, and natural solution pH of 8.51. Subsequently, the postulated photoelectrocatalytic POME treatment mechanism was elucidated by the radical scavenging study and Mott-Schottky (M-S) analysis. The following recycling test affirmed the stability and durability of the photoanode after four continuous repetition usages while the assessed electrical energy efficiency revealed the economic viability of PFC system serving as a post-treatment for abatement of POME. These findings contributed toward enhancing the sustainability criteria and economic viability of palm oil by adopting sustainable and efficient POME post-treatment technology.

[Removal of Cr(â ¥) via a Nickel Ferrite@Activated Carbon Composite Under Batch Experiments: Study of Characterization, Performance, and Mechanism].

A magnetic activated carbon adsorbent named NiFe2O4@AC was synthesized by modifying activated carbon with NiFe2O4 and used for the adsorption of Cr(Ⅵ) ions from waste water. The influencing factors, adsorption kinetics, and adsorption isotherms of Cr(Ⅵ) adsorption by the adsorbent were investigated. The results showed that the removal rate of Cr(Ⅵ) adsorption by NiFe2O4@AC reached 96.92%, and the adsorption amount reached 72.62 mg·g-1 at the adsorption conditions of temperature (298 K), pH 2, Cr(Ⅵ) initial concentration (150 mg·L-1), adsorbent dosage (0.1 g), and contact time (720 min). The experimental data were best described by the proposed secondary kinetics and Langmuir model, indicating that the adsorption process was a monolayer chemisorption process. The increase in temperature favored the adsorption of Cr(Ⅵ) on NiFe2O4@AC because the adsorption process was a spontaneous, heat-absorbing reaction. The adsorption mechanism of NiFe2O4@AC was mainly through complexation and electrostatic attraction to adsorb Cr(Ⅵ); meanwhile, the applied magnetic field could be separated from the solution, which has good application prospects.

Toxicity interactions of azole fungicide mixtures on Chlorella pyrenoidosa.

It is acknowledged that azole fungicides may release into the environment and pose potential toxic risks. The combined toxicity interactions of azole fungicide mixtures, however, are still not fully understood. The combined toxicities and its toxic interactions of 225 binary mixtures and 126 multi-component mixtures on Chlorella pyrenoidosa were performed in this study. The results demonstrated that the negative logarithm 50% effect concentration (pEC50 ) of 10 azole fungicides to Chlorella pyrenoidosa at 96 h ranged from 4.23 (triadimefon) to 7.22 (ketoconazole), while the pEC50 values of the 351 mixtures ranged from 3.91 to 7.44. The high toxicities were found for the mixtures containing epoxiconazole. According to the results of the model deviation ratio (MDR) calculated from the concentration addition (MDRCA ), 243 out of 351 (69.23%) mixtures presented additive effect at the 10% effect, while the 23.08% and 7.69% of mixtures presented synergistic and antagonistic effects, respectively. At the 30% effect, 47.29%, 29.34%, and 23.36% of mixtures presented additive effects, synergism, and antagonism, respectively. At the 50% effect, 44.16%, 34.76%, and 21.08% of mixtures presented additive effects, synergism, and antagonism, respectively. Thus, the toxicity interactions at low concentration (10% effect) were dominated by additive effect (69.23%), whereas 55.84% of mixtures induced synergism and antagonism at high concentration (50% effect). Climbazole and imazalil were the most frequency of components presented in the additive mixtures. Epoxiconazole was the key component induced the synergistic effects, while clotrimazole was the key component in the antagonistic mixtures.

Occurrence and mass loads of N-nitrosamines discharged from different anthropogenic activities in Desheng River, South China.

N-nitrosamines are widespread in various bodies of water, which is of great concern due to their carcinogenic risks and harmful mutagenic effects. Livestock rearing, domestic, agricultural, and industrial wastewaters are the main sources of N-nitrosamines in environmental water. However, information on the amount of N-nitrosamines these different wastewaters contribute to environmental water is scarce. Here, we investigated eight N-nitrosamines and assessed their mass loadings in the Desheng River to quantify the contributions discharged from different anthropogenic activities. N-nitrosodimethylamine (NDMA) (< 1.6-18 ng/L), N-nitrosomethylethylamine (NMEA) (< 2.2 ng/L), N-nitrosodiethylamine (NDEA) (< 1.7-2.4 ng/L), N-nitrosopyrrolidine (NPYR) (< 1.8-18 ng/L), N-nitrosomorpholine (NMOR) (< 2.0-3.5 ng/L), N-nitrosopiperidine (NPIP) (< 2.2-2.5 ng/L), and N-nitrosodi-n-butylamine (NDBA) (< 3.3-16 ng/L) were detected. NDMA and NDBA were the dominant compounds contributing 89% and 92% to the total N-nitrosamine concentrations. The mean cumulative concentrations of N-nitrosamines in the livestock rearing area (26 ± 11 ng/L) and industrial area (24 ± 4.8 ng/L) were higher than those in the residential area (16 ± 6.3 ng/L) and farmland area (15 ± 5.1 ng/L). The mean concentration of N-nitrosamines in the tributaries (22 ng/L) was slightly higher than that in the mainstem (17 ng/L), probably due to the dilution effect of the mainstem. However, the mass loading assessment based on the river's flow and water concentrations suggested the negligible mass emission of N-nitrosamines into the mainstem from tributaries, which could be due to the small water flow of tributaries. The average mass loads of N-nitrosamines discharged into the mainstem were ranked as the livestock rearing area (742.7 g/d), industrial area (558.6 g/d), farmland area (93.9 g/d), and residential areas (83.2 g/d). In the livestock rearing, residential, and industrial area, NDMA (60.9%, 53.6%, and 46.7%) and NDBA (34.6%, 33.3%, and 44.9%) contributed the most mass loads; NDMA (23.4%), NDEA (15.8%), NPYR (10.1%), NPIP (12.8%), and NDBA (37.8%) contributed almost all the mass loads in the farmland area. Photodegradation amounts of NDMA (0.65 ~ 5.25 µg/(m3·day)), NDBA (0.37 ~ 0.91 µg/(m3·day)), and NDEA (0 ~ 0.66 µg/(m3·day)) were also calculated according to the mass loading. Quantifying the contribution of different anthropogenic activities to the river will provide important information for regional river water quality protection. Risk quotient (RQ) values showed the negligible ecological risks for fish, daphnid, and green algae.

Degradation Characteristics and Remediation Ability of Contaminated Soils by Using ß-HCH Degrading Bacteria.

Three degradation strains that can utilize ß-Hexachlorocyclohexanes (ß-HCH) as the sole carbon source were isolated from the soil substrate of constructed wetland under long-term ß-HCH stress, and they were named A1, J1, and M1. Strains A1 and M1 were identified as Ochrobactrum sp. and strain J1 was identified as Microbacterium oxydans sp. by 16S rRNA gene sequence analysis. The optimum conditions for degradation with these three strains, A1, J1, and M1, were pH = 7, 30 °C, and 5% inoculum amount, and the degradation rates of 50 µg/L ß-HCH under these conditions were 58.33%, 51.96%, and 50.28%, respectively. Degradation characteristics experiments showed that root exudates could increase the degradation effects of A1 and M1 on ß-HCH by 6.95% and 5.82%, respectively. In addition, the degradation bacteria A1 and J1 mixed in a ratio of 1:1 had the highest degradation rate of ß-HCH, which was 69.57%. An experiment on simulated soil remediation showed that the compound bacteria AJ had the best effect on promoting the degradation of ß-HCH in soil within 98 d, and the degradation rate of ß-HCH in soil without root exudates was 60.22%, whereas it reached 75.02% in the presence of root exudates. The addition of degradation bacteria or degradation bacteria-root exudates during soil remediation led to dramatic changes in the community structure of the soil microorganisms, as well as a significant increase in the proportion of aerobic and Gram-negative bacterial groups. This study can enrich the resources of ß-HCH degrading strains and provided a theoretical basis for the on-site engineering treatment of ß-HCH contamination.

Endocrine Disruption of Propylparaben in the Male Mosquitofish (Gambusia affinis): Tissue Injuries and Abnormal Gene Expressions of Hypothalamic-Pituitary-Gonadal-Liver Axis.

Propylparaben (PrP) is a widely used preservative that is constantly detected in aquatic environments and poses a potential threat to aquatic ecosystems. In the present work, adult male mosquitofish were acutely (4d) and chronically (32d) exposed to environmentally and humanly realistic concentrations of PrP (0, 0.15, 6.00 and 240 µg/L), aimed to investigate the toxic effects, endocrine disruption and possible mechanisms of PrP. Histological analysis showed time- and dose-dependent manners in the morphological injuries of brain, liver and testes. Histopathological alterations in the liver were found in 4d and severe damage was identified in 32d, including hepatic sinus dilatation, cytoplasmic vacuolation, cytolysis and nuclear aggregation. Tissue impairments in the brain and testes were detected in 32d; cell cavitation, cytomorphosis and blurred cell boundaries appeared in the brain, while the testes lesions contained spermatogenic cell lesion, decreased mature seminal vesicle, sperm cells gathering, seminiferous tubules disorder and dilated intercellular space. Furthermore, delayed spermatogenesis had occurred. The transcriptional changes of 19 genes along the hypothalamus-pituitary-gonadal-liver (HPGL) axis were investigated across the three organs. The disrupted expression of genes such as Ers, Ars, Vtgs, cyp19a, star, hsd3b, hsd17b3 and shh indicated the possible abnormal steroidogenesis, estrogenic or antiandrogen effects of PrP. Overall, the present results provided evidences for the toxigenicity and endocrine disruptive effects on the male mosquitofish of chronic PrP exposure, which highlights the need for more investigations of its potential health risks.

Synergistically interactive P-Co-N bonding states in cobalt phosphide-decorated covalent organic frameworks for enhanced photocatalytic hydrogen evolution.

Non-noble materials with high efficiency and stability are essential for renewable energy applications. Herein, cobalt phosphide nanoparticles-decorated covalent organic frameworks (CTF-CoP) are synthesized via an in situ self-assembly method combined with the calcination process. In such a configuration, an intimate interaction between CoP and CTF matrix is gained through the Co-N chemical bonds, which not only significantly enhance the recyclability of CoP nanoparticles but also significantly improve the charge separation efficiency. Besides, the synergistically interactive Pδ--Coδ+-Nδ- states induced by the polarization effect of N-anchoring sites benefit for the adsorption and dissociation of water molecules in CTF-CoP. Consequently, CTF-CoP exhibits a higher photocatalytic hydrogen evolution rate (261.7 µmol g-1 h-1) and better durability as compared with the physically fixed CTF/CoP composite (64.8 µmol g-1 h-1) and even the noble metal-based CTF-Pt (191.3 µmol g-1 h-1). This work provides an avenue to construct highly stable non-noble photocatalyst for energy conversion and also emphasizes the potential of CTFs in constructing efficient heterojunctions.