[Research Progress on Pollution Characteristics, Degradation, and Transformation of Typical PPCPs in the Process of Wastewater Treatment].

Pharmaceuticals and personal care products (PPCPs) have received extensive attention as a new type of pollutant inin the 21st century, and the ecological and health risks caused by PPCPs have gradually been recognized by government regulatory agencies. Daily use of PPCPs has led to their frequent detection and high concentrations in the influent, effluent, and sludge of wastewater treatment plants, but traditional wastewater treatment processes can't remove them effectively. Most research about enhancing the removal of PPCPs through microbial degradation, photodegradation, and ozonation is still in the laboratory research stage, and the removal effects are not satisfactory when applied to actual sewage treatment. Therefore, the effective removal of PPCPs from domestic wastewater is a critical technical problem that urgently needs to be studied and solved in the coming years. At present, many scholars do not have a comprehensive understanding about the degradation and transformation behaviors of microbes, ultraviolet, and ozone for typical PPCPs in the wastewater treatment process, so it is necessary to conduct a systematic analysis and discussion. In this study, 16 typical PPCPs frequently detected in sewage treatment plants were selected as research objects through a literature review. The occurrence, removal characteristics, and sludge adsorption properties of typical PPCPs in wastewater treatment plants were analyzed and summarized. The degradation and transformation behavior of typical PPCPs under microbial, ultraviolet, and ozone treatments in the wastewater treatment process were also discussed. Finally, based on current research gaps, some research directions for the removal and transformation of PPCPs in wastewater were proposed:① investigation into the removal characteristics of PPCPs by actual biochemical treatment; ② study on the mechanism of microbial degradation and transformation of typical PPCPs during biochemical treatment; ③ study on the degradation and transformation mechanism of typical PPCPs by UV/ozone in an actual sewage system; and ④ research on the application technology of removing PPCPs from sewage via microbial degradation, photodegradation, ozone oxidation, etc. The relevant results of this study can provide a reference for the pollution control of typical PPCPs in the sewage treatment process.

Identification and quantification of nanoplastics in different crops using pyrolysis gas chromatography-mass spectrometry.

Quantitative studies of nanoplastics (NPs) abundance on agricultural crops are crucial for understanding the environmental impact and potential health risks of NPs. However, the actual extent of NP contamination in different crops remains unclear, and therefore insufficient quantitative data are available for adequate exposure assessments. Herein, a method with nitric acid digestion, multiple organic extraction combined with pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) quantification was used to determine the chemical composition and mass concentration of NPs in different crops (cowpea, flowering cabbage, rutabagas, and chieh-qua). Recoveries of 74.2-109.3% were obtained for different NPs in standard products (N = 6, RSD <9.6%). The limit of detection (LOD) and the limit of quantitation (LOQ) were 0.02-0.5 µg and 0.06-1.5 µg, respectively. The detection method for NPs exhibited good external calibration curves and linearity with 0.99. The results showed that poly (vinylchloride) (PVC), poly (ethylene terephthalate) (PET), polyethylene (PE), and polyadiohexylenediamine (PA66) NPs could be detected in crop samples, although the accumulation levels associated with the various crops varied significantly. PVC (N.D.-954.3 mg kg-1, dry weight (DW)) and PE (101.3-462.9 mg kg-1, DW) NPs were the dominant components in the samples of all four crop species, while high levels of PET (414.3-1430.1 mg kg-1, DW) NPs were detected in cowpea samples. Furthermore, there were notable differences in the accumulation levels of various edible crop parts, such as stems (60.2%) > leaves (39.8%) in flowering cabbage samples and peas (58.8%) > pods (41.2%) in cowpea samples. This study revealed the actual extent of NP contamination in different types of crops and provided crucial reference data for future research.

Effects of polyethylene microplastics occurrence on estrogens degradation in soil.

Growing focus has been drawn to the continuous detection of high estrogens levels in the soil environment. Additionally, microplastics (MPs) are also of growing concern worldwide, which may affect the environmental behavior of estrogens. However, little is known about effects of MPs occurrence on estrogens degradation in soil. In this study, polyethylene microplastics (PE-MPs) were chosen to examine the influence on six common estrogens (estrone (E1), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2), estriol (E3), diethylstilbestrol (DES), and 17α-ethinylestradiol (17α-EE2)) degradation. The results indicated that PE-MPs had little effect on the degradation of E3 and DES, and slightly affected the degradation of 17α-E2, however, significantly inhibited the degradation of E1, 17α-EE2, and 17ß-E2. It was explained that (i) obvious oxidation reaction occurred on the surface of PE-MPs, indicating that PE-MPs might compete with estrogens for oxidation sites, such as redox and biological oxidation; (ii) PE-MPs significantly changed the bacterial community in soil, resulting in a decline in the abundance of some bacterial communities that biodegraded estrogens. Moreover, the rough surface of PE-MPs facilitated the estrogen-degrading bacterial species (especially for E1, E2, and EE2) to adhere, which decreased their reaction to estrogens. These findings are expected to deepen the understanding of the environmental behavior of typical estrogens in the coexisting system of MPs.

Effect comparisons of different conditioners and microbial agents on the degradation of estrogens during dairy manure composting.

To investigate the degradation efficiency of conditioners and commercial microbial agents on estrogens (E1, 17α-E2, 17ß-E2, E3, EE2, and DES) in the composting process of dairy manure, seven different treatments (RHB-BF, OSP-BF, SD-BF, MR-BF, MR-FS, MR-EM, and MR-CK) under forced ventilation conditions were composted and monitored regularly for 30 days. The results indicated that the removal rates of estrogens in seven treatments ranged from 95.35% to 99.63%, meanwhile the degradation effect of the composting process on 17ß-Estradiol equivalent (EEQ) was evaluated, and the removal rate of ΣEEQ ranged from 96.42% to 99.72%. With the combined addition of rice husk biochar (RHB) or oyster shell powder (OSP) and bio-bacterial fertilizer starter cultures (BF), namely RHB-BF and OSP-BF obviously promoted the rapid degradation of estrogens. 17ß-E2 was completely degraded on the fifth day of composting in OSP-BF. Microbial agents have some promotional effect and enhances the microbial degradation of synthetic estrogen (EE2, DES). According to the results of RDA, pH and EC were the main environmental factors affecting on the composition and succession of estrogen-related degrading bacteria in composting system. As predominant estrogens-degrading genera, Acinetobacter, Bacillus, and Pseudomonas effected obviously on the change of estrogens contents. The research results provide a practical reference for effective composting of dairy manure to enhancing estrogens removal and decreasing ecological risk.

Fulvic acid enhanced peroxymonosulfate activation over Co-Fe binary metals for efficient degradation of emerging bisphenols.

Bisphenol F (BPF) and bisphenol S (BPS) are emerging bisphenols, which have become the main substitutes for bisphenol A (BPA) in industrial production and are also considered as new environmental pollution challenges. Thus, the necessity for an effective approach to remove BPF and BPS is essential. In this study, fulvic acid (FA) was used to modify Co-Fe binary metals (CFO) for peroxymonosulfate (PMS) activation. The characterization results demonstrated that CFO changed significantly in morphology after compounding with FA, with smaller particle size and 5.6 times larger specific surface area, greatly increasing the active sites of catalyst; Moreover, humic acid-like compounds increased the surface functional groups of CFO, especially phenolic hydroxyl, which could effectively prolong the PMS activation. The concentration of all reactive species, such as SO4•-, •OH, O2•-, and 1O2 increased in FA@CFO/PMS system. As a result, the degradation efficiency of CFO for both BPF and BPS was significantly improved after compounding FA, which also had a wide range of pH applications. The degradation pathways of both BPF and BPS were proposed based on liquid chromatography-mass spectrometry (LC-MS) analysis and the density functional theory (DFT) calculations. Our findings are expected to provide new strategies and methods for remediation of environmental pollution caused by emerging bisphenols.

[Sorption Characteristics and Site Energy Distribution Theory of Typical Estrogens on Microplastics].

Microplastics (MPs) and estrogens are high-profile emerging contaminants at present, and MPs might become the carrier of estrogens in the environment and induce combined pollution. To study the adsorption behavior of polyethylene (PE) microplastics to typical estrogens, the adsorption isothermal properties of the six estrogens[estrone (E1), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2), estriol (E3), diethylstilbestrol (DES), and ethinylestradiol (17α-EE2)] in single-solute and mixed-solute systems were studied through batch equilibrium adsorption experiments, in which the PE microplastics before and after adsorption were characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Then, the site energy distribution theory of the adsorption of six estrogens on PE microplastics was further analyzed based on the Freundlich model. The results showed that the adsorption process of selected estrogens with two concentrations (100 µg·L-1 and 1000 µg·L-1) on PE were more consistent with the pseudo-second order kinetic model. The increase in initial concentration reduced the equilibrium time of adsorption and increased the adsorbing capacity of estrogens on PE. In the single system (one estrogen) or mixed system (six estrogens) with different concentrations (10 µg·L-1-2000 µg·L-1), the Freundlich model showed the best fitting effect for the adsorption isotherm data (R2>0.94). The results of isothermal adsorption experiments and XPS and FTIR spectra showed that the adsorption of estrogens on PE in the two systems was heterogeneous adsorption, and hydrophobic distribution and van der Waals forces were the principal factors in the process of adsorption. The occurrence of C-O-C (in only the DES and 17α-EE2 systems) and O-C[FY=,1]O (in only the 17α-EE2 system) indicated that the adsorption of synthetic estrogens on PE was affected slightly by chemical bonding function, but no obvious effects were observed for natural estrogens. The results of site energy distribution analysis showed that, compared with the single system, the adsorption site energy of each estrogen shifted to the high-energy region in its entirety in the mixed system, and the site energy increased by 2.15%-40.98%. The energy change in DES was the most significant among all of the estrogens, indicating its competitive advantage in the mixed system. The above results of this study can provide some reference for the study of adsorption behavior, mechanism of action, and environmental risks under the coexisting condition of organic pollutants and MPs.

Emission of volatile organic compounds (VOCs) from application of commercial pesticides in China.

Applying pesticides can result in emissions of volatile organic compounds (VOCs), but little is known about VOC emission characteristics and the quantities in particular regions. We investigated the use of pesticides in China based on a large-scale survey of 330 counties in 31 provinces and evaluated the national pesticide VOC emission potentials based on thermogravimetric analysis of 1930 commercial pesticides. The results showed that herbicides were the most extensively used pesticide category in China, accounting for 43.47%; emulsifiable concentrate (EC), suspension concentrate, and wettable powder were the dominant pesticide formulations, with proportions of 26.75%, 17.68%, and 17.31%, respectively. The VOC emission potential coefficient (EP) of the liquid formulations was higher than the solid formulations, and the maximum mean EP was 45.59% for EC and the minimum was 0.76% for WP. Among 437 high-VOC pesticide products used in China, EC accounted for 83.52%, and 16.93% of those contained abamectin. The total VOC emissions derived from commercial pesticides in China were 280 kt (kilotons) in 2018, and 65.35% of the contribution was derived from EC. Shandong, Hunan, and Henan were the three provinces with the highest pesticide VOC emissions (>21 kt/y). The emission rate of VOCs from pesticides was 24.80 t/d in China, which was higher than in San Joaquin Valley, California. These findings suggest that some comprehensive measures (e.g., perfecting pesticide management policy, strict supervision for pesticide production and use, and strengthening pesticide reduction publicity) should be taken to reduce VOC emissions from pesticide applications.

Comparisons of pollution characteristics, emission situations, and mass loads for heavy metals in the manures of different livestock and poultry in China.

The application of livestock and poultry manures was the predominant source of heavy metals in agricultural soils, particularly in China. It is important to systematically compare the pollution characteristics, emission situations and mass loads for heavy metals in the manures of different livestock and poultry in China. According to analysis and estimation based on the reported concentration levels of eight heavy metals (Zn, Cu, Pb, Cd, Cr, Hg, As, and Ni) and the feed quantities of livestock (pig, cattle, and sheep) and poultry in 2017, the concentrations of Zn and Cu and the over-standard frequencies of Zn, Cu, Cd, and As were much higher than those of other heavy metals, especially in pig manure. In 2017, the total emission of livestock and poultry manure in China was 1.64 × 109 t (FW), which was mainly excreted from cattle (45.77%); while the total emission of heavy metals sourced from manures was 2.86 × 105 t (DW), with the predominant contribution originating from pig manure (71.52%). The highest mass loads of manures and heavy metals were observed in Shandong, Tianjin, Henan, and Shanghai, where heavy metal contamination may be occurring (especially for Zn and Cu). The heavy metal concentrations in livestock and poultry manures of China were similar to other countries; however, more heavy metals were discharged into agricultural land through manure (especially for Zn and Cu). For many countries, abundant Zn and Cu exist in agricultural soils, principally contributed by livestock and poultry manures. These heavy metals originate from their addition to livestock and poultry feeds. Therefore, reducing the addition of Zn and Cu in feeds is an effective measure to lower their input into agricultural soils.

[Discussion of Emissions and Health Risk of Polycyclic Aromatic Hydrocarbons (PAHs) from the Retreading Process of Waste Tires].

The emissions characteristics of 16 kinds of polycyclic aromatic hydrocarbons (PAHs) in ambient air during the waste tire retreading process (open-air storage, mixing, vulcanization, and grinding processes) and in workers' dormitory were analyzed. In addition, the occupational health risk of the workers was evaluated. Results showed that PAHs were detected in all retreading processes and in the workers' dormitory. The highest concentration site was the mixing process, followed by open-air storage and vulcanization process. The lowest concentration point was in the grinding process. The average concentration of PAHs in the workers' dormitory was 11.1 ng·m-3. The PAHs at all sampling points were largely phenanthrene (Phe), fluoranthene (Flu), anthracene (Ant), and pyrene (Pry), which also had a stronger linear correlation with the total PAH concentration. An analysis of the benzene rings showed that three ring and four ring were the majority, while two ring, five ring, and six ring components accounted for less than 10%. Results of the possible influencing factors of the PAHs revealed that the open-air storage and dormitory might be affected by a combustion source, but the mixing, vulcanization, and grinding processes might be affected by rubber oil. The principal component analysis (PCA) and cluster analysis showed that the spatial location of all sites would significantly influence the distribution of PAHs during the tire retreading process. The health risk assessment showed that occupational workers had a lower risk of lifelong cancer, and there was little influence on life expectancy.

Residual veterinary antibiotics in pig excreta after oral administration of sulfonamides.

Sulfonamides (SAs) are applied widely as feed additives in the farming of livestock and poultry. It can lead to the excretion of large amounts of SAs in manure and result in persistent environmental pollution. We evaluated the fate of four SAs, sulfamerazine (SM1), sulfachloropyridazine (SCP), sulfadimoxine (SDM') and sulfaquinoxaline (SQ), from oral administration to excretion in urine and feces in pigs. The four SAs were added to homemade feed to make them reach the required concentration gradient, which were 0, 50 and 100 mg/kg (low, normal and high concentrations, respectively). In different treatments, excretions of the four SAs were 35.68-86.88 %. With regard to total excretion, the order was SQ > SCP > SM1 > SDM' for all treatments. The concentration of SAs in the feed had significant effects on the amount of the four SAs excreted every day. The concentration of SAs in feces and in the urine for different treatments was 15.03-26.55 and 14.54-69.22 %, respectively. In each treatment, excretions of SCP, SDM' and SQ in feces were lower than that in urine. The four SAs remained longer in urine than in feces. Excretions in urine and feces were lower if SAs were administered orally rather than by injection.

Characterization and distribution of heavy metals, polybrominated diphenyl ethers and perfluoroalkyl substances in surface sediment from the Dayan River, South China.

In this study, surface sediment samples were collected from 11 sites in the Dayan River near an electronic waste site in Qingyuan. Heavy metals, polychlorinated biphenyls (PBDEs) and perfluoroalkyl substances (PFASs) were detected. The concentrations of Cu, Zn, Pb and Cd ranged from 12.1 to 641, 47.1 to 891, 39.2 to 641, 0.12 to 2.07 mg/kg dw, respectively. Total PBDEs ranged between 0.052 and 126.64 ng/g dw. BDE-47 and BDE-99 were the predominant PBDEs. The concentrations of PFASs in sediments ranged between 0.01 and 3.72 ng/g dw. The perfluorooctane sulfonate was predominantly PFASs. The strong positive correlations among Cu, Zn, perfluorooctanoic acid and PBDEs indicate that these contaminants were associated with each other and may share a common anthropogenic source in the sediments of the Dayan River.

Biomass fuels and coke plants are important sources of human exposure to polycyclic aromatic hydrocarbons, benzene and toluene.

Large amounts of carcinogenic polycyclic aromatic hydrocarbons (PAHs), benzene and toluene (BT) might be emitted from incomplete combustion reactions in both coal tar factories and biomass fuels in rural China. The health effects arising from exposure to PAHs and BT are a concern for residents of rural areas close to coal tar plants. To assess the environmental risk and major exposure sources, 100 coke plant workers and 25 farmers in Qujing, China were recruited. The levels of 10 mono-hydroxylated PAHs (OH-PAHs), four BT metabolites and 8-hydroxy-2'-deoxyguanosine (8-OHdG) in the urine collected from the subjects were measured. The 8-OHdG levels in the urine were determined to evaluate the oxidative DNA damage induced by the PAHs and BT. The results showed that the levels of the OH-PAHs, particularly those of 1-hydroxynathalene and 1-hydroxypyrene, in the farmers were 1-7 times higher than those in the workers. The concentrations of the BT metabolites were comparable between the workers and farmers. Although the exact work location within a coke oven plant might affect the levels of the OH-PAHs, one-way ANOVA revealed no significant differences for either the OH-PAHs levels or the BT concentrations among the three groups working at different work sites. The geometric mean concentration (9.17 µg/g creatinine) of 8-OHdG was significantly higher in the farmers than in the plant workers (6.27 µg/g creatinine). The levels of 8-OHdG did not correlate with the total concentrations of OH-PAHs and the total levels of BT metabolites. Incompletely combusted biomass fuels might be the major exposure source, contributing more PAHs and BT to the local residents of Qujing. The estimated daily intakes (EDIs) of naphthalene and fluorene for all of the workers and most of the farmers were below the reference doses (RfDs) recommended by the U.S. Environmental Protection Agency (EPA), except for the pyrene levels in two farmers. However, the EDIs of benzene in the workers and local farmers ranged from 590 to 7239 µg/day, and these levels were 2- to 30-fold higher than the RfDs recommended by the EPA. Biomass fuel combustion and industrial activities related to coal tar were the major sources of the PAH and BT exposure in the local residents. Using biomass fuels for household cooking and heating explains the higher exposure levels observed in the farmers relative to the workers at the nearby coal tar-related industrial facility.

[Determination of aniline in water and fish by liquid chromatography-tandem mass spectrometry].

A fast analytical method for the determination of aniline in water and fish meat by liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed. The water sample was mixed with acetonitrile by 4:1 (v/v) and the fish sample was extracted by 2.00 mL acetonitrile for each gram of sample, and then the extracts of water and fish samples were centrifuged at 5,000 r/min for 5 min. The separation was performed on a reversed-phase C18 column using mobile phases of acetonitrile-0.5% (v/v) formic acid aqueous solution (85:15, v/v). Aniline was separated within 3 min. The calibration curve was linear in the range of 0.5-500 pg/L with R2 > 0.999. The limits of detection (LODs) were 0.50 µg/L and 1.00 µg/kg and the limits of quantification (LOQs) were 1.00 µg/L and 2.00 µg/kg for aniline in water and fish meat, respectively. The average recoveries of aniline in water were 93.7% at the spiked level of 40 ng and 86.7% at the spiked level of 400 ng (n = 5). The average recoveries of aniline in fish were 96.8%, 92.6% and 81.8% at the spiked levels of 5, 50 and 500 ng respectively (n = 5). The relative standard deviations were 1.5%-9.2%. Thirteen water samples and twelve fish samples were collected from a reservoir polluted by aniline and the maximum contents found were 1,943. 6 µg/L in water and 60.8 µg/kg in fish. The method is suitable for the determination of aniline residues in water and fish with the characteristics of easy operation, high accuracy and precision.