Removal characteristics of microplastics in sewage flowing through a long-term operation surface flow wetland.

Microplastics (MPs) in sewage pose significant threats to aquatic system. Surface flow wetland (SFW) is a common natural wetland type, and is also used as a cheap and easy-to-build sewage treatment system for small and scattered settlements. However, seasonal variation patterns of MPs in sewage removed by SFW are still limited. Therefore, a field investigation was conducted in an SFW that has been operated for 17 years. The concentration of microplastics in the influent of the SFW (CMPs, in) ranged from 56 ± 6 to 250 ± 14 items L-1. The dominant plastic types were fibers and polyethylene terephthalate (PET). CMPs, in were high in summer and winter, significantly related to the seasonal dressing habits. The removal efficiencies of MPs in SFW were 48.03-92.32 % in different seasons, and the mechanisms of MP removal were different with traditional pollutants. Before flowing out occasionally or by heavy precipitation, MPs were primarily trapped in the SFW and underwent certain oxidation. Simulation experiments demonstrated that 47.5-92.9 % of MPs would be trapped in the SFW, and plants would significantly enhance the trapping capacities. This study sheds light on the seasonal variation characteristics and patterns of MPs in actual sewage, and clarifies the fate of MPs in a long-term operation SFW.

Organic ligands activate the dark formation of hydroxyl radicals (HO•) in surface soil/sediment: Yields, mechanisms, and applications.

Soil is an important sink for various pollutants. Recent findings suggest that soil and sediment would spontaneously form HO• through Fenton or Fenton-like reactions under natural conditions. In this study, the effects and mechanisms of organic ligands (OLs) on the occurrence of HO• in surface soil/sediment were experimentally and computationally examined. Results confirmed that HO• generation was ND-12.92 nmol/g in surface soil/sediment, and the addition of EDTA-2Na would significantly enhance the yields of HO• by 1.4-352 times. Moisture was the decisive factor of soil HO• generation. The release of Fe(II) from solid into the aqueous phase was essential for the stimulation of HO• in EDTA-2Na suspensions. Furthermore, complexation reactions between Fe(II) and OLs would enhance single electron transfer (SET) reactions and the formation of O2•-. Interestingly, for specific OLs, their stimulations on SET and formation of O2•- would depress HO• generation. Provoking HO• generation by OLs could be efficiently used to degrade sulfamethoxazole in rice field sediment. The study provided new knowledge on how commonly synthetic OLs affect the HO• generation in surface soil/sediment, and it additionally shed light on the engineered stimulation of in-situ Fenton reactions in natural soil/sediment.

Pivotal role of water molecules in the photodegradation of pymetrozine: New insights for developing green pesticides.

Photodegradation of the insecticide pymetrozine (PYM) was studied on surface of wax films, and in aqueous and nonaqueous phase. The half-life of PYM on the wax surface was approximately 250 times longer than in water. Scavenging experiments, laser flash photolysis, and spectra analysis indicated the first singlet excited state of PYM (S1 *PYM) to be the most important photoinduced species initiating the photodegradation. Quantum chemistry calculations identified significant molecular torsion and changes in the structure C-CN-N of S1 *PYM, and the absolute charges of the CN atoms increased and the bond strength weakened. Free energy surface analysis, and O18 labeling experiments further confirmed that the mechanism was two-step photoinduced hydrolysis. The first step is the hydrolysis of S1 *PYM at CN upon reaction with 2-3 water molecules (one H2O molecule as the catalyst). The second step is an intramolecular hydrogen transfer coupled with the cleavage of C-N bond and formation of two cyclic products. During the interactions, water molecules experience catalytic activation by transferring protons, while there is a negligible solvent effect. Clarifying the detailed photodegradation mechanisms of PYM is beneficial for the development of green pesticides that are photostable and effective on leaf surfaces, and photolabile and detoxified in the aquatic environment.

Efficient conversion of sewage sludge into hydrochar by microwave-assisted hydrothermal carbonization.

The treatment of sewage sludge (SS) is an environmental problem worldwide. In recent years, hydrothermal carbonization (HTC) of SS for hydrochar (HC) has attracted extensive attention. This study preliminarily explored the microwave-assisted HTC of SS for the first time. Increasing the reaction temperature (150-250 °C) and reaction time (0-120 min) resulted in a decrease in the HC yield, and it gradually increased with the rising solid-liquid ratio (0.03-0.25 g/mL). Compared with raw SS, the HC products possessed higher aromaticity, carbonization degree, porosity, and polarity, and lower content of soluble nutrients (N/P/K) and leachable heavy metals (Cu, Zn, Pb, Cd, Cr, and Ni), indicating a lower risk of nutrient and heavy metal loss. Attention should be paid to the total contents of Zn and Cd in HC exceeded the permitted value for use in cultivated land with edible crops. The use of CaO as a catalyst improved the yield of HC, made the HC and process water (PW) weakly alkaline, and further passivated the heavy metals in the HC. In the case of H3PO4, although the conversion of SS was enhanced (lower content of volatile organic matter in HC), the contents of soluble nutrients (N/P/K) in HC/PW increased, and the migration of Zn and Cd into process water was enhanced. The HCs obtained in this study had poor combustion properties, but higher ignition temperatures than raw SS. PW must be properly treated or recycled because it still contained high contents of organic matter and nutrients. This fundamental study provides basic insights into the microwave-assisted HTC of SS.

A comparison study of applying natural iron minerals and zero-valent metals as Fenton-like catalysts for the removal of imidacloprid.

Natural iron minerals and zero-valent metals have been widely tested as catalysts for the Fenton-like process, but the systematical comparison study about their catalytic performance was rarely conducted, and the risk of the secondary pollution of toxic heavy metals was still not uncertain. In this paper, a comparison study of applying pyrite, ilmenite, vanadium titano-magnetite (VTM), zero-valent iron (ZVI), and zero-valent copper (ZVC) as Fenton-like catalysts for the removal of imidacloprid was performed. The results showed that ZVI exhibited the highest activity among the recyclable solid catalysts with a removal rate of 96.8% at initial pH 3 using 10.78 mmol/L H2O2, due to iron corrosive dissolution. Vanadium titano-magnetite (VTM) exhibited the best activity at first use among tested minerals but with low reusability. Pyrite with stable morphology showed a medium but sustainable ability to degrade imidacloprid, achieving a removal rate of 10.5% in the fifth use. The reaction much favored the acidic condition of initial pH around 2 or 3. Meanwhile, there was a significant positive correlation between removal efficiency and dissolved Fe or Cu concentration. Pyrite was considered to be a promising catalyst in Fenton-like reaction. It was suggested that the system proceeded predominantly through a homogeneous route via dissolved Fe or Cu ions. Except ZVC and VTM, other tested catalysts showed the low possibility of causing secondary pollution of toxic metals in the application of Fenton-like process.

Effects of rice straw/wood sawdust addition on the transport/conversion behaviors of heavy metals during the liquefaction of sewage sludge.

Lignocellulosic biomass has been widely introduced into the liquefaction process of sewage sludge (SS) to improve the yield/quality of liquefaction products (bio-oil/biochar). This study explores the effect of adding rice straw (RS) and wood sawdust (WS) on the transport/conversion behaviors of heavy metals (HMs) during the liquefaction of SS. The introduction of lignocellulosic biomass, especially for RS, substantially lowers the total content of HMs in biochar. Most HMs (except Cd) still remain in biochar, although the introduction of RS/WS enhances the transport of HMs into bio-oils. The addition of RS/WS raises the percentage of HMs in active form, but the contents of bioavailable/leachable HMs are not considerably increased and even decreased in some cases, especially when RS is introduced. The overall pollution degree and environmental risk of HMs in biochars are lowered to a certain extent with the addition of RS/WS. Considering that the pollution degree and environmental risk of HMs present in biochars are still at a considerable level, appropriate pollution management measures should be undertaken when using such biochars for agricultural use.

Spatial and seasonal variations of antibiotic resistance genes and antibiotics in the surface waters of Poyang Lake in China.

Antibiotic resistance genes (ARGs) and antibiotics in the aquatic environment raise health concerns particularly on the dispersal and persistence of antibiotic resistance. Large lakes, which serve as catch basins of anthropogenic inputs provide an ideal environment for understanding the occurrence and accumulation of ARGs and antibiotics in freshwater environments. Here, the largest freshwater lake in China, Poyang Lake, located in the developing district of Yangtze valley was used to study the characterization of the spatial and seasonal variation of both ARGs and antibiotics. Results showed that twelve tested ARGs (sul1, sul2, sul3, tetA, tetB, tetC, tetH, tetW, tetO, tetM, qnrS, and qnrB) were detected in the surface waters of Poyang Lake, with a detection frequency ranging from 19.2% to 100%, and sul2 and tetA genes were identified as potential indicators of ARG pollution in this region. Among the 11 analyzed antibiotics, sulfonamides were the predominant antibiotics with a contribution of more than 50% to the total concentrations of tested antibiotics. The total concentrations of both ARGs and antibiotics were higher in the dry season than those in the wet season. Furthermore, ARGs and antibiotics in the surface waters also varied with sampling locations, being consistently at riverine tributaries. Positive correlations were also observed between the concentrations of ARGs and antibiotics, as well as the integron gene (intI1), indicating that antibiotics and intI1 may be playing important roles in the occurrence and dispersal of ARGs in the surface waters. Lastly, our results suggest that intensive anthropogenic activities related to antibiotic usage have substantially contributed to the occurrence and persistence of ARGs and antibiotics in Poyang Lake.

Effects of norfloxacin nicotinate on the early life stage of zebrafish (Danio rerio): Developmental toxicity, oxidative stress and immunotoxicity.

Norfloxacin nicotinate (NOR-N), an adduct of norfloxacin (NOR) and nicotinic acid, has been widely used for replacing NOR in animal husbandry and fishery industry. Nowadays, increasing evidences showed that NOR could pose toxic effects on fish and other aquatic organisms, but as its adduct, whether NOR-N could cause adverse effects on aquatic organisms is still unclear. To evaluate the toxic effects of NOR-N on the early life stage of zebrafish, we determined the changes in embryonic development (hatching rate, body length, malformation rate and mortality), antioxidant enzyme (superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (Gpx)) activities, malondialdehyde (MDA) content and gene expression levels related to antioxidant enzymes (Cu/Zn-sod, Mn-sod, CAT and Gpx) and innate immune system (tumor necrosis factor α (TNFα), interferon (IFN), Interleukin-1 beta (IL-1ß), IL-8, CXCL-clc, CC-chemokine, lysozyme (Lzy) and complement factors (C3)) after embryonic exposure to NOR-N till 96 hpf. The results showed that NOR-N exposure could decreased the hatching rate and body length, and increased abnormality and mortality as concentration-dependent during embryonic development process. NOR-N induced oxidative stress in zebrafish larvae through increasing the contents of MDA and the activities of SOD, CAT and Gpx, as well as the mRNA levels of genes related to these antioxidant enzymes. Moreover, the expression of TNFα, IFN, IL-1ß, IL-8, CXCL-clc, CC-chemokine, Lzy and C3 genes were significantly up-regulated after exposure to high concentration (5 and/or 25 mg/L) of NOR-N till 96 hpf, indicating that the innate immune system in zebrafish larvae was disturbed by NOR-N. Overall, our results suggested that NOR-N caused development toxicity, oxidative stress and immunotoxicity on the early life stage of zebrafish. Thus, widespread application of NOR-N might pose potential ecotoxicological risk on aquatic ecosystems.

Levels and human health risk assessments of heavy metals in fish tissue obtained from the agricultural heritage rice-fish-farming system in China.

China began to practice Rice-fish-farming system (RFFS) 1700 years ago. Nowadays, the widely spread of metals could be potential threats to the quality of RFFS fish. In this study, Pb, Cd, Hg, As and Cr as the top five most toxic heavy metals were determined in six species of RFFS fish meat obtained from 7 provinces in south China. The mean concentrations of metals in RFFS fish followed Pb (36.89 µg/kg) > As (33.36 µg/kg) > Cr (18.54 µg/kg) > Hg (16.35 µg/kg) > Cd (2.01 µg/kg), which were mostly lower in comparison with fish from traditional aquaculture systems raised by fish feeds. Grass carp obtained lower metal concentrations compared with other fishes, possibly indicating the importance of feeding habits of RFFS fish. Concentrations of metals in fish and RFFS sediment were in good correlations, and benthic fish obtained high pollution levels, suggesting the accumulation of metals through the direct contact with sediment. Risks assessments coupled with Monte Carlo simulation indicated the potential non-carcinogenic risks and carcinogenic risks decreased following As > Hg > Cr ≈ Pb > Cd, and As > Cr > Cd > Pb, respectively. These results suggested RFFS is still a successful mode of green agriculture.

Photo-induced oxidative damage to dissolved free amino acids by the photosensitizer polycyclic musk tonalide: Transformation kinetics and mechanisms.

Residue from the polycyclic musks (PCMs) in household and personal care products may harm human beings through skin exposure. To understand the health effects of PCMs when exposed to sunlight at molecular level, both experimental and computational methods were employed to investigate the photosensitized oxidation performance of 19 natural amino acids, the most basic unit of life. Results showed that a typical PCM, tonalide, acts as a photosensitizer to significantly increase photo-induced oxidative damage to amino acids. Both common and exceptional transformation pathways occurred during the photosensitization damage of amino acids. Experimental tests further identified the different mechanisms involved. The common transformation pathway occurred through the electron transfer from α amino-group of amino acids, accompanying with the formation of O2•-. This pathway was controlled by the electronic density of N atom in α amino-group. The exceptional transformation pathway was identified only for five amino acids, mainly due to the reactions with reactive oxygen species, e.g. 1O2 and excited triplet state molecules. Additionally, tonalide photo-induced transformation products could further accelerate the photosensitization of all amino acids with the common pathway. This study may support the protection of human health, and suggests the possible need to further restrict polycyclic musks use.

Occurrence and elimination of antibiotic resistance genes in a long-term operation integrated surface flow constructed wetland.

Wetland construction is a recommended domestic sewage treatment technique, owing to its simplicity and cost efficiency. Concentrations of 14 antibiotic resistance genes (ARGs) in an integrated surface flow constructed wetland (ICW) steadily operated over 10 years were investigated in the winter and summer. Domestic sewage was observed to be the primary source of ARGs in the ICW, and 77.8% and 59.5% removal rates of total targeted ARGs in the ICW were achieved in the winter and summer, respectively. Concentrations of five ARGs (sul1, tetA, tetC, tetE, and qnrS) in the winter and of six ARGs (sul1, sul3, tetA, tetC, tetE, and qnrS) in the summer were increased throughout the treatment process. Strong correlations were found between ARGs in water and those found in sediments, especially in the summer, indicating that ARGs may be exchanged between water and sediment. Strong positive correlations were also observed between concentrations of intI1 and several ARGs, implying that mobile genetic elements may play a key role in the dissemination of ARGs in an ICW. Our study results suggest aqueous ARGs could be effectively removed via an ICW and that ICWs can also act as reservoirs of specific ARGs.

Computational consideration on advanced oxidation degradation of phenolic preservative, methylparaben, in water: mechanisms, kinetics, and toxicity assessments.

Hydroxyl radicals ((•)OH) are strong oxidants that can degrade organic pollutants in advanced oxidation processes (AOPs). The mechanisms, kinetics, and toxicity assessment of the (•)OH-initiated oxidative degradation of the phenolic preservative, methylparaben (MPB), were systematically investigated using a computational approach, as the supplementary information for experimental data. Results showed that MPB can be initially attacked by (•)OH via OH-addition and H-abstraction routes. Among these routes, the (•)OH addition to the C atom at the ortho-position of phenolic hydroxyl group was the most significant route. However, the methyl-H-abstraction route also cannot be neglected. Further, the formed transient intermediates, OH-adduct ((•)MPB-OH1) and dehydrogenated radical ((•)MPB(-H)α), could be easily transformed to several stable degradation products in the presence of O2 and (•)OH. To better understand the potential toxicity of MPB and its products to aquatic organisms, both acute and chronic toxicities were assessed computationally at three trophic levels. Both MPB and its products, particularly the OH-addition products, are harmful to aquatic organisms. Therefore, the application of AOPs to remove MPB should be carefully performed for safe water treatment.

Experimental and theoretical insights into photochemical transformation kinetics and mechanisms of aqueous propylparaben and risk assessment of its degradation products.

The kinetics and mechanisms of ultraviolet photochemical transformation of propylparaben (PPB) were studied. Specific kinetics scavenging experiments coupled with quantum yield determinations were used to distinguish the roles of various reactive species induced by self-sensitized and direct photolysis reactions, and the excited triplet state of PPB ((3) PPB*) was identified as the most important species to initiate the photochemical degradation of PPB in aquatic environments. The computational results of time-resolved absorption spectra proved that (3) PPB* is a highly reactive electron acceptor, and a head-to-tail hydrogen transfer mechanism probably occurs through electron coupled with proton transfer. Physical quenching by, or chemical reaction of (3) PPB* with, O2 was confirmed as a key step affecting the initial PPB transformation pathways and degradation mechanisms. The transformation products were identified and the toxicity evolutions of PPB solutions during photochemical degradation under aerobic and anaerobic conditions were compared. The results indicate that anaerobic conditions are more likely than aerobic conditions to lead to the elimination and detoxification of PPB but less likely to lead to PPB mineralization.

Advanced oxidation kinetics and mechanism of preservative propylparaben degradation in aqueous suspension of TiO2 and risk assessment of its degradation products.

The absolute kinetic rate constants of propylparaben (PPB) in water with different free radicals were investigated, and it was found that both hydroxyl radicals (HO(•)) and hydrated electrons could rapidly react with PPB. The advanced oxidation kinetics and mechanisms of PPB were investigated using photocatalytic process as a model technology, and the degradation was found to be a pseudo-first-order model. Oxidative species, particularly HO(•), were the most important reactive oxygen species mediating photocatalytic degradation of PPB, and PPB degradation was found to be significantly affected by pH because it was controlled by the radical reaction mechanism and was postulated to occur primarily via HO(•)-addition or H-abstraction reactions on the basis of pulse radiolysis measurements and observed reaction products. To investigate potential risk of PPB to humans and aqueous organisms, the estrogenic assays and bioassays were performed using 100 µM PPB solution degraded by photocatalysis at specific intervals. The estrogenic activity decreased as PPB was degraded, while the acute toxicity at three trophic levels first increased slowly and then decreased rapidly as the total organic carbon decreased during photocatalytic degradation.