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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–C N–N of S1 *PYM, and the absolute charges of the C N 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 C N 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.

Antibiotic resistance genes (ARGs), as a newly emerging contaminant, are unique because they are disseminated through horizontal gene transfer in the environment. In the present study, a class 1 integron gene (int1) and various ARGs (sul1, sul2, sul3, qnrS, and ermB) were measured in water and sediment samples from the Pearl River (PR) to the Pearl River Estuary (PRE), where there is a distinct gradient in anthropogenic impact. The int1, sul1, and sul2 genes were detected in all samples, and their concentrations exhibited a clear trend of decline consistent with anthropogenic impact. Both the int1 and sul genes had dynamically migrated between water and sediments. The relative abundance of the int1 gene normalized to the 16S rRNA gene correlated significantly with the total concentrations of antibiotics in water and sediments. Good correlations were also observed between the abundance of int1 and each type of sul gene in the samples. However, the sul1 gene showed a much stronger relationship with int1 in different seasons, probably due to the presence of sul1 in the conserved region of class 1 integron. Our results strongly support that integrons play an important role in the dissemination of ARGs in human-impacted aquatic environments.

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.

Antibiotics released into the aquatic environment play an important role in the spread of antibiotic resistance. In the Pearl River Estuary (PRE) and the coastal zone, the concentrations of antibiotics decreased from the Pearl River to the estuary, suggesting that antibiotics primarily originated from river tributaries and terrigenous sources. Within the PRE area, the concentrations of antibiotics in water were higher in the west coast than the east side, reflecting the high density of anthropogenic activities and hydraulic conditions along the west riverbank. Seasonal variations were also observed for most of detected antibiotics in water. The pseudo-partitioning coefficient of norfloxacin had a good correlation with the TOC content of sediments, as did erythromycin-H2O with the pH of water. The results suggest that environmental conditions can significantly affect the distribution of antibiotics between water and sediment. (C) 2013 Elsevier Ltd. All rights reserved.

Antibiotic resistance genes (ARGs) are increasingly a focus of concern because they pose a potential health risk. The Pearl River (PR) and Pearl River Estuary (PRE) show a distinct gradient in anthropogenic impacts, in particular associated with the use of antibiotics, from the river, to the estuary, and on to the coast. In this study, two surveys were conducted in the PR and PRE areas during the winter and summer of 2011, respectively. Seven tet genes consisting of efflux pump (tetA, tetC, and tetH) and ribosomal protection proteins (tetB, tetM, tetO, and tetW) were analyzed using the polymerase chain reaction (PCR) technique. The tet genes, with the exception of tetA and tetH, were widely detected in the PR and PRE environments. The tet genes exhibited a trend of an increase in total concentration and diversity with the degree of anthropogenic impacts from the river to the coast, indicating that riverine input was the main source of ARGs in the region. Significant correlations were observed between tet genes and antibiotic concentrations, as well as among different environmental compartments (water and sediments). The distribution patterns of tet genes were similar between the potential sources of pollution and the highly-impacted sites, but were significantly different between less-impacted sites and highly-impacted ones or pollution sources. The results suggest that ARGs and antibiotics may be released from identical sources, and transported in a similar manner in estuary/coastal environments close to sources of pollution.

Surface sediments can provide useful information on the recent pollution status of an estuary. One recent field survey was carried out in the Pearl River Estuary (PRE), South China in 2011. The comparisons with previous surveys demonstrated that the concentrations of Ni and Pb in the PRE declined over the last decade, but the concentration of Cu increased in the same time frame. The significant decreases in the concentrations of Ni and Pb were probably due to a reduction of anthropogenic inputs, such as industrial wastewater, into the PRE environment, and the ban imposed on leaded gasoline. Statistical analyses have consistently demonstrated that the process of the sedimentation of fine particles was the dominant factor in controlling the transport and distribution of trace metals in the PRE. The riverine trace metals generally displayed a pattern of diffusion from the northwest to the southeast in the estuary. However, the riparian industrial activities at the east bank of the inner PRE caused significant metal contamination in sediments. In general, effective pollution control measures in the PRD region have decreased the levels of some trace metals in the entire PRE over the last decade with the exception of Cu. (C) 2012 Elsevier B.V. All rights reserved.

The toxic effects of triclosan (TCS) on the swordtail fish ( Xiphophorus helleri ) were assessed based on various biomarkers including enzymatic activities of ethoxyresorufin O-deethylase (EROD), erythromycin N-demethylase (ERND) and glutathione-s-transferase (GST) and mRNA expression levels of CYP1A, CYP3A, glutathione S-transferase (GST) and P-glycoprotein (P-gp). The acute toxicity test showed the LC 50 value of 1.47 mg L −1 for TCS. The mRNA expressions of CYP1A, CYP3A, GST and P-gp showed dose–effect relationships in female swordtail fish when exposed to TCS, These mRNA expression levels were found more sensitive to TCS exposure than the enzymatic activities of EROD, ERND and GST do. In addition, the male fish displayed higher gene expression levels and more dramatic changes in enzyme activities than the females did. Our data further demonstrated that TCS was a typical inducer to Phase I and Phase II metabolism enzymes and genes, suggesting it is a potential ecotoxicological risk to aquatic ecosystems.

Organic pollutants, heavy metals and pharmaceuticals are continuously dispersed into the environment and have become a relevant environmental emerging concern. In this study, a situ assay to assess ecotoxicity of mixed pollutants was carried out in three typical sites with different priority contaminations in Guangzhou, China. Chemical analysis of organic pollutants, metals and quinolones in three exposure sites were determined by GC–ECD/MS, ICP-AES and HPLC, as well as, a combination of biomarkers including: ethoxyresorufin O-deethylase (EROD); aminopyrine N-demethylase (APND); erythromycin N-demethylase (ERND); glutathione S-transferase (GST); malondialdehyde (MDA); CYP1A; and P-glycoprotein (P-gp) mRNA expressions were evaluated in Mugilogobius abei. Results of chemical analysis in sediment samples revealed that the dominant chemicals were organic pollutants and heavy metals in Huadi River while quinolones in the pond. Bioassays indicated that differences among sites were in relation to some specific biomarkers. EROD and GST activities significantly increased after 72 h in situ exposure, but no difference was observed among the exposure sites. APND, ERND and MDA exhibited dissimilar change patterns for different priority pollutants. CYP1A and P-gp mRNA expressions were significantly induced at all exposure sites, whilst P-gp activity was typical for S2 with the highest levels of quinolones. The molecular biomarkers seemed to be more susceptible than enzyme activities. These assays confirmed the usefulness of applying a large array of various combined biomarkers at different levels, in assessing the toxic effects of mixed pollutants in a natural aquatic environment.