Xiangping Nie

Photocatalytic degradation kinetics and mechanism of antivirus drug-lamivudine in TiO2 dispersion

Photocatalytic degradation kinetics of antivirus drug-lamivudine in aqueous TiO(2) dispersions was systematically optimized by both single-variable-at-a-time and central composite design based on the response surface methodology. Three variables, TiO(2) content, initial pH and lamivudine concentration, were selected to determine the dependence of degradation efficiencies of lamivudine on independent variables. Response surface methodology modeling results indicated that degradation efficiencies of lamivudine were highly affected by TiO(2) content and initial lamivudine concentration. The highest degradation efficiency was achieved at suitable amount of TiO(2) and with maintaining initial lamivudine concentration to a minimum. In addition, the contribution experiments of various primary reactive species produced during the photocatalysis were investigated with the addition of different scavengers and found that hydroxyl radicals was the major reactive species involved in lamivudine degradation in aqueous TiO(2). Six degradation intermediates were identified using HPLC/MS/MS, and photocatalytic degradation mechanism of lamivudine was proposed by utilizing collective information from both experimental results of HPLC/MS/MS, ion chromatography as well as total organic carbon and theoretical data of frontier electron densities and point charges.

The distribution and partitioning of common antibiotics in water and sediment of the Pearl River Estuary, South China

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.

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.

The role of class I integrons in the dissemination of sulfonamide resistance genes in the Pearl River and Pearl River Estuary, South China

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.

Toxic effects of erythromycin, ciprofloxacin and sulfamethoxazole on photosynthetic apparatus in Selenastrum capricornutum.

The effects of three antibiotics (erythromycin, ciprofloxacin and sulfamethoxazole) on photosynthesis process of Selenastrum capricornutum were investigated by determining a battery of parameters including photosynthetic rate, chlorophyll fluorescence, Hill reaction, and ribulose-1.5-bisphosphate carboxylase activity, etc. The results indicated that three antibiotics could significantly inhibit the physiological progress including primary photochemistry, electron transport, photophosphorylation and carbon assimilation. Erythromycin could induce acute toxic effects at the concentration of 0.06 mg L(-1), while the same results were exhibited for ciprofloxacin and sulfamethoxazole at higher than 1.0 mg L(-1). Erythromycin was considerably more toxic than ciprofloxacin and sulfamethoxazole and may pose a higher potential risk to the aquatic ecosystem. Some indices like chlorophyll fluorescence, Mg(2+)-ATPase activity and RuBPCase activity showed a high specificity and sensitivity to the exposure of erythromycin, and may be potentially used as candidate biomarkers for the exposure of the macrolide antibiotics.

Assessment of toxic effects of triclosan on the swordtail fish (Xiphophorus helleri) by a multi-biomarker approach

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.

Mercury biomagnification in the aquaculture pond ecosystem in the Pearl River Delta.

This is the first study to investigate the rate of mercury (Hg) biomagnification in the aquaculture pond ecosystem of the Pearl River Delta (PRD), China, by analyzing total mercury (THg) and methyl mercury (MeHg) concentrations in various species of fish at different trophic levels (TLs). Species representing a gradient of trophic positions in the aquaculture pond food chains were chosen for analyzing THg and MeHg concentrations. In this study, there were two kinds of the aquaculture pond food chains: (1) omnivorous (fish feeds, zooplankton, grass carp [Ctenopharyngodon idellus], and bighead carp [Aristichthys nobilis]) and (2) predatory (zooplankton, mud carp [Cirrhina molitorella], and mandarin fish [Siniperca kneri]). Bighead carp and mandarin fish had the highest MeHg and THg concentrations, i.e., an order of magnitude higher than other species, in their respective food chains. More than 90% of the THg concentrations detected in bighead carp, mandarin fish, and mud carp were in the methylated form. In this study, %MeHg increased with TLs and MeHg concentrations, reflecting that MeHg is the dominant chemical species of Hg accumulated in higher concentrations in biota, especially biota associated with higher TLs in the food chains. The trophic magnification factors were 2.32 and 2.60 for MeHg and 1.94 and 2.03 for THg in omnivorous and predatory food chains, respectively, in PRD. Hg concentrations in fish tissue correlated to Hg levels in the ambient environment, and sediment seemed to be the major source for Hg accumulated in fish. In addition, feeding habit also affected Hg accumulation in different fish species. Four significant linear relationships were obtained between log-THg and δ15N and between log-MeHg and δ15N. The slope of the regression equations, as biomagnification power, was smaller in magnitude compared with those reported for temperate and arctic marine and freshwater ecosystems, indicating that THg and MeHg biomagnifications were lower in this PRD subtropical aquaculture pond ecosystem. This was probably due to low Hg bioavailability at lower TLs as well as individual feeding behavior of fish.

Mutagenicity assessment of produced water during photoelectrocatalytic degradation.

Oilfield produced water was treated by photocatalysis, electro-oxidation, and photoelectrocatalysis, respectively. The chemical composition and toxicity of the raw effluent and treated products were assessed by chemical and mutagenicity analysis. The raw effluent exhibited mutagenic activity in both strains of Salmonella typhimurium. The lowest concentration of the dichloromethane extract capable of inducing a positive response in strains TA98 and TA100 were as low as 4 and 5 microg/plate, respectively. All three technologies could detoxify direct-acting mutagenic organic pollutants efficiently, although they could not completely eliminate mutagenicity in the water after 60 min of treatment. At equivalent doses, photoelectrocatalysis exhibited the greatest capability to reduce genotoxicity, whereas photocatalysis was the least effective and did not cause appreciable change in mutagenicity. The gas chromatography-mass spectrometry (GC-MS) analysis revealed that n-alkanes (259.4 ng/L) and phenolic compounds (2,501.4 ng/L) were the main organic constituents in the oilfield produced water. Thus, the results of both biological and chemical analysis indicate that photoelectocatalysis was the most effective technology for degradation of oilfield wastewater.

Assessment of typical pollutants in waterborne by combining active biomonitoring and integrated biomarkers response.

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.

Gene response of CYP360A, CYP314, and GST and whole-organism changes in Daphnia magna exposed to ibuprofen.

The fate and ecological impact of non-steroidal anti-inflammatory drugs (NSAIDs) in aquatic environments has gained increasingly concern recently. However, limited information is provided about the toxicity mechanism of NSAIDs to aquatic invertebrates. In the present study, we investigated the expression of CYP360A, CYP314, and GST genes involved in the detoxification process and the responses of their associated enzymes activity, as well as whole-organism changes in Daphnia magna exposed to environmentally relevant concentrations of ibuprofen (IBU). Results showed that the total amount of eggs produced per female, total number of brood per female, and body length were significantly decreased under IBU exposure, suggesting the effects of chronic IBU exposure on growth and reproduction of D. magna cannot be ignored. In gene expression level, the CYP360A gene, homologue to CYP3A in mammalian, showed inhibition at low concentration of IBU (0.5μg·L(-1)) and induction at high concentration of IBU (50μg·L(-1)). GST gene also exhibited a similar performance to CYP3A. CYP314 displayed inhibition for short time exposure (6h) and induced with prolonged exposure time (48h) at low concentration of IBU (0.5μg·L(-1)). Erythromycin N-demethylase (ERND) and aminopyrine N-demethylase (APND) related to cytochrome oxidase P450 (CYPs) were inhibited for short time exposure (6h) to IBU and then activated with prolonged exposure time (48h) at low concentration of IBU (0.5μg·L(-1)), while EROD showed a dose-dependent pattern under IBU exposure. As for antioxidative system, induction of glutathione S-transferase (GST), superoxide dismutase (SOD), and catalase (CAT) was observed in short-term exposure to IBU. Meanwhile, methane dicarboxylic aldehyde (MDA) content increased with the increasing IBU concentration and the delayed exposure time, displaying obvious dose- and time-dependent pattern. In summary, IBU significantly altered some physiological and biochemical parameters and genes expressions associated with detoxification metabolism in D. magna, the integrated approach combining the response in molecule levels with the performance of the whole organism can help elucidate the toxic effects of IBU and provide more insight into the exact mechanism of toxicity in aquatic organisms.