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Characterizing distributions, composition profiles, sources and potential health risk of polybrominated diphenyl ethers (PBDEs) in the coastal sediments from East China Sea
2016
Wang, Guoguang | Peng, Jialin | Zhang, Dahai | Li, Xianguo
Sediment samples (n = 20) were collected from Yangtze River Estuary (YRE) and the adjacent East China Sea (ECS) inner shelf to explore spatial and temporal distributions, environmental fate, sources and potential health risk of polybrominated diphenyl ethers (PBDEs). Concentrations of BDE-209 and total 7 PBDEs (without BDE-209; ∑7PBDEs) ranged from 62.3 to 1758 pg g−1 and from 36.9 to 233.6 pg g−1 dry weight, respectively; both of the highest values occurred near the city of Wenzhou. Concentrations of BDE-209 and ∑7PBDEs both indicated a decreasing trend from inshore areas toward outer shelf. Significantly positive linear correlations were only observed between logBDE-183 concentrations and TOC/grain size (r2 = 0.6734 and 0.5977 for TOC and grain size, respectively) as well as BDE-209 and TOC/grain size (r2 = 0.4137 and 0.5332 for TOC and grain size, respectively) in the north of 28°N, indicating that YR had significant influence on the distribution of higher brominated congeners only in the north part. Depth profiles of PBDEs in a sediment core P01 (n = 1, m = 11) collected from YRE showed that the input of BDE-209 gradually increased from 1930 to 2010, while the levels of ∑7PBDEs peaked in 1986 and obviously decreased in recent years. Partial Least-Squares Regression (PLSR) revealed that PBDEs in the coastal ECS were mainly from direct discharge of local anthropogenic activities (80.7%), followed by surface runoff of contaminated soils (15.1%), microbial degradation after sedimentation (2.6%) and photodegradation during atmospheric transportation (1.6%). The cancer risk of human exposure to BDE-209 at the 95% confidence level was 3.09 × 10−7, 1.67 × 10−7 and 8.86 × 10−7 for children, teens and adults, respectively, significantly lower than the threshold level (10−6). Hazard index (HI) calculated for non-cancer risk was also far less than 1 for the three groups, suggesting no non-cancer risk.
Mostrar más [+] Menos [-]Use of sunlight to degrade oxytetracycline in marine aquaculture's waters
2016
Leal, J.F. | Esteves, V.I. | Santos, E.B.H.
Oxytracycline (OTC) is a broad spectrum antibiotic authorized for use in European aquaculture. Its photo-degradation has been widely studied in synthetic aqueous solutions, sometimes resorting to expensive methods and without proven effectiveness in natural waters. Thus, this work studied the possibility to apply the solar photo-degradation for removal of OTC from marine aquaculture's waters. For that, water samples were collected at different locals of the water treatment circuit, from two different aquaculture companies. Water samples were firstly characterized regarding to pH, salinity, total suspended solids (TSS), organic carbon and UV–Vis spectroscopic characteristics. Then, the samples were spiked with OTC and irradiated using simulated sunlight in order to evaluate the matrix effects on OTC photo-degradation. From kinetic results, the apparent quantum yields and the outdoor half-life times, at 40°N for midsummer and midwinter days were estimated by the first time for these conditions. For a midsummer day, at sea level, the outdoor half-life time predicted for OTC in these aquaculture's waters ranged between 21 and 25 min. Additionally, the pH and salinity effects on the OTC photo-degradation were evaluated and it has been shown that high pH values and the presence of sea salt increase the OTC photo-degradation rate in aquaculture's waters, compared to results in deionised water. The results are very promising to apply this low-cost methodology using the natural sunlight in aquaculture's waters to remove OTC.
Mostrar más [+] Menos [-]The effect of Cu2+ chelation on the direct photolysis of oxytetracycline: A study assisted by spectroscopy analysis and DFT calculation
2016
Jin, Xin | Qiu, Shanshan | Wu, Ke | Jia, Mingyun | Wang, Fang | Gu, Chenggang | Zhang, Aiqian | Jiang, Xin
The extensive usage of OTC and Cu2+ in livestock and poultry industry caused high residues in natural environment. Co-contamination of OTC and Cu2+ was a considerable environmental problem in surface waters. In this study, Cu2+ mediated direct photolysis of OTC was studied. Cu2+ chelating with OTC was found to greatly inhibit OTC photodegradation. To reveal the chelation mechanism of OTC-Cu complexes, multiple methods including UV–Vis absorption spectra, Infrared (IR) spectra, mass spectroscopy, and density functional theoretical (DFT) modeling were performed. Four OTC-Cu complexes were proposed. Cu2+ preferably bond to O11O12 site with the binding constants logK = 8.19 and 7.86 for CuHL+ and CuL±, respectively. The second chelating site was suggested to be O2O3 with the binding constants of logK = 4.41 and 4.62 for Cu2HL3+ and Cu2L2+, respectively. The suppressed quantum yield of OTC by Cu2+ chelation was accused for their intra-/inter-molecular electron transfer, by which the energy in activated states was distributed. The occurrence of electron transfer between BCD ring and A ring also from BCD ring to Cu was evidenced by the TD-DFT result only for the OTC-Cu complexes. Besides, the cyclic voltammetry measurement also suggested one OTC-Cu(II)/OTC-Cu(I) redox couple. These results suggested that the persistence of OTC in environmental surface waters will probably be underestimated for neglecting the chelating effect of Cu2+. The photolysis quantum yield of OTC-Cu complexes, as well as the specific molar absorption constants, the equilibrium binding constants of Cu2+ with OTC could contribute to more accurate kinetic models of OTC.
Mostrar más [+] Menos [-]Initial hazard screening for genotoxicity of photo-transformation products of ciprofloxacin by applying a combination of experimental and in-silico testing
2016
Toolaram, Anju Priya | Haddad, Tarek | Leder, Christoph | Kümmerer, Klaus
Ciprofloxacin (CIP) is a broad-spectrum antibiotic found within μg/L concentration range in the aquatic environment. It is a known contributor of umuC induction in hospital wastewater samples. CIP can undergo photolysis to result in many transformation products (TPs) of mostly unknown toxicity. The aims of this study were to determine the genotoxicity of the UV mixtures and to understand the possible genotoxic role of the stable TPs. As such, CIP and its UV-irradiated mixtures were investigated in a battery of genotoxicity and cytotoxicity in vitro assays. The combination index (CI) analysis of residual CIP in the irradiated mixtures was performed for the umu assay. Further, Quantitative Structure–Activity Relationships (QSARs) predicted selected genotoxicity endpoints of the identified TPs. CIP achieved primary elimination after 128 min of irradiation but was not completely mineralized. Nine photo-TPs were identified. The irradiated mixtures were neither mutagenic in the Ames test nor genotoxic in the in vitro micronucleus (MN) test. Like CIP, the irradiated mixtures were umuC inducing. The CI analysis revealed that the irradiated mixtures and the corresponding CIP concentration in the mixtures shared similar umuC potentials. QSAR predictions suggested that the TPs may be capable of inducing chromosome aberration, MN in vivo, bacterial mutation and mammalian mutation. However, the experimental testing for a few genotoxic endpoints did not show significant genotoxic activity for the TPs present as a component of the whole mixture analysis and therefore, further genotoxic endpoints may need to be investigated to fully confirm this.
Mostrar más [+] Menos [-]Environmental fate and effect assessment of thioridazine and its transformation products formed by photodegradation
2016
Wilde, Marcelo L. | Menz, Jakob | Trautwein, Christoph | Leder, Christoph | Kümmerer, Klaus
An experimental and in silico quantitative structure-activity relationship (QSAR) approach was applied to assess the environmental fate and effects of the antipsychotic drug Thioridazine (THI). The sunlight-driven attenuation of THI was simulated using a Xenon arc lamp. The photodegradation reached the complete primary elimination, whereas 97% of primary elimination and 11% of mineralization was achieved after 256 min of irradiation for the initial concentrations of 500 μg L−1 and 50 mg L−1, respectively. A non-target approach for the identification and monitoring of transformation products (TPs) was adopted. The structure of the TPs was further elucidated using liquid chromatography–high resolution mass spectrometry (LC–HRMS). The proposed photodegradation pathway included sulfoxidation, hydroxylation, dehydroxylation, and S- and N-dealkylation, taking into account direct and indirect photolysis through a self-sensitizing process in the higher concentration studied. The biodegradability of THI and photolytic samples of THI was tested according to OECD 301D and 301F, showing that THI and the mixture of TPs were not readily biodegradable. Furthermore, THI was shown to be highly toxic to environmental bacteria using a modified luminescent bacteria test with Vibrio fischeri. This bacteriotoxic activity of THI was significantly reduced by phototransformation and individual concentration-response analysis confirmed a lowered bacterial toxicity for the sulfoxidation products Thioridazine-2-sulfoxide and Thioridazine-5-sulfoxide. Additionally, the applied QSAR models predicted statistical and rule-based positive alerts of mutagenic activities for carbazole derivative TPs (TP 355 and TP 339) formed through sulfoxide elimination, which would require further confirmatory in vitro validation tests.
Mostrar más [+] Menos [-]In situ investigation into surfactant effects on the clearance of polycyclic aromatic hydrocarbons adsorbed onto soybean leaf surfaces
2016
Sun, Haifeng | Wang, Weipeng | Guo, Shuai | Zhang, Yong
The partitioning of polycyclic aromatic hydrocarbons (PAHs) in agricultural crop leaves, contributes to the exposure of organisms to these chemicals through the dietary pathway. To precisely predict the fate of PAHs and crop safety, the clearance of three-ringed phenanthrene (Phe) and four-ringed pyrene (Pyr) adsorbed individually onto living soybean leaf surfaces, as well as the effects of two surfactants, namely, an ionic surfactant (sodium dodecylbenzene sulfonate, SDBS) and a non-ionic surfactant (polyoxyethyleneglycol dodecyl ether, Brij35), were investigated in situ using the laser-induced nanosecond time-resolved fluorescence (LITRF) method. The effects varied significantly with surfactant types primarily in terms of the elimination rates and the final residues of PAH chemicals. With increasing SDBS and Brij35 concentrations, volatilization rate constants (kC) of both Phe and Pyr initially decreased at fast rates and then at more moderate rates later on, resulting from the plasticizing effect of surfactants adsorbed on leaf surfaces. In addition, the photolysis rate constants (kP) decreased with the presence of SDBS but increased with the presence of Brij35. Overall, the total clearance rates of PAHs (kT) adsorbed onto living soybean leaf surfaces were inhibited by the presence of SDBS but promoted by the presence of Brij35. These observations show that surfactants may significantly alter the clearance of PAHs in agricultural systems, and the potential impact of surfactants on crop safety is closely related to surfactant types in natural environments.
Mostrar más [+] Menos [-]Experimental and in silico assessment of fate and effects of the antipsychotic drug quetiapine and its bio- and phototransformation products in aquatic environments
2016
Herrmann, Manuel | Menz, Jakob | Gassmann, Matthias | Olsson, Oliver | Kümmerer, Klaus
The antipsychotic drug quetiapine (QUT) has been frequently detected in sewage treatment plants. However, information on the fate of QUT in aquatic environments and its behavior during UV treatment is limited. In this study, QUT is shown not to be readily biodegradable in the Closed Bottle Test and the Manometric Respirometry Test according to OECD guidelines. The main biotransformation product (BTP) formed in the tests, a carboxylic acid derivative, was identified by means of high-resolution mass spectrometry. This BTP is presumably a human metabolite and showed higher detection rates than QUT in a river sampling campaign conducted in northern Germany. UV elimination kinetics of QUT at different initial concentrations (226.5, 45.3, 11.3, and 2.3 μmol L−1) were faster at lower initial concentrations. All seven phototransformation products (PTPs) could be still identified at initial concentration of 11.3 μmol L−1. The photolytic mixture generated after 128 min of photolysis of QUT was not better biodegradable than QUT. Initial UV treatment of QUT led to the formation of several additional BTPs. Four of them were identified. The bacterial cytotoxicity and genotoxicity before and after phototransformation of QUT in a modified luminescent bacteria test (LBT) and the umu-test (ISO/FDIS 13829) showed cytotoxic effects in the LBT for QUT. Furthermore, PTPs had similar cytotoxic effects on luminescent bacteria. The umu-test did not reveal any genotoxic activity for QUT or PTPs. In conclusion, the release of QUT into sewage treatment plants and aquatic environments could result in the formation of a main BTP. Additional UV treatment of QUT would lead to the formation of additional BTPs. Moreover, treatment did not result in lower toxicity to tested organisms. In conclusion, UV treatment of QUT should be considered critically as a potential treatment for QUT in aquatic systems.
Mostrar más [+] Menos [-]Degradation of cyclophosphamide and 5-fluorouracil by UV and simulated sunlight treatments: Assessment of the enhancement of the biodegradability and toxicity
2016
Lutterbeck, Carlos Alexandre | Wilde, Marcelo Luís | Baginska, Ewelina | Leder, Christoph | Machado, Ênio Leandro | Kümmerer, Klaus
The presence of pharmaceuticals in the environment has triggered concern among the general population and received considerable attention from the scientific community in recent years. However, only a few publications have focused on anticancer drugs, a class of pharmaceuticals that can exhibit cytotoxic, genotoxic, mutagenic, carcinogenic and teratogenic effects. The present study investigated the photodegradation, biodegradation, bacterial toxicity, mutagenicity and genotoxicity of cyclophosphamide (CP) and 5-fluorouracil (5-FU). The photodegradation experiments were performed at a neutral to slight pH range (7–7.8) using two different lamps (medium-pressure mercury lamp and a xenon lamp). The primary elimination of the parent compounds was monitored by means of liquid chromatography tandem mass spectrometry (LC-IT-MS/MS). NPOC (non-purgeable organic carbon) analyses were carried out in order to assess mineralization rates. The Closed Bottle Test (CBT) was used to assess ready biodegradability. A new method using Vibrio fischeri was adopted to evaluate toxicity. CP was not degraded by any lamp, whereas 5-FU was completely eliminated by irradiation with the mercury lamp but only partially by the Xe lamp. No mineralization was observed for the experiments performed with the Xe lamp, and a NPOC removal of only 18% was registered for 5-FU after 256 min using the UV lamp. Not one of the parent compounds was readily biodegradable in the CBT. Photo transformation products (PTPs) resulting from photolysis were neither better biodegradable nor less toxic than the parent compound 5-FU. In contrast, the results of the tests carried out with the UV lamp indicated that more biodegradable and non-toxic PTPs of 5-FU were generated. Three PTPs were formed during the photodegradation experiments and were identified. The results of the in silico QSAR predictions showed positive mutagenic and genotoxic alerts for 5-FU, whereas only one of the formed PTPs presented positive alerts for the genotoxicity endpoint.
Mostrar más [+] Menos [-]Photodegradation of PAHs in passive water samplers
2016
Allan, Ian J. | Christensen, Guttorm | Bæk, Kine | Evenset, Anita
Losses of deuterated polycyclic aromatic hydrocarbons (PAHs) used as performance reference compounds (PRCs) in semipermeable membrane devices deployed at fifteen coastal sampling sites near Harstad harbour in Northern Norway were used to investigate photodegradation of these photosensitive compounds. Unusual PRC dissipation profiles, especially for samplers exposed <5m below the water surface are indicative of photodegradation. A strong correlation between loss rates for d12-chrysene and d12-benzo[e]pyrene with consistently higher losses of the latter was found. The observed photodegradation rates may be sufficiently high to impact PAH masses absorbed by a factor of two. This study demonstrates that photodegradation during exposure of passive water samplers needs to be taken into account, particularly with deployments close to the water surface, when using SPMD canisters, or when sampling in the Arctic.
Mostrar más [+] Menos [-]Synthesis of TiO2–Reduced Graphene Oxide Nanocomposites for Efficient Adsorption and Photodegradation of Herbicides
2016
Liu, Xue | Hong, Hye-gŏl | Wu, Xiaoli | Wu, Yanhua | Ma, Yongqiang | Guan, Wenbi | Shi, Zhangyu
The elimination of herbicides in aquatic environment is influenced by various biotic or abiotic factors. Thus, efficient, more applicable, and flexible methods are in demand. Photodegradation has been applied to remove three main types of herbicides, phenylurea, triazine, and chloroacetanilide, from water, based on a series of TiO₂–reduced graphene oxide nanocomposites. Experimental results showed that the three types of herbicides could be mostly removed under simulated sunlight irradiation for 5 h with the as-prepared photocatalyst. Compared with pure TiO₂ or P25, the photodegradation efficiency has been markedly increased. Thus, the present work could promote a new strategy dealing with the pollution of herbicides in aquatic ecosystems.
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