Microbial ecotoxicity and mutagenicity of 1-hydroxypyrene and its photoproducts.

1-Hydroxypyrene (1-HP) is a carcinogenic and slightly water-soluble polycyclic aromatic hydrocarbon. Ecotoxicity and mutagenicity of 1-HP and its photoproducts, and the effect of Mn2+ and Cu2+ on their mutagenicity were measured with microbial assay in this study. The assay includes spread plate counting, direct counting, microbial mineralization of 14C-UL-D-glucose and Mutatox Test. At the concentration examined (0.8 microM), the photoproducts (after 1.5 h solar irradiation) of 1-HP inhibited microbial glucose mineralization activity (by 64%) after microbial assemblages of a local reservoir site were exposed for 1 day. However, heterotrophic bacteria were able to utilize 1-HP photoproducts as the growth substrates and increase viability counts by up to 4.75-folds. 1-HP exhibited positive response to Mutatox Test in both direct medium and S-9 medium, with the lowest observable effective concentration of 0.625 microM in the test with direct medium. After photolysis, 1-HP decreased its mutagenicity. Mn2+ (312.5 microM-5 mM) and Cu2+ (6.25-100 microM) themselves are not mutagenic. However, addition of the metal ions before or after photolysis modifies the light readings of 1-HP during the test. Therefore, presence of metal ions could affect the genotoxicity of 1-HP in aquatic environments, depending on timing of the addition.     

Changes in toxicity and genotoxicity of industrial sewage sludge samples containing nitro- and amino-aromatic compounds following treatment in bioreactors with different oxygen regimes

Goals, Scope and Background

From 2005, deposition of organic waste will be banned in Sweden. Likewise, in Germany and Austria, similar bans are being planned, and further countries will probably follow. Thus, there is a need to develop new methods and to refine established techniques for sludge management in the whole of the European Union. For this end, there is also an urgent need for appropriate ecotoxicological approaches to elucidate and assess the hazard potential of sewage sludge. Therefore, the present study was designed to assess the capacity of various established sludge treatment methods using different oxygen regimes to degrade recalcitrant nitro-substituted organic compounds and reduce their toxicity. Sewage sludge samples from a wastewater treatment plant in Sweden (Cambrex Karlskoga AB, industrial area Björkborn) receiving wastewater from industries manufacturing pharmaceutical substances, chemical intermediates and explosives were processed with different sludge treatment methods. Among other treatment methods, bioreactors (for anaerobic and aerobic sludge treatment) were used. In the present investigation, a battery ofin vitro bioassays was employed to compare the cytotoxic and genotoxic potentials of different fractions of sludge samples in order to elucidate whether the treatments were suitable to reduce the toxicity of the sludge.

Methods

In order to investigate the cytotoxicity of the extracts of treated and untreated sludge samples, the acute cytotoxicity test with the permanent cell line RTL-W1 was used. Genotoxicity was tested by means of the comet assay (single cell gel electro-phoresis) with RTL-W1cells, and mutagenicity was assessed with the Ames test using the Salmonella typhimurium strains TA98, TA98NR and TA100. Sludge toxicity was tested in different fractions of organic extracts produced by acetone and hexane extractions. The subsequent clean-up procedure (silica gel chro-matography and elution with hexane and dichloromethane) resulted in two fractions, a lipophilic hexane-fraction and a semi-lipophilic dichloromethane-fraction. For the genotoxicity and mutagenicity tests, these fractions were reunited at equal ratios.

Results and Discussion

The acute cytotoxicity test with RTL-Wl cells revealed a high cytotoxic potential for the semi-li-pophilic DM-fractions of all sludge samples with NR₅₀ values (= effective concentration for 50% cell death in the neutral red test) from 8.9 up to 20 mg sludge d.w./ml medium. A low cytotoxic potential for the hexane fractions of the untreated sludge samples (NR₅₀ 400 to < 400 mg sludge d.w./ml medium) was observed, whereas the hexane fractions of the treated sludge samples showed elevated cytotoxicity increasing further with treatment in the bioreactors. The comet assay indicated that three out of eight of the reunited fractions had a significant genotoxic potential. Whereas the genotoxic potential of one sample treated anaerobically was very high with an induction factor of 11.6, a similar sample (taken from the same anaerobic reactor four months later) and one untreated sample showed lower potentials. The samples treated in another anaerobic bioreactor as well as the samples treated aerobically showed no genotoxic potential. Results indicate that aerobic treatment was basically adequate for reducing the genotoxicity of the sludge, whereas anaerobic treatment was only partly useful for reduction of genotoxicity. The Ames test revealed a very high mutagenic potential for the reunited fractions of the untreated sludge samples with strain TA98 (maximum induction factors (IF_max up to 45) and a relatively high potential for one of the samples treated aerobically (S2, IF_max = 18 (TA98, S9-)), thus documenting the suitability of both anaerobic and aerobic treatments to reduce the mutagenicity of the samples, however, with the aerobic treatment being less effective. Conclusions. Overall, none of the microbiological treatments for wastewater sludge in bioreactors was found to be ideal for general toxicity reduction of the sludge samples. Whereas cytotoxicity of the sludge increased or levelled off in most cases following either treatment, genotoxicity both increased or decreased after anaerobic treatment, depending on the specific sample. However, mutagenicity could generally be reduced by anaerobic treatment and, to a lesser degree, by aerobic treatment. Recommendationsand Perspectives. The complex modification of the diverse damage potentials of sludge sample extracts by use of anin vitro biotest battery following treatment for toxicity reduction in bioreactors showed that considerations of different toxicological endpoints is essential for an adequate hazard assessment. Whereas in the case of cytotoxicity reduction, the reactors proved ineffective, mutagenicity could be reduced significantly at least in some cases in this case study.

     

包装垃圾添加脱氯半焦制备SRF的燃烧特性及动力学分析

利用热重分析仪对添加了不同比例混合含氯塑料经微波低温脱氯后的脱氯半焦制备而成的固体衍生燃料（SRF）的燃烧特性及热反应动力学进行了实验研究,考察了脱氯半焦不同添加比例制备的SRF的着火点、燃尽温度、最大燃烧速率、燃尽特征指数和综合燃烧指数等燃烧特征参数。并用Coats-Redfern积分法对其进行了燃烧动力学分析,确定了燃烧动力学方程,求出了反应活化能和指前因子。结果表明：随着脱氯半焦的添加比例从5%增加至20%,TG曲线向低温区移动,着火点降低,燃尽温度降低,燃尽性能提升,综合燃烧特性指数S均高于不添加脱氯半焦的燃料,综合燃烧性能更好;当脱氯半焦添加比例为10%,综合燃烧特征参数最佳;在第三燃烧阶段,添加了脱氯半焦的燃料的活化能显著低于未添加脱氯半焦的燃料,指前因子降低了4~5个数量级。混合含氯废塑料,经过微波低温脱氯处理形成半焦作为添加剂制备SRF,不仅降低了SRF燃烧过程中氯化氢的产生量,同时提高了燃料的燃烧性能,是含氯塑料废弃物利用的一种新的方向和途径。     

Effect of a base-catalyzed dechlorination process on the genotoxicity of PCB-contaminated soil

We evaluated the genotoxicity of dichloromethane (DCM) extracts of PCB-contaminated soil before and after the soil had been treated by a base-catalyzed dechlorination process. The treatment process involves heating a mixture of the soil, polyethylene glycol (or hydrocarbons with boiling points of 310–387°C), and sodium hydroxide to 250–350°C. Dechlorination reduced by >99% the PCB concentration of the soil, which was initially 2,200 ppm. The DCM extracts of both control and treated soils were not mutagenic in strain TA100 of Salmonella, but they were mutagenic in strain TA98. Based on results in strain TA98, the base-catalyzed dechlorination process reduced the mutagenic potency of the soil by approximately one-half. The DCM extracts of the soils before and after treatment were equally genotoxic in a prophage-induction assay in . , which detects some chlorinated organic carcinogens that are not detected by the Salmonella mutagenicity assay. These results suggest that treatment of PCB-contaminated soil by base-catalyzed dechlorination reduced the mutagenicity of the soil slightly.     

Combination of in vitro bioassays for the determination of cytotoxic and genotoxic potential of wastewater, surface water and drinking water samples

In this study we evaluated genotoxicity and cytotoxicity of native samples of wastewaters (15 samples), surface waters (28 samples) and potable waters (8 samples) with the SOS/umuC assay with Salmonella typhimurium TA1535/pSK1002 and MTT assay with human hepatoma HepG2 cells. The genotoxicity of selected samples was confirmed with the comet assay with HepG2 cells. In the SOS/umuC assay 13 out of the 51 samples were genotoxic: two effluent samples from chemical industry; one sample of wastewater treatment plant effluent; two hospital wastewater samples; three river water samples and four lake water samples. Six samples were cytotoxic for HepG2 cells: both effluent samples of chemical industry, two wastewater treatment plant effluent samples, and two river water samples, however, only the chemical industry effluent samples were genotoxic and cytotoxic, indicating that different contaminants are responsible for genotoxic and toxic effects. Comparing genotoxicity of river and lake water samples with the chemical analytical data of the presence of the residues of pharmaceutical and personal care products (non-steroidal anti-inflammatory drugs, UV filters and disinfectants) in these samples, indicated that the presence of UV filters might be linked to the genotoxicity of these samples. The results showed that the application of the bacterial SOS/umuC assay and mammalian cell assays (MTT and comet assay) with HepG2 cells was suitably sensitive combination of assays to monitor genotoxicity and cytotoxicity of native samples of wastewaters and surface waters. With this study we also confirmed that the toxicity/genotoxicity bioassays should be an integral tool in the evaluation of toxicity of complex wastewaters before the release into environment, as well as for the monitoring of surface water quality, providing data useful in risk assessment.     

Degradation of chlordecone and beta-hexachlorocyclohexane by photolysis, (photo-)fenton oxidation and ozonation

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlorocyclohexane (β-HCH) in 1 mg L^?1 synthetic aqueous solutions by means of photolysis, (photo-) Fenton oxidation and ozonation processes. Fenton oxidation is not efficient for CLD and yields less than 15% reduction of β-HCH concentration in 5 h. Conversely, both molecules can be quantitatively converted under UV-Vis irradiation reaching 100% of degradation in 5 h, while combination with hydrogen peroxide and ferrous iron does not show any significant improvement except in high wavelength range (>280 nm). Ozonation exhibits comparable but lower degradation rates than UV processes. Preliminary identification of degradation products indicated that hydrochlordecone was formed during photo-Fenton oxidation of CLD, while for β-HCH the major product peak exhibited C₃H₃Cl₂ as most abundant fragment.     

Physicochemical characteristics,mutagenicity and genotoxicity of airborne particles under industrial and rural influences in Northern Lebanon

In this work, the main objectives were to assess the mutagenic and genotoxic effects of fine particulate matter collected in an industrial influenced site in comparison with a non-industrial influenced one (rural site) and to relate the particulate matter (PM) composition to the observed genotoxic effects. At the industrial influenced site, higher concentrations of phosphates, trace metals, and polycyclic aromatic hydrocarbons (PAHs) in particles could be related to the contributions of quarries, fertilizer producer, cement plants, and tires burning. Gasoline and diesel combustion contributions were evidenced in particles collected at both sites. Particles collected under industrial influence showed a higher mutagenic potential on three tested strains of Salmonella typhimurium (TA98, YG1041, and TA102), and especially on the YG1041, compared to particles from the rural site. Furthermore, only particles collected in the vicinity of the industrial site showed a tendency to activate the SOS responses in Escherichia coli PQ37, which is indicative of DNA damage as a result of exposure of the bacteria cells to the action of mutagenic samples. The mutagenicity and genotoxicity of the industrial PM_2.5–0.3 particulates may be attributed to its composition especially in organic compounds. This study showed that proximity of industries can affect local PM composition as well as PM genotoxic and mutagenic potential.     

Making chlorine greener: performance of alternative dechlorination agents in wastewater

The residual chlorine in chlorine-disinfected and dechlorinated wastewater was characterized using a liquid chromatograph that was switched between reversed-phase separation and flow injection analysis modes, permitting measurement of fractionated and total residual chlorine, respectively. Residuals were detected in the effluent of an operating wastewater treatment plant employing chlorine disinfection and sulfite dechlorination. Despite dechlorination, an estimated total residual chlorine of 3 microM (0.2 ppm as Cl2) was detected in the effluent. To improve dechlorination effectiveness, four alternative agents (ascorbic acid, iron, sulfite plus iodide mediator, thiosulfate) were compared to sulfite on laboratory-chlorinated wastewater. Listed in order of decreasing relative effectiveness, we found: iron metal > sulfite plus iodide approximately = thiosulfate > sulfite > ascorbic acid. Only the iron metal column was completely effective at rapidly removing all traces of residual chlorine.     

Genotoxic potential of selected cytostatic drugs in human and zebrafish cells

Due to their increasing use, the residues of anti-neoplastic drugs have become emerging pollutants in aquatic environments. Most of them directly or indirectly interfere with the cell’s genome, which classifies them into a group of particularly dangerous compounds. The aim of the present study was to conduct a comparative in vitro toxicological characterisation of three commonly used cytostatics with different mechanisms of action (5-fluorouracil [5-FU], cisplatin [CDDP] and etoposide [ET]) towards zebrafish liver (ZFL) cell line, human hepatoma (HepG2) cells and human peripheral blood lymphocytes (HPBLs). Cytotoxicity was determined by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and acridine orange/ethidium bromide staining. All three drugs induced time- and dose-dependent decreases in cell viability. The sensitivity of ZFL and HepG2 cells towards the cytotoxicity of 5-FU was comparable (half maximal inhibitory concentration (IC₅₀) 5.3 to 10.4 μg/mL). ZFL cells were more sensitive towards ET- (IC₅₀ 0.4 μg/mL) and HepG2 towards CDDP- (IC₅₀ 1.4 μg/mL) induced cytotoxicity. Genotoxicity was determined by comet assay and cytokinesis block micronucleus (CBMN) assay. ZFL cells were the most sensitive, and HPBLs were the least sensitive. In ZFL cells, induction of DNA strand breaks was a more sensitive genotoxicity endpoint than micronuclei (MNi) induction; the lowest effective concentration (LOEC) for DNA strand break induction was 0.001 μg/mL for ET, 0.01 μg/mL for 5-FU and 0.1 μg/mL for CDDP. In HepG2 cells, MNi induction was a more sensitive genotoxicity endpoint. The LOEC values were 0.01 μg/mL for ET, 0.1 μg/mL for 5-FU and 1 μg/mL for CDDP. The higher sensitivity of ZFL cells to cytostatic drugs raises the question of the impact of such compounds in aquatic ecosystem. Since little is known on the effect of such drugs on aquatic organisms, our results demonstrate that ZFL cells provide a relevant and sensitive tool to screen genotoxic potential of environmental pollutant in the frame of hazard assessment.     

Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.     

Relative bioavailability of tropical volcanic soil-bound chlordecone in laying hens (Gallus domesticus)

The former use of chlordecone (CLD) in the French West Indies has resulted in long-term pollution of soils and of food chains. CLD may be transferred into eggs of hens reared outdoors, through polluted soil ingestion. Tropical volcanic soils display variable capacities of pollutant retention: CLD is less available and more persistent in andosol than in nitisol. The impact of soil type on CLD bioavailability to hens was tested through a relative bioavailability study. The deposition of CLD in egg yolk and in abdominal fat was measured in 42 individually housed laying hens fed with diets containing graded levels of CLD from polluted andosol, nitisol, or spiked oil during 23 days. Within each ingested matrix, the concentration of CLD in yolk and in abdominal fat linearly increased with the amount of ingested CLD (P < 0.001). However, the response to andosol diets and to nitisol diets was not different from the response to oil diets (P > 0.1), indicating that CLD was equally bioavailable to laying hens, irrespective of the matrix. This suggests that the hen's gastrointestinal tract efficiently extracts CLD from the two tropical volcanic soils, regardless of their retention capacity. Thus, hens reared on polluted soils with CLD may lay contaminated eggs.     

Degradation of terbutylazine (2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (2-chloro-4,6-dimethoxy-1,3,5-triazine) by zero valent iron and electrochemical reduction

To help elucidate the mechanism of dechlorination of chlorinated triazines via metallic iron, terbutylazine (TBA: 2-chloro-4-ethylamino-6-terbutylamino-1,3,5-triazine), deisopropyl atrazine (DIA: 2-amino-4-chloro-6-ethylamino-1,3,5-triazine), and chlorinated dimethoxy triazine (CDMT: 2-chloro-4,6-dimethoxy-1,3,5-triazine) were degraded via zero valent iron under controlled pH conditions. The lower the solution pH the faster the degradation, with surface area normalized pseudo first order rate constants ranging from 2 (+/- 1)x10(-3) min(-1) m(-2) l for TBA at pH 2.0 to 4 (+/- 2)x10(-5) min(-1) m(-2) l for CDMT at pH 4.0. Hydrogenolysis (dechlorinated) products were observed for TBA and CDMT. Electrochemical reduction on mercury showed similar behavior for all of the triazines studied; the initial product of CDMT bulk electrolysis was the dechlorinated compound. The iron results are consistent with a mechanism involving the addition of surface hydrogen to the surface associated triazine.     

Decision support tool for soil sampling of heterogeneous pesticide (chlordecone) pollution

When field pollution is heterogeneous due to localized pesticide application, as is the case of chlordecone (CLD), the mean level of pollution is difficult to assess. Our objective was to design a decision support tool to optimize soil sampling. We analyzed the CLD heterogeneity of soil content at 0–30- and 30–60-cm depth. This was done within and between nine plots (0.4 to 1.8 ha) on andosol and ferralsol. We determined that 20 pooled subsamples per plot were a satisfactory compromise with respect to both cost and accuracy. Globally, CLD content was greater for andosols and the upper soil horizon (0–30 cm). Soil organic carbon cannot account for CLD intra-field variability. Cropping systems and tillage practices influence the CLD content and distribution; that is CLD pollution was higher under intensive banana cropping systems and, while upper soil horizon was more polluted than the lower one with shallow tillage (<40 cm), deeper tillage led to a homogenization and a dilution of the pollution in the soil profile. The decision tool we proposed compiles and organizes these results to better assess CLD soil pollution in terms of sampling depth, distance, and unit at field scale. It accounts for sampling objectives, farming practices (cropping system, tillage), type of soil, and topographical characteristics (slope) to design a relevant sampling plan. This decision support tool is also adaptable to other types of heterogeneous agricultural pollution at field level.     

Estimating mutagenic compounds generated during photolysis of fenitrothion--by HPLC fractionation followed by mutagenicity testing and high-resolution GC-MS analysis

We aimed to: (1) evaluate the change in mutagenicity of a fenitrothion-containing solution during photolysis and (2) elucidate mutagenic compounds that were possible major contributors to mutagenicity. A batch test involving irradiation by natural sunlight was conducted on the solution, and then HPLC fractionation, mutagenicity testing, and gas chromatography-mass spectrometry (GC-MS) analysis were performed on the irradiated solution. During the 15-day photolysis, fenitrothion was almost completely decomposed, and 34 transformed products (TPs) were generated. Photolysis decreased the mutagenicity of the fenitrothion-containing solution for base-pair-substitution-detecting tester strains (YG1026 and YG1029) but increased mutagenicity for frameshift-detecting tester strains (YG1021 and YG1024). One TP was identified as a potential source of the increased mutagenicity; its molecular formula was estimated to be (CH(3)O)(2)PS-O-C(8)H(6)NO.     

Formation and decomposition of chloroaromatic compounds in chlorine-containing benzene/oxygen flames

Premixed chlorine-containing, fuel-rich, low-pressure benzene/oxygen flames were analysed for the formation of (oxygenated) chloroaromatic compounds and their radicals by means of the condensation/radical-scavenging method (Hausmann, M., Homann, K.-H., 1995. Ber. Busenges. Phys. Chem. 99, 853-862). Several chlorinated organic compounds (methyl chloride, t-butyl chloride, chlorobenzene, chloroform) were used as additives within a maximum concentration of 10% of total fuel. Product identification and quantification were performed by GC/MS. The extent of formation of chloroaromatic compounds in these flames was largest in the cases of chlorobenzene and chloroform as additives. For chlorobenzene, 12 different chloroaromatics could be analysed in between C7H7Cl and C12H9Cl. Their formation is mainly due to conversion of initial chlorobenzene into substituted or oxidised derivatives, or growth products. Additional chlorination of aromatics is shown to be of minor importance in chlorobenzene-containing flames. Three isomeric (o/m/p) scavenging products could be identified for the chlorophenyl radical. In the chloroform case, 15 chloroaromatics could be analysed in between C6H5Cl and C14H9Cl. The weak C-Cl bond in chloroform is responsible for the high extent of chloroaromatics formation, either by Cl abstraction from the additive or by chlorination reactions via Cl radicals. Additionally, specific pathways to (di)chloroaromatics and chlorinated fulvene-type structures are outlined via CHCl2 and CCl2 radicals.     

Detoxification of hexachlorobenzene by dechlorination with potassium-sodium alloy

Dechlorination of hexachlorobenzene (HCB) was achieved by a liquid potassium–sodium (K–Na)-alloy. HCB in a cyclohexane/benzene solution (22 mmol/l, 4.67 g/l as chlorine) was dechlorinated by almost 100% after a 30-min reaction, indicating high reactivity of K–Na alloy and high proton donating power of cyclohexane. Decreasing orders of chlorobenzenes identified after a 15-min reaction, by amount were 1,2,3,4- > 1,2,3,5- > 1,2,4,5- for tetrachlorobenzenes, 1,2,4- > 1,2,3- > 1,3,5- for trichlorobenzenes, and 1,4- > 1,3- > 1,2- for dichlorobenzenes. It was hypothesized that once one chlorine atom in HCB was replaced with a proton, the adjacent chlorine atom to the proton tended to be replaced with another hydrogen atom. A total of 63 PCBs formed via the Wurtz–Fittig reaction were identified as by-products in the sample after a 15-min reaction. Among PCBs found, 2,3^′,4^′,5-tetrachlorobiphenyl, which was a product from 1,2,4-trichlorobenzene formed via the Wurtz–Fittig reaction, was detected in relatively high concentration (48.9 nmol/ml). The sample obtained from a reaction mixture after 30 min contained only 14 PCBs in trace amounts, indicating that the PCBs formed were also further dechlorinated by K–Na alloy. Non-chlorinated compounds––such as methylbenzene, dimethylbenzene, dimer of tetrahydrofuran, and dicyclohexyl (dimer of cyclohexane)––were also identified in the samples. A method using K–Na alloy developed in the present study dechlorinated satisfactorily HCB at room temperature.     

Effects of dissolved oxygen, pH, and anions on the 2,3-dichlorophenol degradation by photocatalytic reaction with anodic TiO(2) nanotube films

In this study, the highly-ordered TiO(2) nanotube (TNT) arrays on titanium sheets were prepared by an anodic oxidation method. Under UV illumination, the TNT films demonstrated the higher photocatalytic activity in terms of 2,3-dichlorophenol (2,3-DCP) degradation in aqueous solution than the conventional TiO(2) thin films prepared by a sol-gel method. The effects of dissolved oxygen (DO) and pH on the photocatalytic degradation of 2,3-DCP were investigated. The results showed that the role of DO in the 2,3-DCP degradation with the TNT film was significant. It was found that 2,3-DCP in alkaline solution was degraded and dechlorinated faster than that in acidic solution whereas dissolved organic carbon removal presented an opposite order in dependence of pH. In the meantime, some main intermediate products from 2,3-DCP degradation were identified by a (1)H NMR technique to explore a possible degradation pathway. A major intermediate, 2-chlororesorcinol, was identified from the 2,3-DCP decomposition as a new species compared to the findings in previous reports. Photocatalytic deactivation was also evaluated in the presence of individual anions (NO(3)(-), Cl(-), SO(4)(2-), and H(2)PO(4)(-)). The inhibition degree of photocatalytic degradation of 2,3-DCP caused by these anions can be ranked from high to low as SO(4)(2-)>Cl(-)>H(2)PO(4)(-)>NO(3)(-). The observed inhibition effect can be attributed to the competitive adsorption and the formation of less reactive radicals during the photocatalytic reaction.     

Perfluorooctanoic acid (PFOA) acts as a tumor promoter on Syrian hamster embryo (SHE) cells

Perfluorooctane sulfonate (PFOS) (C(8)F(17)SO(3)) and perfluorooctanoic acid (PFOA) (C(8)HF(15)O(2)) are synthetic chemicals widely used in industrial applications for their hydrophobic and oleophobic properties. They are persistent, bioaccumulative, and toxic to mammalian species. Their widespread distribution on earth and contamination of human serum raised concerns about long-term side effects. They are suspected to be carcinogenic through a nongenotoxic mode of action, a mechanism supported by recent findings that PFOS induced cell transformation but no genotoxicity in Syrian hamster embryo (SHE) cells. In the present study, we evaluated carcinogenic potential of PFOA using the cell transformation assay on SHE cells. The chemical was applied alone or in combination with a nontransformant concentration of benzo[a]pyrene (BaP, 0.4?μM) in order to detect PFOA ability to act as tumor initiator or tumor promoter. The results showed that PFOA tested alone in the range 3.7?×?10(-5) to 300?μM did not induce SHE cell transformation frequency in a 7-day treatment. On the other side, the combination BaP/PFOA induced cell transformation at all PFOA concentrations tested, which revealed synergistic effects. No genotoxicity of PFOA on SHE cells was detected using the comet assay after 5 and 24?h of exposure. No significant increase in DNA breakage was found in BaP-initiated cells exposed to PFOA in a 7-day treatment. The whole results showed that PFOA acts as a tumor promoter and a nongenotoxic carcinogen. Cell transformation in initiated cells was observed at concentrations equivalent to the ones found in human serum of nonoccupationally and occupationally exposed populations. An involvement of PFOA in increased incidence of cancer recorded in occupationally exposed population cannot be ruled out.     

Genotoxicity of two novel pesticides for the earthworm, Eisenia fetida

In this paper, several studies were conducted to evaluate the genotoxicity of two pesticides, Imidacloprid and RH-5849, for earthworm (Eisenia fetida). Earthworms were exposed in different exposure systems to evaluate their acute toxicity and the genotoxicity of the two pesticides was evaluated by using the method of sperm deformity assessment, micronucleus test of root tip cells in Vicia faba, a mouse bone-marrow micronucleus test, and comet assay. LC(50) (interpolated concentration at which 50% mortality of test population occurs) for earthworms varied in different exposure systems. The results indicated that Imidacloprid was consistently more toxic than RH-5849 in all exposure systems. In this study, sperm deformity test was used to detect the potential adverse influences of pesticides on the reproduction of earthworms. The results demonstrated that significant induction of sperm deformity (p<0.01) and a dose-effect relationship displayed at Imidacloprid concentrations higher than 0.5 mg/kg dry soil. However, the sperm deformity frequency of groups exposed to RH-5849 did not show significant difference (p>0.05) from the control until the dose reached 100 mg/kg dry soil. The results of the V. faba micronucleus tests showed that micronuclei frequency of the exposed group did not show significant difference (p>0.05) from the control until the concentration of Imidacloprid and RH-5849 reached 100 mg/ml. The results of the mouse bone-marrow micronuclei test also indicate that two pesticides did not show significant effects (p>0.05) on the micronuclei frequency in mice bone-marrow cells until the dose reached 100 mg/kg for Imidacloprid and 300 mg/kg for RH-5849 (2/3 LD(50)). Although no genotoxicity was detected by using the micronucleus tests, the results of the comet assay showed that the two pesticides induce significant DNA damage (p<0.01) in earthworms and dose-effect relationships were displayed. The 'earthworm comet assay' is a rapid and sensitive way to screen chemicals or terrestrial environments for their DNA-damaging properties.     

Correlation of gas chromatographic properties of chlorobenzenes and polychlorinated biphenyls with the occurrence of reductive dechlorination by untamed microorganisms

To understand the dechlorination ability of chlorobenzenes (CBs) and polychlorinated biphenyls (PCBs) by untamed microorganisms under anaerobic condition and to correlate gas chromatographic properties with the occurrence of reductive dechlorination, introduction of CBs and PCBs in the culture medium inoculated with microorganisms from sludge and sediment, respectively, were performed. Three kinds of culture media preparing from sludge, river water and a synthetic medium were used in the experiments. HCB was degraded to 1,3,5-trichlorobenzene (1,3,5-TCB) and 1,3-dichlorobenzene (1,3-DCB) in both sludge medium and synthetic medium with inoculated microorganisms. Three PCB congeners including 2,3,4-, 3,4,5- and 2,3,4,5-CBp (chlorinated biphenyl) were not found to be dechlorinated in the river water medium with inoculation culture but to be dechlorinated in the synthetic medium. MNDO methodology was used to compute theoretical dechlorination reaction heats and GC-ECD techniques were used to estimate chromatographic data of CB and PCB congeners. Both CB and PCB congeners showed that dechlorination by untamed microorganisms under anaerobic mixed cultures were more likely to occur when larger amounts of energy were released and greater deltaln RRT value between the parent congener and the daughter product was observed. Deltaln RRT provided a more precise information on the singularity of PCBs ortho-dechlorination in an aspect of thermodynamic favorable rule.