Photolysis of vinclozolin

Following photolysis of vinclozolin in methanol five products were detected and identified: 3,5-dichlorophenylisocyanate, 3,5-dichloroaniline, methyl 3,5-dichlorophenylcarbamate, 3-(3-chlorophenyl)-5-methyl-5-vinyl-oxazolidine-2,4-dione and methyl (3,5-dichlorophenyl) (2-hydroxy-2-methyl-1-oxo-buten-3-yl) carbamate. The major component identified from photolysis in benzene solution, 3-(3-chlorobiphenyl)-5-methyl-5-vinyl-oxazolidine-2,4-dione, was produced by replacement of one chlorine atom by a solvent molecule.     

二氧化钛/碳纳米管/壳聚糖薄膜的制备及对苯的降解性能

研究了光催化降解挥发性有机化合物过程中催化剂二氧化钛/碳纳米管/壳聚糖薄膜的制备以及该催化剂对苯的光催化性能。首先采用溶胶-凝胶法制备纳米复合材料二氧化钛/碳纳米管,然后利用壳聚糖作为交联剂,制得二氧化钛/碳纳米管/壳聚糖复合材料催化薄膜。通过傅立叶红外光谱(FT-IR)、X射线衍射(XRD)透射电镜扫描(TEM)和紫外-可见光漫反射(UV-Vis)等技术分析了复合材料薄膜的组成、结构、形貌和对光的吸收性能,然后使用该催化剂对室内常见的污染物苯进行降解,并在同样的实验条件下,使用催化剂二氧化钛(P25)/壳聚糖对苯进行降解,对两者催化性能进行对比,结果表明,二氧化钛/碳纳米管/壳聚糖对苯有更强的吸附能力和更高的催化活性。     

Light-induced degradation of perfluorocarboxylic acids in the presence of titanium dioxide

The UV-photon-induced degradation of heptafluorobutanoic acid was investigated in acidic aqueous solutions in the presence of titanium dioxide. Heptafluorobutanoic acid could be degraded with this photocatalyst in a light-induced reaction generating carbon dioxide and fluoride anions. Carbon dioxide evolution in a significant amount occurred only in the presence of molecular oxygen and the photocatalyst. The light-induced degradation of trifluoroacetic acid, pentafluoropropanoic acid, nonafluorobutanoic acid, pentadecafluorooctanoic acid, nonafluorobutanesulfonic acid, and heptadecafluorooctanesulfonic acid in the presence of titanium dioxide was also studied. The perfluorocarboxylic acids under investigation are degraded to generate CO(2) and fluoride anions while both perfluorinated sulfonic acids are persistent under the experimental conditions employed in this study. For all compounds photonic efficiencies of the mineralization reaction were estimated to be smaller than 1x10(-5). To increase the photocatalytic activity mixed systems containing homogeneous phosphotungstic acid and heterogeneous titanium dioxide catalysts were also investigated. In the mixtures of these two photocatalysts, the formation rate of CO(2) increased with illumination time.     

Carbamazepine degradation by photolysis and titanium dioxide photocatalysis

We investigated the degradation of carbamazepine by photolysis/ultraviolet (UV)-C only and titanium dioxide photocatalysis. The degradation of carbamazepine by UV-only and titanium-dioxide-only (adsorption) reactions were inefficient, however, complete degradation of carbamazepine was observed by titanium dioxide photocatalysis within 30 min. The rate of degradation increased as initial carbamazepine concentration decreased, and the removal kinetics fit well with the Langmuir-Hinshelwood model. The addition of methanol, a radical scavenger, decreased carbamazepine removal, suggesting that the hydroxide radical played an important role during carbamazepine degradation. The addition of oxygen during titanium dioxide photocatalysis accelerated hydroxide radical production, thus improving mineralization activity. The photocatalytic degradation was more efficient at a higher pH, whereas the removal of carbamazepine and acridine (a major intermediate) were more efficient under aerobic conditions. The mineralization of carbamazepine during photocatalysis produced various ionic by-products such as ammonium and nitrate by way of nitrogen dioxide.     

Photodegradation of chlorinated pesticides dispersed on sand

The photochemical behaviour of several chlorinated pesticides, namely 4-chloro-2-methylphenoxyacetic acid (MCPA), dichlorophen (DCPH), flamprop-methyl (FPM) and vinclozolin (VCZ) is studied on various kinds of sand: Fontainebleau sand (almost pure silica), Touggourt sand (coloured sand from Sahara) and Jijel sand (dark marine sand). The photodegradation of MCPA is more rapid on Fontainebleau sand than on the two others, because the former is almost colourless pure silica and the others adsorb on the internal surface of the reactor. The degradation rate decreases in the order MCPA, DCPH, FPM, VCZ. The main products identified are 4-chloro-2-methylphenol with MCPA and reduction product with DCPH.     

The pH and anion effects on the heterogeneous photocatalytic degradation of o-methylbenzoic acid in TiO2 aqueous suspension

This investigation used UV light of 365 nm and titanium dioxide in aqueous suspension to study the photocatalytic reaction of o-methylbenzoic acid under the influence of pH values, anion additives and the varieties of titanium dioxide. From experimental results, under the condition of 5 g/l TiO2, pH 3 and light intensity of 2.45 mW/cm2, 0.1 mM of o-methylbenzoic acid could be completely decomposed in 2 h. The reaction was faster with lowering pH, and was found to be apparent first-order following Langmuir-Hinshelwood model. In the presence of anion additives, the inhibitive effect of chloride ions was larger than that of sulfate ions under acidic condition for Degussa brand titanium dioxide, but without influence using Janssen brand. Both brands, however, promoted the mineralization of o-methylbenzoic acid (o-MBA).     

Microfibrous mesh coated with titanium dioxide: a self-sterilizing,self-cleaning filter

The utility of metal microfibrous mesh coated with titanium dioxide as a self-sterilizing, self-cleaning filter for air is explored. The low-cost mesh is produced via a roll-to-roll process similar to paper manufacturing. The titanium dioxide is applied by spraying an aqueous suspension of the photocatalyst on the surface of the mesh using an airbrush. Photocatalytic activity comparable to a powder layer is achieved at one quarter of the mass loading. The coating enhanced the separation of Escherichia coli (E. coli) from aqueous suspension, but also led to an increase in pressure drop in an air stream flowing through the mesh. The self-cleaning property of the coated mesh is established by recovery of pressure drop performance lost due to biofilm buildup. This is accomplished via a photocatalytic regeneration process involving exposing the mesh to ultraviolet light in air. Oxidation is confirmed by monitoring CO2 evolution during the regeneration. Scanning electron photomicrographs also provide visual evidence of successful regeneration via photocatalysis.     

超细TiO2粒子的超滤分离及回用特性

针对TiO2超细粒子的超滤分离特性进行了试验研究,探讨了操作压力、膜面流速、TiO2投量、pH、电解质等参数条件对膜通量的影响规律及作用机理,证实了浓差极化及滤饼层阻力是影响通量变化的主导因素,在此基础上确定了适宜的超滤工艺条件及膜清洗方式.以甲基橙为降解基质分别测试了经混凝与超滤分离后的TiO2光催化活性,结果表明,超滤不仅可实现TiO2粒子与水的彻底分离,且分离后TiO2催化活性与初次使用相当.研究表明超滤用于悬浮光催化体系的固液分离及催化剂再用是可行的.     

铂铈共掺杂纳米TiO2的制备、表征及光催化性能

以钛酸四丁酯为前驱体,过氧化氢为氧化剂,采用简单易行的低温氧化法制备出晶粒尺寸较小（平均尺寸25nm）的二氧化钛纳米粒子。通过贵金属Pt掺杂TiO2（Pt-TiO2）、稀土元素Ce掺杂TiO2（Ce-TiO2）和Pt、Ce共掺杂TiO2（Pt／Ce-TiO2）的掺杂的方法对二氧化钛进行改性。通过XRD,XPS,TEM,紫外漫反射等表征手段对制备的样品进行表征。通过可见光下降解罗丹明B来测试其光催化活性。实验结果表明,由ce掺杂的TiO2光催化剂对有机污染物的最大降解能力略大于Pt掺杂的TiO2,2种元素进行共同掺杂时对应的TiO2光催化剂降解能力最大。     

Photocatalytic degradation of atrazine by porphyrin and phthalocyanine complexes

This study principally focused on a new kind of photochemical reaction catalyst: porphyrin and phthalocyanine complexes. In a first step, the preparation of the catalysts was optimized. A resin has been chosen to be the support of the complexes. Efficiency of catalytic activity is performed on the degradation of a pesticide: atrazine. The best atrazine degradation occurs with 4.6% of complexes versus substrate. The role of the surface has also been shown to be important. Then, their performances were demonstrated in terms of kinetics and degradation routes, compared to a classical catalyst: titanium dioxide. This study seeks to assess the efficiency of these systems both in a mercury lamp reactor and under solar irradiation which reduces energy costs. The best atrazine degradation half-life found for the complexes is about 200 min with the iron phthalocyanine. These catalysts exhibit particular oxidation activities. Indeed, the degradation routes have been found different between the semi-conductor and the metallic complexes. These complexes are able to cleave the triazinic ring more efficiently than the titanium dioxide.     

铂铈共掺杂纳米TiO2的制备、表征及光催化性能

以钛酸四丁酯为前驱体,过氧化氢为氧化剂,采用简单易行的低温氧化法制备出晶粒尺寸较小(平均尺寸25 nm)的二氧化钛纳米粒子。通过贵金属Pt掺杂TiO₂(Pt-TiO₂)、稀土元素Ce掺杂TiO₂(Ce-TiO₂)和Pt、Ce共掺杂TiO₂(Pt/Ce-TiO₂)的掺杂的方法对二氧化钛进行改性。通过XRD,XPS,TEM,紫外漫反射等表征手段对制备的样品进行表征。通过可见光下降解罗丹明B来测试其光催化活性。实验结果表明,由Ce掺杂的TiO₂光催化剂对有机污染物的最大降解能力略大于Pt掺杂的TiO₂,2种元素进行共同掺杂时对应的TiO₂光催化剂降解能力最大。     

Carbofuran removal in continuous-photocatalytic reactor: Reactor optimization,rate-constant determination and carbofuran degradation pathway analysis

Carbofuran (CBF) removal in a continuous-flow photocatalytic reactor with granular activated carbon supported titanium dioxide (GAC-TiO₂) catalyst was investigated. The effects of feed flow rate, TiO₂ concentration and addition of supplementary oxidants on CBF removal were investigated. The central composite design (CCD) was used to design the experiments and to estimate the effects of feed flow rate and TiO₂ concentration on CBF removal. The outcome of CCD experiments demonstrated that reactor performance was influenced mainly by feed flow rate compared to TiO₂ concentration. A second-order polynomial model developed based on CCD experiments fitted the experimental data with good correlation (R² ～ 0.964). The addition of 1 mL min^?1 hydrogen peroxide has shown complete CBF degradation and 76% chemical oxygen demand removal under the following operating conditions of CBF ～50 mg L^?1, TiO₂ ～5 mg L^?1 and feed flow rate ～82.5 mL min^?1. Rate constant of the photodegradation process was also calculated by applying the kinetic data in pseudo-first-order kinetics. Four major degradation intermediates of CBF were identified using GC-MS analysis. As a whole, the reactor system and GAC-TiO₂ catalyst used could be constructive in cost-effective CBF removal with no impact to receiving environment through getaway of photocatalyst.     

Microbial conversion of fungicide vinclozolin

An ecological safety study of using vinclozolin in field and laboratory experiments showed that the effect of the preparation led to a decrease in the abundance of actinomycetes and mycelial fungi and an enhancement of nitrification. The residual amounts of vinclozolin in soil after 12 months were 6-12% of the dose introduced. The persistent chlorinated derivatives of the toxicant were found. Microbial strains pertaining to the genera Pseudomonas and Bacillus were isolated that utilized vinclozolin as the sole source of carbon and energy.     

Photodegradation of monochlorobenzene in titanium dioxide aqueous suspensions

The photocatalytic degradation of monochlorobenzene using titanium dioxide aqueous suspensions was performed under solar-simulated irradiation. The effects of concentration of monochlorobenzene, amount of titanium dioxide and pH of solution on the degradation were examined. The intermediates identified were three monochlorophenols, chlorohydroquinone and hydroxy-hydroquinone.     

Evaluation of a sequential extraction process used for determining mercury binding mechanisms to coal combustion byproducts

Leaching of mercury from coal combustion byproducts is a concern because of the toxicity of mercury. Leachability of mercury can be assessed by using sequential extraction procedures. Sequential extraction procedures are commonly used to determine the speciation and mobility of trace metals in solid samples and are designed to differentiate among metals bound by different mechanisms and to different solid phases. This study evaluated the selectivity and effectiveness of a sequential extraction process used to determine mercury binding mechanisms to various materials. A six-step sequential extraction process was applied to laboratory-synthesized materials with known mercury concentrations and binding mechanisms. These materials were calcite, hematite, goethite, and titanium dioxide. Fly ash from a full-scale power plant was also investigated. The concentrations of mercury were measured using inductively coupled plasma (ICP) mass spectrometry, whereas the major elements were measured by ICP atomic emission spectrometry. The materials were characterized by X-ray powder diffraction and scanning electron microscopy with energy dispersive spectroscopy. The sequential extraction procedure provided information about the solid phases with which mercury was associated in the solid sample. The procedure effectively extracted mercury from the target phases. The procedure was generally selective in extracting mercury. However, some steps in the procedure extracted mercury from nontarget phases, and others resulted in mercury redistribution. Iron from hematite and goethite was only leached in the reducible and residual extraction steps. Some mercury associated with goethite was extracted in the ion exchangeable step, whereas mercury associated with hematite was extracted almost entirely in the residual step. Calcium in calcite and mercury associated with calcite were primarily removed in the acid-soluble extraction step. Titanium in titanium dioxide and mercury adsorbed onto titanium dioxide were extracted almost entirely in the residual step.     

Selected endocrine disrupting compounds (Vinclozolin,Flutamide, Ketoconazole and Dicofol): Effects on survival,occurrence of males,growth, molting and reproduction of <Emphasis Type="Italic">Daphnia magna</Emphasis>

BACKGROUND, AIM AND SCOPE: Pollution-induced endocrine disruption in vertebrates and invertebrates is a worldwide environmental problem, but relatively little is known about effects of endocrine disrupting compounds (EDCs) in planktonic crustaceans (including Daphnia magna). Aims of the present study were to investigate acute 48 h toxicity and sub-chronic (4-6 days) and chronic (21 days) effects of selected EDCs in D. magna. We have investigated both traditional endpoints as well as other parameters such as sex determination, maturation, molting or embryogenesis in order to evaluate the sensitivity and possible use of these endpoints in ecological risk assessment. MATERIALS AND METHODS: We have studied effects of four model EDCs (vinclozolin, flutamide, ketoconazole and dicofol) on D. magna using (i) an acute 48 h immobilization assay, (ii) a sub-chronic, 4-6 day assay evaluating development and the sex ratio of neonates, and (iii) a chronic, 21 day assay studying number of neonates, sex of neonates, molting frequency, day of maturation and the growth of maternal organisms. RESULTS: Acute EC50 values in the 48 h immobilization test were as follows (mg/L): dicofol 0.2, ketoconazole 1.5, flutamide 2.7, vinclozolin >3. Short-term, 4-6 day assays with sublethal concentrations showed that the sex ratio in Daphnia was modulated by vinclozolin (decreased number of neonate males at 1 mg/L) and dicofol (increase in males at 0.1 mg/L). Flutamide (up to 1 mg/L) had no effect on the sex of neonates, but inhibited embryonic development at certain stages during chronic assay, resulting in abortions. Ketoconazole had no significant effects on the studied processes up to 1 mg/L. DISCUSSION: Sex ratio modulations by some chemicals (vinclozolin and dicofol) corresponded to the known action of these compounds in vertebrates (i.e. anti-androgenicity and anti-oestrogenicity, respectively). Our study revealed that some chemicals known to affect steroid-regulated processes in vertebrates can also affect sublethal endpoints (e.g. embryonic sex determination and/or reproduction) in invertebrates such as D. magna. CONCLUSIONS: A series of model vertebrate endocrine disrupters affected various sub-chronic and chronic parameters in D. magna including several endpoints that have not been previously studied in detail (such as sex determination in neonates, embryogenesis, molting and maturation). Evaluations of traditional reproduction parameters (obtained from the 21 day chronic assay). as well as the results from a rapid, 4-6 day, sub-chronic assay provide complementary information on non-lethal effects of suspected organic endocrine disrupters. RECOMMENDATIONS AND PERSPECTIVES: It seems that there are analogies between vertebrates and invertebrates in toxicity mechanisms and in vivo effects of endocrine disruptors. However, general physiological status of organisms may also indirectly affect endpoints that are traditionally considered 'hormone regulated' (especially at higher effective concentrations as observed in this study) and these factors should be carefully considered. Further research of D. magna physiology and comparative studies with various EDCs will help to understand mechanisms of action as well as ecological risks of EDCs in the environment.     

Screening differentially expressed genes in an amphipod (Hyalella azteca) exposed to fungicide vinclozolin by suppression subtractive hybridization

Vinclozolin, a dicarboximide fungicide, is an endocrine disrupting chemical that competes with an androgenic endocrine disruptor compound. Most research has focused on the epigenetic effect of vinclozolin in humans. In terms of ecotoxicology, understanding the effect of vinclozolin on non-target organisms is important. The expression profile of a comprehensive set of genes in the amphipod Hyalella azteca exposed to vinclozolin was examined. The expressed sequence tags in low-dose vinclozolin-treated and -untreated amphipods were isolated and identified by suppression subtractive hybridization. DNA dot blotting was used to confirm the results and establish a subtracted cDNA library for comparing all differentially expressed sequences with and without vinclozolin treatment. In total, 494 differentially expressed genes, including hemocyanin, heatshock protein, cytochrome, cytochrome oxidase and NADH dehydrogenase were detected. Hemocyanin was the most abundant gene. DNA dot blotting revealed 55 genes with significant differential expression. These genes included larval serum protein 1 alpha, E3 ubiquitin-protein ligase, mitochondrial cytochrome c oxidase, mitochondrial protein, proteasome inhibitor, hemocyanin, zinc-finger–containing protein, mitochondrial NADH-ubiquinone oxidoreductase and epididymal sperm-binding protein. Vinclozolin appears to upregulate stress-related genes and hemocyanin, related to immunity. Moreover, vinclozolin downregulated NADH dehydrogenase, related to respiration. Thus, even a non-lethal concentration of vinclozolin still has an effect at the genetic level in H. azteca and presents a potential risk, especially as it would affect non-target organism hormone metabolism.     

Environmental fate of pesticides used in Australian viticulture: Behaviour of dithianon and vinclozolin in the soils of the South Australian Riverland

The red calcareous earth soils of the South Australian Riverland produce more than one-third of the grapes used in Australian winemaking. As part of on-going investigations into pesticide transport in Australian vineyard soils, the movement of the fungicides dithianon and vinclozolin through such strongly alkaline soils was investigated. Small, undisturbed soil cores were extracted from the inter-row topsoil of a vineyard adjacent to the River Murray, approximately 10 km S.W. of Overland Corner, South Australia. The vines were grown in a deep (1 – 4 m) reddish brown, strongly alkaline, sandy loam with a low organic carbon content (1 – 2 %). Surface fluxes of pesticide were applied at the maximum recommended application rates to the surface of the cores, which were then irrigated, and pesticide residues in the leachate determined by HPLC. No leaching of either dithianon or vinclozolin occurred. Dithianon was immobilised in the top 2 cm of the soil. Dithianon concentrations were low ( 0 – 37 % applied dose) suggesting that rapid degradation of this compound occurs in these soils (63 – 100 % degradation in 10 days). Extremely low concentrations of vinclozolin were found throughout the soil core profiles (0.05 – 1.4 % applied dose) suggesting that this fungicide was somewhat mobile, but also that it too was unstable in such alkaline soils (> 98 % degradation in 10 days). These results suggest that the irrigated vineyard soils of this region are unlikely to be prone to leaching of dithianon or vinclozolin, and therefore that groundwater supplies in this area are unlikely to be at any significant risk of contamination through viticultural use of these compounds.     

Photocatalytic and combined anaerobic-photocatalytic treatment of textile dyes

A photocatalytic process based on immobilized titanium dioxide was used to treat crude solutions of azo, anthraquinone and phthalocyanine textile dyes. In addition, the process was applied to the treat autoxidized chemically reduced azo dyes, i.e. representatives of recalcitrant dye residues after biological sequential anaerobic-aerobic treatment. Photocatalysis was able to remove more than 90% color from crude as well as autoxidized chemically reduced dye solutions. UV-absorbance and COD were also removed but to a lower extent (50% in average). The end products of photocatalytic treatment were not toxic toward methanogenic bacteria. The results demonstrate that photocatalysis can be used as a pre- or post-treatment method to biological anaerobic treatment of dye-containing textile wastewater.     

Transfer of the fungicide vinclozolin from treated to untreated plants via volatilization

Head lettuce plantlets (Lactuca sativa L. var. capitata) were potted, treated with vinclozolin at the six-leaf stage according to application standards and allowed to dry for 24 h. The potted plantlets were then placed in either growth chambers with controlled temperature (20 and 25 degrees C, respectively) or in a greenhouse (approximately 12 degrees C), together with untreated spinach (Spinacia oleracea L.) and standardized grass cultures (Lolium multiflorum Lam. ssp.) While the treated lettuce pots remained in the respective growing compartments until the end of the experiments, spinach and grass were exposed to the compartment air for 24 h and their shoot material was analyzed for vinclozolin by GC-ECD and GC-high resolution mass spectrometry. Exposure and analysis of untreated spinach and grass were carried out at two- or three-day intervals during the course of the experiments. Also, air samples were taken from the compartments at intervals and analyzed for vinclozolin. Maximum vinclozolin concentration in the growth chamber air was about 330 ng m(-3) while vinclozolin contamination of the untreated plants ranged from 50 to 200 microg kg(-1) FW (fresh weight). In the greenhouse atmospheric vinclozolin concentration reached approximately 15 ngm(-3) and maximum contamination of spinach and grass were 30-40 microg kg(-1) FW. Our data clearly show that unintended contamination of plants growing in the vicinity of vinclozolin-treated plants can occur even if the fungicide layer is completely dry. Implications for safety testing and food plants are discussed.