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.     

Degradation of chlorophenols in aqueous media using UV XeBr excilamp in a flow-through reactor

2-Chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) at initial concentrations of 10, 20, 50 and 100mg l(-1) were degraded in aqueous media by direct UV photolysis using dielectric barrier discharge XeBr( *) excilamp (283nm) in a flow-through photoreactor. The pseudo-first order rate constants were highest and half-life times were lowest for 4-CP. The rates of photolysis under the experimental conditions increased in the order: 2-CP<2,4-DCP<4-CP. The intermediates of photolysis were identified by GC-MS and HPLC. The evolution of hydroquinone and p-benzoquinone as major intermediates of 4-CP photolysis was monitored.     

The photodecomposition of fenitrothion [0, 0-dimethyl-0-(3-methyl-4-nitrophenol) phosphorothioate]

The photolysis of fenitrothion in vapor and liquid phase has been examined, using radiation available in the solar spectrum, i.e., λ> 300 nm. In both the vapor phase and in ethanol solution, two primary products are produced, the major one being p-nitrocresol (4-nitro-3-methyl-phenol). Prolonged irradiation yields additional products probably due to secondary photolysis. The photodecomposition of fenitrothion may be one of the reasons for the rapid disappearance of this material when it is introduced into the environment.     

Light-induced disappearance of nitrite in the presence of iron (III)

Understanding of rapid disappearance of nitrite in natural waters and its impact on nitrogen natural cycling has remained limited. We found that NO2- disappeared rapidly in pH 3.2 aqueous Fe(III) solutions both in sunlight and in 356 nm light. Quantum yields of the NO2- loss at 356 nm were 0.049-0.14 for initial levels of 10-80 microns NO2- and 200 microns Fe(III). The NO2- loss (at 356 nm) followed apparent first-order kinetics. The rate constants were 1.3 x 10(-3) (40 microns NO2-) and 4.1 x 10(-4) s-1 (80 microns NO2-) for 100 microns Fe(III), and 2.3 x 10(-3) (40 microns NO2-) and 7.5 x 10(-4) s-1 (80 microns NO2(-1)) for 200 microns Fe(III) (t1/2 = 8.7, 27.9, 5.1, and 15.3 min, respectively). The rate constants were directly proportional to [Fe(III)]0 and inversely proportional to [NO2-]0. Agreement between the rate constants obtained experimentally and those calculated mechanistically supports the hypothesis that NO2- was oxidized to NO2 by .OH radicals from photolysis of FeOH2+ complexes, and at high [NO2-]0 (e.g., 80 microns) relative to [Fe(III)]0, hydrolysis of NO2 or N2O4 to form NO3- and NO2- could be significant. This study showed that light and Fe(III)-induced oxidation of NO2- (rate = approximately 10(-1)-10(-2) microns s-1) was more rapid than its direct photolysis (rate = approximately 10(-4) microns s-1), and the photolysis could be a significant source of .OH radicals only in cases where the Fe(III) level is much lower than the NO2- level ([Fe(III)]/[NO2-] < 1/80). This study suggests that the light and Fe(III)-induced oxidation of NO2- would be one potential important pathway responsible for the rapid transformation of NO2- in acidic surface waters, especially those affected by acid-mine drainage or volcanic activities. This study also may be of interest for modeling certain acidic atmospheric water environments.     

Photodegradation of the steroid hormones 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in dilute aqueous solution

The photochemical transformation of natural estrogenic steroid 17beta-estradiol (E2) and the synthetic oral contraceptive 17alpha-ethinylestradiol (EE2) has been studied in dilute non buffered aqueous solution (pH 5.5-6.0) upon monochromatic (254 nm) and polychromatic (lambda>290 nm) irradiation. Upon irradiation at 254 nm, the quantum yields of E2 and EE2 photolysis were similar and evaluated to be 0.067+/-0.007 and 0.062+/-0.007, respectively. Upon polychromatic excitation, and by using phenol as chemical actinometer, the photolysis efficiencies have been determined to be 0.07+/-0.01 and 0.08+/-0.01 for E2 and EE2, respectively. For both estrogens, photodegradation by-products were identified with GC/MS and LC/MS. In a first step, a model compound--5,6,7,8-tetrahydro-2-naphthol (THN)--, which represents the photoactive phenolic group, was used to obtain basic photoproduct structural informations. Numerous primary and secondary products were observed, corresponding to hydroxylated phenolic- or quinone-type compounds.     

Further study on the photochemistry of non-ortho substituted PCBs by UV irradiation in alkaline 2-propanol

The photochemical behaviors of six non-ortho substituted PCB congeners, i.e., 3,4-DiCB, 3,5-DiCB, 3,3',5-TriCB, 3,4,5-TriCB, 3,3',4,5-TetraCB, and 3,4,4',5-TetraCB, irradiated at 254 nm in alkaline 2-propanol were investigated. Besides the determination of the photodechlorination pathways of these compounds, the presence of photorearrangement was observed in the case of 3, 4-DiCB with its products being identified. The results indicate that dechlorination is much more important than rearrangement during the process of PCB photolysis.     

LP/LIF study of the formation and consumption of mercury (I) chloride: kinetics of mercury chlorination

The laser photolysis/laser induced fluorescence (LP/LIF) technique has been applied to studies of gas-phase mercury (Hg) chlorination. Mercury (I) chloride (HgCl) was been detected via LIF at 272 nm from reactions of elemental Hg with Cl atoms generated from the 193 nm photolysis of carbon tetrachloride. While the formation of HgCl was too fast to be observed on millisecond time scales, the kinetics of the consumption of HgCl have been determined at temperatures characteristic of post-combustion conditions. Rate coefficients and Arrhenius parameters for the reaction of HgCl with Cl2, HCl and Cl atoms were determined. The reaction of HgCl with Cl2 was the fastest reaction studied, while the reaction of HgCl with HCl was the only reaction to show any measurable temperature dependence. Estimates of the rate coefficient for the reaction Hg + Cl --> HgCl were determined using a modeling approach. Comparisons of these new measurements with model predictions are discussed.     

The direct photolysis and photocatalytic degradation of alachlor at different TiO2 and UV sources

Direct photolysis and photocatalytic degradations of alachlor, a widely used herbicide, were studied using three different monochromatic UV lamps (254, 300 and 350 nm) and two TiO(2) sources. Both the direct photolysis and photocatalytic degradations of alachlor follow pseudo-first-order decay kinetics. TiO(2)-P25 was found to be an effective photocatalyst compared to TiO(2)-BDH. The direct photolysis of alachlor was dominant at 254 nm even if TiO(2) was present in the solution. Among the three UV wavelengths used, the highest photocatalysis quantum yield was obtained at 300 nm. The photocatalytic degradation rate of alachlor increased with the dosages of TiO(2), but an overdose of TiO(2) would retard the reaction due to light attenuation. Photocatalytic reactions were slightly enhanced in an alkaline medium, and the different proton sources causing various degrees of rate retardation were due to the presence of the corresponding counter anions. This effect was diminished at a later stage after the reaction intermediates were formed.     

Surfactant effect on persistence of oxadiazolyl 3(2H)-pyridazinones against Pseudaletia separata walker

The photodynamic decomposition of two new insect-growth inhibitors (IGRs), 2-tert-butyl-5-[5′-aryl-2′-(1′,3′,4′-oxadiazolyl)methoxy]-3(2H)-pyridazinones (OPB) and its 4-chloro substituted derivative (OPC), and effect of surfactants on persistence of their bioactivity were taken into investigation. Both chemicals were significantly induced to photolysis by ultraviolet light at 365 nm wavelength and their inhibitory activities against Pseudaletia separata larvae decreased with the increasing irradiation time. However, irradiation at 254 nm wavelength didn't cause their photodegradation. Triton X-100 and Succinic-sulfonie acidic sodium but not Tween 60 possessed strong capability to slow down the decomposition and obviously prolonged the half life of OPC in laboratory and field whilst effects of the three surfactants almost did not preserve the inhibitory activity of OPB. Data suggested that electron-withdrawing halogen (?Cl) on the π electron system in planar benzene-oxadialyl structures might reduce the efficiency of OPC on ultraviolet (UV) photoabsorption, and its hydrophobic interaction with the surfactants might be beneficial for forming stable micellar solubilization, thus sustaining the chemical's bioactivity.     

Gas phase trichloroethylene (TCE) photooxidation and byproduct formation: photolysis vs. titania/silica based photocatalysis

Photooxidation of trichloroethylene (TCE) was examined in comparative study using photolysis and photocatalysis. Degussa P25 titania coated on reactor wall and deposited on silica based microporous support were used as photocatalyst. The destruction of TCE and formation of potential byproducts were investigated under steady state conditions using annular photoreactors. Experimental work involved passing polluted air containing TCE through the UV photoreactor at varying concentrations and residence times. Ultraviolet illumination was provided by low pressure mercury lamps with outputs at either 254 nm, 365 nm, or 185/254 nm. Silica supported photocatalyst yielded maximum removal capacity of up to about 6 kg TCE per m3 per hour, nearly twice that provided by the coated titania. Direct photolysis with ozone generating UV also provided very high TCE conversion of up to 6kg TCE per m3 per hour. However, major quantities of phosgene and dichloroacetyle chloride (DCAC) were produced as byproducts. TCE removal using silica based photocatalyst did not result in any detectable DCAC. Only phosgene along with trace amounts of chloroform and carbon tetrachloride were identified as oxidation byproducts with silica based photocatalyst.     

Photolytic degradation of hexacyanoferrate (II) in aqueous media: the determination of the degradation kinetics

Upon exposure to ultraviolet (UV) radiation, non-toxic hexacyanoferrate (II) (Fe(CN)6(-4)) undergoes direct photolysis, resulting in the liberation of toxic free cyanide (HCN,CN-). This experimental study employed manipulation of several environmental parameters with the objective of characterizing their effects on the photolysis rate of hexacyanoferrate (II). The photolysis rate was not affected significantly by varying (1) the initial hexacyanoferrate (II) concentration (from 10 to 400 microg/l as total CN), (2) the solution turbidity (kaolin clay concentration from 0 to 5 mg/l), and (3) pH (from pH 4 to 12). Parameters that exhibited a significant effect (significance level, alpha < 0.05) on the photolysis rate included the intensity of incident ultraviolet radiation (from 30 to 110 micromol/m2s photons) and the concentration of dissolved organic matter (color) from added humic acid (from 0 to 10 mg/l). In addition, observations made by spiking both deionized and natural waters demonstrated that the rate of hexacyanoferrate (II) photolysis (1) significantly exceeded the rate of free cyanide formation from photolysis and (2) exhibited significant retardation that directly depended on the free cyanide concentration in solution. The hexacyanoferrate (II) photolysis data were consistent with a simple, semi-empirical kinetic model that included the reversible formation of at least one cyanoferrate intermediate. The reverse reaction, in turn, behaved in a manner that was consistent with a second order rate law with respect to free cyanide concentration.     

紫外光(UV)光解油田采出水中多环芳烃

为了探讨紫外光光解人工模拟油田采出水中多环芳烃的降解效率,利用自制反应装置对油田采出水中多环芳烃(PAHs)的紫外光光解做了一个初步研究。研究结果证明,紫外光光解对油田采出水中的多环芳烃萘和芴有显著的降解能力。实验室的测试表明,与紫外UVA(365 nm)、UVB(308 nm)的光照相比,紫外UVC(254 nm)在光照60 min的条件下,2种多环芳烃各自的去除率都近似达到了99%。可见,在光解效力和暴露时间两方面,紫外UVC对采出水中萘和芴的去除具有相对稳定和比较高的效率。     

Persistence of carbofuran in marine sand and water

Marine sand and seawater samples were collected in March 2002 from Laysan Island in the Hawaiian Islands National Wildlife Refuge, where a small area was contaminated by the carbamate insecticide carbofuran. Carbofuran was still detected at microg g(-1) levels in the Laysan sand after its identification in 1998 and initial observation of the toxicity in 1988. The persistence of carbofuran in the marine sand was investigated in the dark in a 30 degrees C oven, and in distilled deionized water and seawater samples exposed to artificial 300 nm light and to direct sunlight. The laboratory study showed a half-life (t1/2) of approximately 40 days for carbofuran in the native sand and in Ottawa sand. The photolysis of carbofuran was faster in seawater than in distilled deionized water when it was exposed to 300 nm light (t1/2, 0.1 vs. 3.1 h) and to direct sunlight (t1/2, 7.5 vs. 41.6 h). The large difference between the laboratory results and the field observation of carbofuran dissipation suggests that carbofuran degradation at the remote, undisturbed marine site may be governed by its unique environmental factors.     

UV/ozone degradation of gaseous hexamethyldisilazane (HMDS)

As a carcinogen, hexamethyldisilazane (HMDS) is extensively adopted in life science microscopy, materials science and nanotechnology. However, no appropriate technology has been devised for treating HMDS in gas streams. This investigation evaluated the feasibility and effectiveness of the UV (185+254nm) and UV (254nm)/O(3) processes for degradation of gaseous HMDS. Tests were performed in two batch reactors with initial HMDS concentrations of 32-41mgm(-3) under various initial ozone dosages (O(3) (mg)/HMDS (mg)=1-5), atmospheres (N(2), O(2), and air), temperatures (28, 46, 65 and 80 degrees C), relative humilities (20%, 50%, 65%, 99%) and volumetric UV power inputs (0.87, 1.74, 4.07 and 8.16Wl(-1)) to assess their effects on the HMDS degradation rate. Results indicate that for all conditions, the decomposition rates for the UV (185+254nm) irradiation exceeded those for the UV (254nm)/O(3) process. UV (185+254nm) decompositions of HMDS displayed an apparent first-order kinetics. A process with irradiation of UV (185+254nm) to HMDS in air saturated with water at temperatures of 46-80 degrees C favors the HMDS degradation. With the condition as above and a P/V of around 8Wl(-1), k was approximately 0.20s(-1) and a reaction time of just 12s was required to degrade over 90% of the initial HMDS. The main mechanisms for the HMDS in wet air streams irradiated with UV (185+254nm) were found to be caused by OH free-radical oxidation produced from photolysis of water or O((1)D) produced from photolysis of oxygen. The economic evaluation factors of UV (185+254nm) and UV (254nm)/O(3) processes at different UV power inputs were also estimated.     

Surfactant effect on persistence of oxadiazolyl 3(2H)-pyridazinones against Pseudaletia separata walker

The photodynamic decomposition of two new insect-growth inhibitors (IGRs), 2-tert-butyl-5-[5'-aryl-2'-(1',3',4'-oxadiazolyl)methoxy]-3(2H)-pyridazinones (OPB) and its 4-chloro substituted derivative (OPC), and effect of surfactants on persistence of their bioactivity were taken into investigation. Both chemicals were significantly induced to photolysis by ultraviolet light at 365 nm wavelength and their inhibitory activities against Pseudaletia separata larvae decreased with the increasing irradiation time. However, irradiation at 254 nm wavelength didn't cause their photodegradation. Triton X-100 and Succinic-sulfonie acidic sodium but not Tween 60 possessed strong capability to slow down the decomposition and obviously prolonged the half life of OPC in laboratory and field whilst effects of the three surfactants almost did not preserve the inhibitory activity of OPB. Data suggested that electron-withdrawing halogen (-Cl) on the pi electron system in planar benzene-oxadialyl structures might reduce the efficiency of OPC on ultraviolet (UV) photoabsorption, and its hydrophobic interaction with the surfactants might be beneficial for forming stable micellar solubilization, thus sustaining the chemical's bioactivity.     

Multiresidue method for high-performance liquid chromatography determination of carbamate pesticides residues in tea samples

A multiresidue method was developed to determine 19 carbamate pesticides in tea samples. Optimizations of different parameters, such as the type of extraction solvents, clean-up cartridges, and elution solvents were carried out. The developed method used acetonitrile as extraction solvent, amino cartridge for adsorbents and acetone-n-hexane as the eluting solution. Nineteen carbamate residues were then analyzed by high-pressure liquid chromatography (HPLC) with fluorescence detector. The present results showed good linearity by correlation coefficients of more than 0.9999 for all analyses. Limits of detection and quantification varied from 0.0005–0.023 mg L^{? 1}, 0.008–0.077 mg L^{? 1}, respectively. Recoveries of sixteen carbamate pesticides ranged from 65% to 135% at the spiked level of 0.5, 1.0 and 2.0 mg L^{? 1}. The relative standard deviations were lower than 20% and coefficient of variations were lower than 15%. The results indicate that the proposed method provides an effective multi and trace level screening determination of carbamate pesticides residues for tea samples.     

Sequential treatment via Trametes versicolor and UV/TiO2/Ru(x)Se(y) to reduce contaminants in waste water resulting from the bleaching process during paper production

An efficient sequential, biological and photocatalytic treatment to reduce the pollutant levels in wastewater due to the bleaching process during paper production is reported. For a biological pre-treatment, 800 ml of non-sterilized effluent was inoculated with Trametes versicolor immobilized in polyurethane foam, with 25 g l(-1) glucose, 6.75 mM CuSO(4), and 0.22 mM MnSO(4) added, and cultured at 25 degrees C with an air flow of 800 ml min(-1) for 8d. The fungus did not inhibit growth of the heterotropic populations of the effluent. After 4d of culture, the chemical oxygen demand (COD) reduction and colour removal (CR) were 82% and 80%, respectively, with laccase (LAC) and manganese peroxidase (MnP) activities of 345 U l(-1) and 78 U l(-1), respectively. The COD reduction and CR correlated positively (p<0.0001) with LAC and MnP activities. Chlorophenol removal was 99% of pentachlorophenol, 99% of 2,3,4,6-tetrachlorophenol (2,3,4,6-TCP), 98% of 3,4-dichlorophenol (3,4-DCP) and 77% of 4-chlorophenol (4-CP), while 2,4,5-trichlorophenol (2,4,5-TCP) increased to 0.2 mg l(-1). The pre-treated effluent was then exposed to a photocatalytic treatment. The treatment with photolysis resulted in 9% CR and 46% COD reduction, 42% CR and 60% COD reduction by photocatalysis, and 62% CR and 85% COD reduction by heterogeneous photocatalysis with the system TiO(2)/Ru(x)Se(y) (Fig. 4). With this treatment the bacterial and fungal populations also decreased by 5 logarithmic units with respect to the biological treatment alone (Fig. 5). The total sequential treatment resulted in a 92% CR (from 5800 UC), 97% COD reduction (from 59 g l(-1)) and 99% chlorophenol removal at 96 h and 20 min.     

Determination of quantum yields for the photolysis of Fe(III)-hydroxo complexes in aqueous solution using a novel kinetic method

The determination of quantum yields for the photolysis of Fe(III)-hydroxo complexes is important for the quantitative investigation of hydroxyl radical (*OH) production, not only in a natural water body, but also in the photo-Fenton process. A novel kinetic method, using a *OH probe compound, was established for the determination of the quantum yields in this study. The method was based on measuring the pseudo-first-order rate constant of the photodecomposition of dimethylsulfoxide (DMSO) in which DMSO and its primary products scavenged the *OH at an identical rate. The preliminary experiments for the photodecomposition kinetics supported the suitability of DMSOs as a probe compound for determining quantum yields. The individual quantum yields for the photolysis of the monomeric Fe(III) complexes, in the wavelength range 240-380 nm, were determined by the photodecomposition kinetics of the hydroxyl radical (*OH) probe compound (DMSO). The determined values of the individual quantum yields were 0.046+/-0.00052 for Fe3+ (H2O)6 (hexaaquo ion) and 0.69+/-0.025 for Fe(OH)2+ (H2O)5 (hydroxypentaaquo ion) at 254 nm, and showed decreasing values with increasing wavelength, in the ranges of 240-380 nm. The quantum yields between 240 and 280 nm were newly reported in this study, and the values obtained between 280 and 380 nm were in good agreement with the literature values.     

The rate and mechanism of the gas-phase oxidation of hydroxyacetone

The rate and mechanism for gas-phase destruction of hydroxyacetone, CH₃C(O)CH₂OH, by reaction with OH, Cl-atoms, and by photolysis have been determined. The first quantitative UV absorption spectrum of hydroxyacetone is reported over the wavelength range 235 to 340 nm; the spectrum is blue-shifted by about 15 nm relative to that of acetone and peaks at 266 nm, with a maximum absorption cross section of (6.7±0.6) ×10^-20 cm² molecule^-1. Measurable absorption extends out to about 330 nm. The quantum yield for photolysis of hydroxyacetone in the region relevant to the troposphere (λ>290 nm) was found to be significantly less than unity. Rate coefficients for the reaction of hydroxyacetone with OH radicals and Cl-atoms were determined at 298 K using the relative rate technique. The rate coefficient for reaction with OH was found to be (3.0±0.7)×10^-12 cm³ molecule^-1 s^-1, while the rate coefficient for reaction with Cl-atoms was found to be (5.6±0.7)×10^-11 cm³ molecule^-1 s^-1. Both values agree well with previous studies. The data were used to determine the lifetime of hydroxyacetone in the troposphere. Reaction with OH is the major gas-phase destruction mechanism for this compound, limiting its lifetime to about 4 days, while photolysis is found to be only of minor importance.     

Effect of carbaryl (carbamate insecticide) on acetylcholinesterase activity of two strains of Daphnia magna (Crustacea,Cladocera)

The present study was designed to investigate the effect of carbaryl (carbamate insecticide) on the acetylcholinesterase activity in two strains (same clone A) of the crustacean cladoceran Daphnia magna. Four carbaryl concentrations (0.4, 0.9, 1.8 and 3.7 µg L^?1) were compared against control AChE activity. Our results showed that after 48 h of carbaryl exposure, all treatments induced a significant decrease of AChE activities whatever the two considered strains. However, different responses were registered in terms of lowest observed effect concentrations (LOEC: 0.4 µg L^?1 for strain 1 and 0.9 µg L^?1 for strains 2) revealing differences in sensitivity among the two tested strains of D. magna. These results suggest that after carbaryl exposure, the AChE activity responses can be also used as a biomarker of susceptibility. Moreover, our results show that strain1 is less sensitive than strain 2 in terms of IC50-48 h of AChE activity. Comparing the EC50-48 h of standard ecotoxicity test and IC50-48 h of AChE inhibition, there is the same order of sensitivity with both strains.