Photodegradation and volatility of pesticides

BACKGROUND AND OBJECTIVES: Among the factors affecting the environmental fate of surface-applied pesticides several biological as well as abiotic factors, such as volatilization and photochemical transformations are of particular interest. Whereas reliable measurement methods and models for estimating direct photodegradation are already available for the compartments of water and atmosphere and individual subprocesses have already been described in detail, there is still a need for further elucidation concerning the key processes of heterogeneous photodegradation of environmental chemicals on surfaces. METHODS: In order to systematically examine the direct and indirect photodegradation of 14C-labeled pesticides on various surfaces and their volatilization behavior, a new laboratory device ('photovolatility chamber') was designed according to US EPA Guideline 161-3. Model experiments under controlled conditions were conducted investigating the impact of different surfaces, i.e. glass, soil dust and radish plants, and environmental factors, i.e. irradiation and atmospheric ozone (O3), on the photodegradation and volatilization of surface-deposited [phenyl-UL-14C]parathion-methyl (PM). RESULTS AND DISCUSSION: Depending on the experimental conditions, parathion-methyl was converted to paraoxon-methyl, 4-nitrophenol, unknown polar products and 14CO2. With respect to the direct photodegradation of PM (experiments without O3), the major products were polar compounds and 14CO2, due to the rapid photochemical mineralization of 4-nitrophenol to 14CO2. Paraoxon-methyl and 4-nitrophenol formation was mainly mediated by the combination of light, O3, and *OH radicals. In radish experiments PM photodegradation was presumably located in the cuticle compartment, which exhibited a sensitized photodegradation, as more unknown products were yielded compared to the glass and soil dust experiments. This could be explained by intensifying the inherent PM degradation in the dark with the same product spectrum. Due to photochemical product formation, which is an antagonistic process to the volatilization of parent compound, the volatilization of unaltered parathion-methyl from each surface generally decreased in the presence of light, particularly in combination with increasing O3 concentrations and *OH radical production rates. CONCLUSION: First results demonstrated that the photovolatility chamber provides a special tool for the systematic evaluation of (a) photodegradation of surface-located pesticide residues, i.e. measuring qualitative aspects of direct and indirect photodegradation together with relative photodegradation rates, and (b) volatilization of pesticides on surfaces by including and optionally varying relevant parameters such as light, atmospheric O3 concentration, surface temperature, air temperature, air flow rate. OUTLOOK: The experimental facility represents an important complement to lysimeter and field studies, in particular for experiments on the volatilization of pesticides using the wind tunnel system. With the photovolatility chamber special experiments on photodegradation, volatilization and plant uptake can be conducted to study key processes in more detail and this will lead to a better understanding of the effects of certain environmental processes on the fate of released agrochemicals contributing to an improved risk assessment.     

Photochemical nitro-nitrite rearrangement in methyl parathion decay under tropical conditions

This work presents a study of the abiotic degradation of commercially available methyl parathion in aqueous solution at two different concentrations (88 mg/L and 200 μg/L). The effects of solar irradiation and the presence of humic acids were evaluated and revealed a synergistic response between them. The half-life of methyl parathion ranged from 4.9 to 37 days, and the experimental data also show that photochemical processes were the most relevant in this case. The only byproduct found in samples submitted to shadowed conditions was 4-nitrophenol. On the other hand, 4-nitrophenol, methyl paraoxon and a new degradation product (O,O-dimethyl O-p-hydroxyphenyl phosphorothioate) were detected when the samples were exposed directly to sunlight. This newly identified compound was prepared in the laboratory by thiophosphorylation of hydroquinone, and coelution experiments with authentic samples provided unambiguous confirmation of the presence of O,O-dimethyl O-p-hydroxy phenylphosphorothioate in samples.     

Photochemical behavior of chlorsulfuronR in water and in adsorbed phase

The photochemistry of the herbicide chlorsulfuron^R (2-chloro-N-[[4-methoxy-6-methyl-1.3.5-triazinyl-2-amino]carbonyl]benzene sulfonamide) was investigated in methanol, distilled water, natural creek-water, on silica gel and on montmorillonit surfaces. The rate of degradation was determined in outdoor and indoor experiments simulating tropospheric conditions (λ>290 nm). Two major photoproducts were identified in all cases.     

Photolysis of polycyclic aromatic hydrocarbons adsorbed on spruce [Picea abies (L) Karst] needles under sunlight irradiation

Photolysis of polycyclic aromatic hydrocarbons (PAHs) sorbed on surfaces of spruce [Picea abies (L.) Karst.] needles under sunlight irradiation was investigated. PAHs were produced by combustion of polyvinyl chloride (PVC), wood, high-density polyethylene (HDPE), and styrene in a stove. The factors of sunlight irradiation on the surfaces of spruce needles were taken into consideration when investigating the kinetic parameters. The photolysis of the 18 PAHs under study follows first-order kinetics. The photolysis half-lives range from 15 h for dibenzo(a,h)anthracene to 75 h for phenanthrene. Photolysis of some PAHs on surfaces of spruce needles may play an important role on the fate of PAHs in the environment.     

Simultaneous determination of chlorothalonil and its metabolite 4-hydroxychlorothalonil in greenhouse air: dissipation process of chlorothalonil

An analytical method was developed and tested for the simultaneous determination of chlorothalonil and its main metabolite 4-hydroxychlorothalonil, in airborne samples. High performance liquid chromatography equipped with Ultra-violet detector was used to separate and quantify the analytes. Glass microfibre filters for the collection of the analytes' particles were tested. Solid sorbents, such as Tenax, Florisil, XAD-2 and silica gel, were studied to find out the most suitable material for the collection of the analytes in the gas phase. The results have shown that only chlorothalonil was trapped in the vapor phase with highest results obtained when silica gel was the sorbent of choice. Linearity was demonstrated in a wide concentration range 0.01-10.00 mg L(-1). Recoveries from spiked glass microfibre filters and silica gel cartridges for chlorothalonil and 4-hydroxychlorothalonil were almost quantitative. The quantification limits were calculated to be 8.4 and 19.6 ng m(-3) in air for chlorothalonil and 4-hydroxychlorothalonil, respectively. The two analytes spiked on the GF/A filters and silica gel cartridges were proven to be stable for more than 15 days, at 4degrees C and ambient temperature. The applicability of the present method was demonstrated by the analysis of the chlorothalonil and its metabolite in greenhouse air.     

Studies on photochemistry of aromatic hydrocarbons V: Photochemical reaction of chlorobenzene with nitrogen oxides in air

The investigations on the photochemical reaction of chlorobenzene with nitrogen oxides in air were carried out using the reaction vessels made of Pyrex glass and quartz, respectively. The irradiation of chlorobenzene in the Pyrex glass vessel gave m-chloronitrobenzene, 2-chloro-6-nitrophenol, 2-chloro-4-nitrophenol and 4-chloro-2-nitrophenol, while the irradiation of chlorobenzene in the quartz vessel resulted in m-chloronitrobenzene, p-nitrophenol, 2-chloro-4-nitrophenol, 3-chloro-2-nitrophenol, 3-chloro-6-nitrophenol and 3-chloro-4-nitrophenol.The formation mechanism of these chloronitrophenols was considered using the theory of the nitro-nitrite rearrangement of chloronitrobenzenes.     

Photodegradation of organic pollutants on the spruce needle wax surface under laboratory conditions

The photochemistry of selected organic compounds, including common pollutants, on the paraffin (as a model matrix) and spruce wax surfaces was studied under laboratory conditions. Two model transformations were evaluated: (1) intramolecular rearrangements of valerophenone and 2-nitrobenzaldehyde, and (2) hydrogen abstraction between an excited benzophenone and the hydrocarbon paraffin/wax chains. The steric or polar influence of the solid matrix on conformational and translational motion, its optical properties, hydrogen abstraction probabilities, and consequences of the guest-molecule segregation are discussed in this work. Furthermore, the photochemical reactivity of some common anthropogenic pollutants, such as chlorinated biphenyls (4-chlorobiphenyl, 2,4-dichlorobiphenyl, and 4,4'-dichlorobiphenyl), 4-chlorophenol, and DDT, was evaluated. The surface of spruce wax is presented as probable reaction medium for photochemical transformations. Although the matrix presents certain restrictions for bimolecular reactions, common photodegradations should be generally feasible in nature. In addition, paraffin was found to be a suitable model matrix for the studies of possible photochemical transformations that can occur on natural plant surfaces.     

Abatement and degradation pathways of toluene in indoor air by positive corona discharge

Indoor air concentrations of volatile organic compounds often exceed outdoor levels by a factor of 5. There is much interest in developing new technologies in order to improve indoor air quality. In this work non-thermal plasma (DC positive corona discharge) is explored as an innovative technology for indoor air purification. An inlet gas stream of 10 l min(-1) containing 0.50+/-0.02 ppm toluene was treated by the plasma reactor in atmospheric conditions. Toluene removal proved to be achievable with a characteristic energy density epsilon(0) of 50 J l(-1). Removal efficiencies were higher for 26% relative humidity (epsilon(0)=35 J l(-1)), compared with those at increased humidities (50% relative humidity, epsilon(0)=49 J l(-1)). Reaction products such as formic acid, benzaldehyde, benzyl alcohol, 3-methyl-4-nitrophenol, 4-methyl-2-nitrophenol, 4-methyl-2-propyl furan, 5-methyl-2-nitrophenol, 4-nitrophenol, 2-methyl-4,6-dinitrophenol are identified by means of mass spectrometry. Based on these by-products a toluene degradation mechanism is proposed.     

Phototransformation of alphacypermethrin as thin film on glass and soil surface

Photodegradation of alphacypermethrin ((RS)-alpha cyano-3-phenoxy benzyl (1RS) cis-3-(2,2,dichlorovinyl)-2,2-dimethyl cyclopropane carboxylate) was studied as a thin film on glass surface and on black and red soil surfaces. A number of photoproducts from glass surfaces have been isolated, characterized and identified by gas chromatography-mass spectroscopy (GC-MS). However, only two of them viz. 3-phenoxy benzyl alcohol and [2,2-dichlorovinyl-3(2,2,dimethyl) cyclopropane carboxylate] could be identified from both the soil. Rate of photodegradation on glass and soil surface under UV and sunlight followed first order kinetics with significant correlation coefficients. The rate of photodegradation was greater on black than on red soil.     

Minimization of blank values of the miniature silica gel column

Several methods involving silica gel separations of polychlorinated biphenyls from chlorinated insecticides are already described in literature. Our intention was to find a system of solvent and silica gel of the lowest blank values. The first step was to find a solvent mixture which will keep the homogenity of a silica gel column. PCBs elution was performed with pentane, while the chlorinated insecticides eluated with diethylether, acetone, methanol, and benzene. The elution of pesticides gave the best results for the following solvent systems: diethylether + hexane (1:1), acetone + hexane (1:4), methanole + pentane (1:8) and benzene.Separation of pesticides from polychlorinated biphenyls found in a synthetic mixture was also examined. It was found that all solvent systems used gave similar results of separation. However, only if benzene is used as eluant, the silica gel column can be used for four successive separations after the “on column” regeneration. In order to obtain the lowest blank values silica gel was cleaned with several solvents. The eluates after the silica gel separation were also cleaned up by means of deactivation alumina and concentrated sulphuric acid.     

Modified SBA-15 mesoporous silica for heavy metal ions remediation

N-Propylsalicylaldimino-functionalized SBA-15 mesoporous silica was prepared, characterized and used as an adsorbent for heavy metal ions. The organic-inorganic hybrid material was obtained using successive grafting procedures of SBA-15 silica with 3-aminopropyl-triethoxysilane and salicylaldehyde, respectively. For comparison an amorphous silica gel was functionalized using the same procedure. The structure and physicochemical properties of the materials were characterized by means of elemental analysis, X-ray diffraction (XRD), nitrogen adsorption-desorption, thermogravimetric analysis and FTIR spectroscopy. The organic functional groups were successfully grafted on the SBA-15 surfaces and the ordering of the support was not affected by the chemical modification. The behavior of the grafted solids for the adsorption of heavy metals ions from aqueous solutions was investigated. The hybrid materials showed high adsorption capacity and high selectivity for copper ions. Other ions, such as nickel, zinc, and cobalt were adsorbed by the modified SBA-15 material. The adsorbent can be regenerated by acid treatment without altering its properties.     

Phototransformation of Alphacypermethrin as Thin Film on Glass and Soil Surface∗

Photodegradation of alphacypermethrin ((RS)-α cyano-3-phenoxy benzyl (1RS) cis-3-(2,2,dichlorovinyl)-2,2-dimethyl cyclopropane carboxylate) was studied as a thin film on glass surface and on black and red soil surfaces. A number of photoproducts from glass surfaces have been isolated, characterized and identified by gas chromatography-mass spectroscopy (GC-MS). However, only two of them viz. 3-phenoxy benzyl alcohol and [2,2-dichlorovinyl-3(2,2,dimethyl) cyclopropane carboxylate] could be identified from both the soil. Rate of photodegradation on glass and soil surface under UV and sunlight followed first order kinetics with significant correlation coefficients. The rate of photodegradation was greater on black than on red soil.

     

Effective photodegradation of methomyl pesticide in concentrated solutions by novel enhancement of the photocatalytic activity of TiO2 using CdSO4 nanoparticles

Annihilation of electrons–holes recombination process is the main remedy to enhance the photocatalytic activity of the semiconductors photocatalysts. Doping of this class of photocatalysts by foreign nanoparticles is usually utilized to create high Schottky barrier that facilitates electron capture. In the literature, because nonpolar nanoparticles (usually pristine metals, e.g., Ag, Pt, Au, etc.) were utilized in the doping process, the corresponding improvement was relatively low. In this study, CdSO₄-doped TiO₂ nanoparticles are introduced as a powerful and reusable photocatalyst for the photocatalytic degradation of methomyl pesticide in concentrated aqueous solutions. The utilized CdSO₄ nanoparticles form polar grains in the TiO₂ matrix due to the electrons leaving characteristic of the sulfate anion. The introduced nanoparticles could successfully eliminate the harmful pesticide under the sunlight radiation within a very short time (less than 1 h), with a removal capacity reaching 1,000 mg pesticide per gram of the introduced photocatalyst. Moreover, increase in the initial concentration of the methomyl did not affect the photocatalytic performance; typically 300, 500, 1,000, and 2,000 mg/l solutions were completely treated within 30, 30, 40, and 60 min, respectively, using 100 mg catalyst. Interestingly, the photocatalytic efficiency was not affected upon multiple use of the photocatalyst. Moreover, negative activation energy was obtained which reveals super activity of the introduced photocatalyst. The distinct photocatalytic activity indicates the complete annihilation of the electrons–holes recombination process and abundant existence of electrons on the catalyst surfaces due to strong electrons capturing the operation of the utilized polar CdSO₄ nanoparticles. The introduced photocatalyst has been prepared using the sol–gel technique. Overall, the simplicity of the synthesizing procedure and the obtained featured photocatalytic activity strongly recommend the introduced nanoparticles to treat the methomyl-containing polluted water.     

Intermediate distributions and primary yields of phenolic products in nitrobenzene degradation by Fenton's reagent

Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.     

Effect of amorphous silica and silica sand on removal of chromium(VI) by zero-valent iron

The effect of two surfaces (amorphous silica and silica sand) on the reduction of chromium(VI) by zero-valent iron (Fe(0)) was investigated using batch reactors. The amendment of both surfaces significantly increased the rate and extent of Cr(VI) removal. The rate enhancement by amended surfaces is presumed to result from scavenging of Fe(0)-Cr(VI) reaction products by the provided surfaces, which minimized surface deactivation of Fe(0). The rate enhancing effect was greater for silica compared to sand, and the difference is attributed to silica's higher surface area, greater affinity for reaction products and pH buffering effect. For a given mass of Fe(0), the reactivity and longevity of Fe(0) to treat Cr(VI) increased with increasing dose of silica. Elemental analyses of the reacted iron and silica revealed that chromium removed from the solution was associated with both surfaces, with its mass distribution being approximately 1:1 per mass of iron and silica. The overall result suggests reductive precipitation was a predominant Cr(VI) removal pathway, which involves initial reduction of Cr(VI) to Cr(III), followed by formation of Cr(III)/Fe(III) hydroxides precipitates.     

Competitive adsorption of alkylbenzene and water vapors on predominantly mineral surfaces

Competitive adsorption of ethylbenzene (EB) and water on bentonite and of p-xylene (pXYL) and water on kaolin and silica gel was studied using a technique that allowed the amount of adsorbed water and alkylbenzene to be measured independently. EB adsorption on bentonite was not affected by water at relative humidities (RH) near 0.23 but was reduced significantly at RH's near 0.50. pXYL adsorption on kaolin and silica gel decreased with increasing RH, especially above a RH of about 0.2. Increasing RH not only decreased the amount of alkylbenzene adsorption but also resulted in a change from Type-II adsorption isotherms to ones that were essentially linear. Linear isotherms for the adsorption of hydrophobic organic compounds on hydrated soil have generally been attributed to partitioning into organic carbon (OC). However, since the clays and oxide used here had very low to trace amounts of OC, it is suggested that processes involving only mineral surfaces can give rise to linear isotherms. Based on solubility considerations alone, partitioning of EB and pXYL into adsorbed water films was not considered to be an important adsorption mechanism in this study. The effect of cation hydration on the amount of water adsorbed from a mixture of water and pXYL vapors was evaluated by comparing adsorption on Li- and Na-saturated kaolin.     

Optimization of the purification method for dioxin analysis in human serum and temporal changes in background dioxin levels in the general population

To perform high quality and high throughput measurements, complicated purification procedure by two rounds of open column chromatography was simplified by appraising the components and adding a sufficient amount of adsorbents to the column. The procedure consists of two open column techniques using a multi-layer silica gel column and an active carbon dispersed silica gel column. This purification procedure is used in "Standard manual for dioxin analysis in human blood" published in 2000 (Ministry of Health and Welfare, Japan, 2000). Consequently, a purification procedure using only 1 g of 10% AgNO(3)/silica gel can remove the matrix of blood serum as effectively as a multi-layer silica gel column. In addition, 0.1 g of carbon silica gel, equivalent to 1/10 the weight used currently in analyses, separates and recovers the dioxins in purified extract of blood serum. Furthermore, changes in the background level in the general population were clarified by monitoring the dioxin concentrations in human blood. The dioxin concentrations and ratios in blood in the general population remained at a tolerable level for three months. Therefore, the blood serum was available for the detection of a remarkable elevation in dioxins level considered to be indicative of contamination due to high-density exposure.     

Radiolysis of aqueous 4-nitrophenol solution with Al2O3 or TiO2 nanoparticles

Aqueous 4-nitrophenol solutions containing TiO₂ or Al₂O₃ nanoparticles were irradiated with electron beam. 4-nitrophenol was decomposed by the ionizing radiation process in the absence of the nanoparticles. The addition of TiO₂ or Al₂O₃ (2 g l⁻¹) before irradiation improved the removal of 4-nitrophenol, total organic carbon (TOC) but also nitrogen (TN). To identify the origin of the loss (catalysis or simply adsorption), TiO₂ or Al₂O₃ nanoparticles were added after irradiation. Experiments show that the effect of the presence of TiO₂ or Al₂O₃ during irradiation is just due to adsorption.     

4-硝基酚的污泥减量化作用及对污泥性质的影响

为了有效减少活性污泥法中剩余污泥的产生,采用解偶联剂4-硝基酚对活性污泥工艺中的剩余污泥进行减量化研究。研究了4-硝基酚对污泥的增长速率、基质去除率以及污泥性质的影响。结果表明:4-硝基酚对污泥的减量化作用明显,在对微生物解偶联的过程中并不影响微生物对基质的利用能力;对出水中的氨氮影响甚小,总氮、总磷浓度有轻微的升高。4-硝基酚能够刺激污泥中微生物的活性,比耗氧速率增加,促进能量解偶联,从而降低污泥产率。4-硝基酚使污泥中微生物的群落结构发生了轻微的变化,但对污泥的松散程度和絮凝沉降性能影响甚小。     

Systematic analysis and overall toxicity evaluation of dioxins and hexachlorobenzene in human milk

A systematic method for analyzing dioxins (PCDDs, PCDFs and dioxin-like PCBs), hexachlorobenzene (HCB), heptachlor epoxide and beta-hexachlorocyclohexane (HCH) in human milk was developed to determine the residual amount of HCB in human milk and to evaluate the overall toxicity of both dioxins and HCB in human milk. The fractionation behavior of HCB on chromatography with silica gel, alumina, and activated carbon/silica gel, and the concentrated sulfuric acid decomposition method, which is widely used as a dioxin cleanup method, were studied in order to make the preprocessing operation for HCB measurement compatible with that for conventional dioxin measurement. HCB was found to be eluted in the 2% dichloromethane (DCM)/hexane 60 ml fraction from an alumina column. Heptachlor epoxide and a part of beta-HCH were eluted in the 10% DCM/hexane 50 ml fraction from a silica gel column, while the remaining beta-HCH was eluted in the 25% DCM/hexane 60 ml fraction from an activated carbon/silica gel column. Moreover, HCB showed significant correlation with dioxin congeners having high toxicity equivalence factors (TEFs). The results suggest that the exposure route to HCB and its accumulation behavior in the human body are similar to those of the dioxins.