Quantum Yield for the Aqueous Photochemical Degradation of Chlorantraniliprole and Simulation of Its Environmental Fate in a Model California Rice Field.

The photochemical degradation of chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was characterized under simulated solar light with 2-nitrobenzaldehyde (2NB) actinometry. Overall, aqueous CAP degraded quickly via direct photodegradation with no significant difference observed between high-purity water and filtered rice field water. The 24-h average half-life normalized to summer sunlight using 2NB was 34.5 ± 4.0 h (jCAP,env = 0.020 ± 0.0023 h-1 , n = 3), and the calculated apparent quantum yield in simulated sunlight was 0.0099 ± 0.00060. These new values were used-alongside previously characterized data for air/and soil/water partitioning, degradation in soil, and hydrolysis-in the Pesticides in Flooded Applications Model to simulate CAP dissipation in a model California (USA) rice field. The model estimates an environmental half-life of 26 d in the aqueous phase, but the bulk of applied CAP remains in the benthic zone and degrades, with estimated half-lives of 29 and 92 d in flooded and drained fields, respectively. Environ Toxicol Chem 2020;39:1929-1935. © 2020 SETAC.

Reduction of Pesticide Toxicity Under Field-Relevant Conditions? The Interaction of Titanium Dioxide Nanoparticles, Ultraviolet, and Natural Organic Matter.

In surface waters, the illumination of photoactive engineered nanomaterials (ENMs) with ultraviolet (UV) light triggers the formation of reactive intermediates, consequently altering the ecotoxicological potential of co-occurring organic micropollutants including pesticides due to catalytic degradation. Simultaneously, omnipresent natural organic matter (NOM) adsorbs onto ENM surfaces, altering the ENM surface properties. Also, NOM absorbs light, reducing the photo(cata)lytic transformation of pesticides. Interactions between these environmental factors impact 1) directly the ecotoxicity of photoactive ENMs, and 2) indirectly the degradation of pesticides. We assessed the impact of field-relevant UV radiation (up to 2.6 W UVA/m²), NOM (4 mg TOC/L), and photoactive ENM (nTiO2, 50 µg/L) on the acute toxicity of 6 pesticides in Daphnia magna. We selected azoxystrobin, dimethoate, malathion, parathion, permethrin, and pirimicarb because of their varying photo- and hydrolytic stabilities. Increasing UVA alone partially reduced pesticide toxicity, seemingly due to enhanced degradation. Even at 50 µg/L, nano-sized titanium dioxide (nTiO2) reduced but also increased pesticide toxicity (depending on the applied pesticide), which is attributable to 1) more efficient degradation and potentially 2) photocatalytically induced formation of toxic by-products. Natural organic matter 1) partially reduced pesticide toxicity, not evidently accompanied by enhanced pesticide degradation, but also 2) inhibited pesticide degradation, effectively increasing the pesticide toxicity. Predicting the ecotoxicological potential of pesticides based on their interaction with UV light or interaction with NOM was hardly possible, which was even more difficult in the presence of nTiO2. Environ Toxicol Chem 2020;39:2237-2246. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Photolysis-Induced Neurotoxicity Enhancement of Chlorpyrifos in Aquatic System: A Case Investigation on Caenorhabditis elegans.

Contamination of the environment by toxic pesticides has become of great concern in agricultural countries. Chlorpyrifos (CP) is among the pesticides most commonly detected in the environment owing to its wide agricultural applications. The aim of this study was to compare potential changes in the toxicity of CP after irradiation. To this end, photolysis of CP was conducted under simulated sunlight, and neurotoxicity assessment was carried out at CP of 20 and 50 µg L-1 and its corresponding irradiated mixture solutions which contain a mixture of identified intermediates using the nematode, Caenorhabditis elegans as a model organism. Photodegradation of 20 µg L-1 CP for 1 h produced no obvious reduction of physiological damage, and more serious effects on animal movement were detected after exposure of the animals to a solution of 50 µg L-1 for 1 h irradiation compared with unirradiated solution. GABAergic and cholinergic neurons were selectively vulnerable to CP exposure, and maximal neuropathological alterations were observed after 1 h irradiation of the CP solutions in coherence with the behavioral impairment. The generation of photoproducts was considered to be responsible for the enhanced disturbance on those biological processes. This work provided useful information on the toxicological assessments of chemicals that were produced during the environmental transformation of pesticides.

Influence of water depth and season on the photodegradation of micropollutants in a free-water surface constructed wetland receiving treated wastewater.

Micropollutants such as pharmaceutical products and pesticides are still present in treated wastewater. Several of these compounds are photoactive, either by direct or indirect photodegradation. An innovative on-site experimental protocol was designed to investigate the contribution of photodegradation processes to eliminate micropolluants in constructed wetland (CW). The solar photodegradation of 23 organic micropollutants was studied using in situ photoreactors at different depths. A CW-photodegradation model was designed and calibrated to further scrutinize the contribution of direct and indirect photodegradation processes in the elimination of micropollutants. The results show that photodegradation is most effective in the first 10 cm of the water column. A classification of micropollutants in 3 groups was developed to characterize their photodegradation. A significant increase of the half-life by direct photodegradation was observed in winter compared to summer due to a lower light intensity in winter. On the opposite, for direct + indirect photodegradation, no significant difference was observed between seasons. The decrease in light intensity in winter was compensated by higher nitrates concentration which promoted the formation of hydroxyl radicals and increased indirect photodegradation. The CW-photodegradation model successfully simulated the measured concentrations for direct and indirect photodegradation for 23 micropolluants. Nonetheless, it overestimated the indirect photodegradation with hydroxyl radicals when using default parameter values derived for surface waters. Hence, the consumption of hydroxyl radicals was increased by a factor of 20 for treated water. This model highlighted the predominance of direct photodegradation in the elimination of all micropollutants, except sotalol for the winter campaign.

UV/H2O2 advanced oxidation for abatement of organophosphorous pesticides and the effects on various toxicity screening assays.

Advanced oxidation processes (AOPs) are utilized due to their ability to treat emerging contaminants with the fast reacting and non-selective hydroxyl radical (OH). Organophosphorous insecticides are common drinking water contaminants, with 12 different compounds of this class being found on the US EPA's most recent Candidate Contaminant List (CCL4). The use of the AOP UV/H2O2 for the treatment of organophosphorous insecticides was explored in this study, by coupling biological and analytical tools to follow the abatement of the target compounds. Four insecticides were explored for advanced oxidation treatment: acephate, dicrotophos, fenamiphos, and methamidophos. All four compounds were fast reacting with OH, all reacting with second order rate constants ≥5.5 × 109 M-1s-1. Three major endpoints of toxicity were studied: estrogenicity, genotoxicity (mutagenicity) and neurotoxicity. None of the target compounds showed any estrogenic activity, while all compounds showed an active genotoxic (mutagenic) response (AMES II assay) and most compounds had some level of neurotoxic activity. AOP treatment did not induce any estrogenic activity, and reduced the compounds' neurotoxicity and genotoxicity in all but one case. Methamidophos degradation by UV/H2O2 resulted in an increase in genotoxicity, likely due to the formation of toxic transformation products. The increase in toxicity gradually decreased with time, possibly due to hydrolysis of the transformation products formed. This study provides insights into parent compound abatement and the changes in toxicity due to transformation products.

Electrospun and functionalized PVDF/PAN nanocatalyst-loaded composite for dechlorination and photodegradation of pesticides in contaminated water.

A novel approach for the electrospinning and functionalization of nanocatalyst-loaded polyvinylidene fluoride/polyacrylonitrile (PVDF/PAN) composite grafted with acrylic acid (AA; which form polyacrylic acid (PAA) brush) and decorated with silver (Ag/PAN/PVDF-g-PAA-TiO2/Fe-Pd) designed for the dechlorination and photodegradation of pesticides was carried out. PAN was used both as a nitrogen dopant as well as a co-polymer. Smooth nanofibers were obtained by electrospinning a solution of 12:2 wt.% PVDF/PAN blend using dimethylformamide (DMF) as solvent. The nanofibers were grafted with AA by free-radical polymerization using 2,2'azobis(2-methylpropionitrile) (AIBN) as initiator. Both bimetallic iron-palladium (Fe-Pd) and titania (TiO2) nanoparticles (NP) were anchored on the grafted nanofibers via the carboxylate groups by in situ and ex situ synthesis. The Fe-Pd and nitrogen-doped TiO2 nanoparticles were subsequently used for dechlorination and oxidation of target pollutants (dieldrin, chlorpyrifos, diuron, and fipronil) to benign products. Structural and chemical characterizations of the composites were done using various techniques. These include surface area and porosity analyzer (ASAP) using the technique by Brunner Emmett Teller (BET), Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM) analyses were done. After dechlorination, the transformation products (TPs) for dieldrin, chlorpyrifos, diuron, and fipronil were obtained and identified using two-dimensional gas chromatography (time-of-flight) with a mass spectrometer detector (GCxGC-TOFMS). Analysis of total organic carbon (TOC) was carried out and used to extrapolate percentage mineralization. Experimental results showed that dechlorination efficiencies of 96, 93, 96, and 90 % for 1, 2, 2, and 3 h treatment period were respectively achieved for 5 ppm solutions of dieldrin, chlorpyrifos, diuron, and fipronil. The dechlorination of dieldrin, diuron, and fipronil follows first-order kinetics while that of chlorpyrifos followed pseudo-first order. Mineralization performance of 34 to 45 % were recorded when Fe-Pd was used, however upon electrospinning, doping, and grafting (Ag/PAN/PVDF-g-PAA-TiO2/Fe-Pd composite); it significantly increased to 99.9999 %. This composite reveals great potential for dechlorination and mineralization of pesticides in contaminated water.

Adsorption and photocatalytic degradation of pharmaceuticals and pesticides by carbon doped-TiO2 coated on zeolites under solar light irradiation.

To evaluate the performance of zeolite-supported carbon-doped TiO(2) composite catalysts toward target pollutants under solar light irradiation, the adsorption and photocatalytic degradation of 18 pharmaceuticals and pesticides with distinguishing features (molecular size and volume, and photolysis) were investigated using mordenite zeolites with SiO(2)/Al(2)O(3) ratios of 18 and 240. Different quantities of carbon-doped TiO(2) were coated on the zeolites, and then the finished composite catalysts were tested in demineralized, surface, and hospital wastewater samples, respectively. The composite photocatalysts were characterized by X-ray diffraction, field emission scanning electron microscopy, and surface area and porosity analyses. Results showed that a dispersed layer of carbon-doped TiO(2) is formed on the zeolite surface; this layer blocks the micropores of zeolites and reduces their surface area. However, these reductions did not significantly affect adsorption onto the zeolites. Our results demonstrated that zeolite-supported carbon-doped TiO(2) systems can effectively degrade 18 pharmaceuticals and pesticides in demineralized water under natural and simulated solar light irradiation. In surface and hospital wastewaters, zeolite-supported carbon-doped TiO(2) systems present excellent anti-interference capability against radical scavengers and competitive organics for pollutants removal, and higher pollutants adsorption on zeolites evidently enhances the removal rate of target pollutants in surface and hospital wastewater samples with a complicated matrix.

Cu(2+) and Fe(2+) mediated photodegradation studies of soil-incorporated chlorpyrifos.

The influences of Cu(2+) and Fe(2+) on the photodegradation of soil-incorporated chlorpyrifos were investigated in the present study. The soil samples spiked with chlorpyrifos and selected metal ions were irradiated with UV light for different intervals of time and analyzed by HPLC. The unsterile and sterile control soil samples amended with pesticides and selected metals were incubated in the dark at 25 °C for the same time intervals. The results of the study evidenced that photodegradation of chlorpyrifos followed the first-order kinetics. The dissipation t0.5 of chlorpyrifos was found to decrease from 41 to 20 days under UV irradiation. The rate of chlorpyrifos photodegradation was increased in the presence of both metals, i.e., Cu(2+) and Fe(2+). Thus, initially observed t0.5 of 19.8 days was decreased to 4.39 days in the case of Cu(+2) and 19.25 days for Fe(+2). Copper was found to increase the rate of photodegradation by 4.5 orders of magnitude while the microbial degradation of chlorpyrifos was increased only twofold. The microbial degradation of chlorpyrifos was only negligibly affected by Fe(2+) amendment. The studied trace metals also affected the abiotic degradation of the pesticide in the order Cu(2+) > Fe(2+).

Exposición ambiental a plaguicidas: biomarcadores en matrices de la tríada madre-placenta-feto / Environmental exposure to pesticides: biomarkers in matrices of the mother-placenta-fetus triad / Exposição ambiental aos agrotóxicos: biomarcadores em matrizes do tríade mãe-placenta-feto

El biomonitoreo tiene un papel fundamental en la evaluación de la salud ambiental de poblaciones expuestas a contaminantes. Este artículo analiza información referente a biomarcadores de exposición y susceptibilidad así como también a biomarcadores de efecto que pueden ser útiles en estrategias diagnósticas y preventivas en la exposición a plaguicidas persistentes (órganoclorados) y a plaguicidas moderadamente persistentes (órganofosforados), en un período de alta vulnerabilidad como el embarazo. También revisa diferentes estudios en los que se ha observado correlación entre biomarcadores de exposición en matrices de la tríada madre-placentafeto y el impacto en el desarrollo del embarazo y el crecimiento intrauterino así como también en la funcionalidad del cerebro en la infancia. Finalmente, este trabajo describe noveles biomarcadores inespecíficos entre los que se incluyen biomarcadores epigenéticos, de estrés oxidativo, de disrupción endocrina y de expresión genética.

Biomonitoring plays a key role in the assessment of environmental health of populations exposed to pollutants. This paper analyzes information regarding biomarkers of exposure and biomarkers of susceptibility as well as biomarkers of effect that may be useful in diagnostic and preventive strategies in the exposure to persistent pesticides (organochlorine) and moderately persistent pesticides (organophosphates) in a period of high vulnerability as pregnancy. It also reviews different studies where correlation between biomarkers of exposure in matrices of the mother-placenta-feto triad and the impact on the course of pregnancy and fetal growth as well as the functionality of the brain in childhood has been observed. Finally, this work describes nonspecific novel biomarkers including epigenetic biomarkers, biomarkers of oxidative stress, endocrine disruption and gene expression.

O biomonitoramento desempenha um papel fundamental na avaliação da saúde ambiental de populações expostas a contaminantes. Este artigo analisa informações sobre biomarcadores de exposição e de susceptibilidade, bem como biomarcadores de efeito, que podem ser úteis em estratégias de diagnóstico e de prevenção na exposição a pesticidas persistentes (organoclorados) e a pesticidas moderadamente persistentes (organofosforados), em um período de alta vulnerabilidade, tal como a gravidez. Ele também revisa vários estudos nos quais tem sido observada correlação entre biomarcadores de exposição em matrizes da tríade mãe-placenta-feto e o impacto no desenvolvimento da gestação e no crescimento intra-uterino, bem como na funcionalidade do cérebro na infância. Finalmente, este artigo descreve biomarcadores inespecíficos nóveis incluindo biomarcadores epigenéticos, de estresse oxidativo, de disrupção endócrina e de expressão gênica.

Determination of imidacloprid in water samples via photochemically induced fluorescence and second-order multivariate calibration.

This paper presents a new method for the determination of imidacloprid in water samples; one of the most widely used neonicotinoid pesticides in the farming industry. The method is based on the measurement of excitation-emission spectra of photo-induced fluorescence (PIF-EEMs) associated with second-order multivariate calibration with a parallel factor analysis (PARAFAC) and unfolded partial least squares coupled to residual bilinearization (U-PLS/RBL). The second order advantage permitted the determination of imidacloprid in the presence of potential interferences, which also shows photo-induced fluorescence (other pesticides and/or unexpected compounds of the real samples). The photoreaction was performed in 100-µl disposable micropipettes. As a preliminary step, solid phase extraction on C18 (SPE-C18) was applied to concentrate the analyte and diminish the limit of detection. The LOD was approximately 1 ng mL(-1), which is suitable for detecting imidacloprid in water according to the guidelines established in North America and Europe. The PIF-EEMs coupled to PARAFAC or U-PLS/RBL was successfully applied for the determination of imidacloprid in different real water samples, with an average recovery of 101±10%.

A review of photochemical approaches for the treatment of a wide range of pesticides.

Pesticides are renowned as some of the most pernicious chemicals known to humankind. Nine out of twelve most hazardous and persistent organic chemicals on planet have been identified as pesticides and their derivatives. Because of their strong recalcitrant nature, it often becomes a difficult task to treat them by conventional approaches. It is well perceived that many factors can interfere with the degradation of pesticides under ambient conditions, e.g., media, light intensity, humic content, and other biological components. However, for the effective treatment of pesticides, photochemical methods are viewed as having clear and perceivable advantages. In this article, we provide a review of the fundamental characteristics of photochemical approaches for pesticide treatment and the factors governing their capacity and potential in such a process.

Recent updates on electrochemical degradation of bio-refractory organic pollutants using BDD anode: a mini review.

Boron-doped diamond (BDD) is playing an important role in environmental electrochemistry and has been successfully applied to the degradation of various bio-refractory organic pollutants. However, the review concerning recent progress in this research area is still very limited. This mini-review updated recent advances on the removal of three kinds of bio-refractory wastewaters including pharmaceuticals, pesticides, and dyes using BDD electrode. It summarized the important parameters in three electrochemical oxidation processes, i.e., anodic oxidation (AO), electro-Fenton (EF), and photoelectro-Fenton (PEF) and compared their different degradation mechanisms and behaviors. As an attractive improvement of PEF, solar photoelectro-Fenton using sunlight as UV/vis source presented cost-effectiveness, in which the energy consumption for enrofloxacin removal was 0.246 kWh/(g TOC), which was much lower than that of 0.743 and 0.467 kWh/(g TOC) by AO and EF under similar conditions. Finally the existing problems and future prospects in research were suggested.

Pesticide photolysis in prairie potholes: probing photosensitized processes.

Prairie pothole lakes (PPLs) are glacially derived, ecologically important water bodies found in central North America and represent a unique setting in which extensive agriculture occurs within wetland ecosystems. In the Prairie Pothole Region (PPR), elevated pesticide use and increasing hydrologic connectivity have raised concerns about the impact of nonpoint source agricultural pollution on the water quality of PPLs and downstream aquatic systems. Despite containing high dissolved organic matter (DOM) levels, the photoreactivity of the PPL water and the photochemical fate of pesticides entering PPLs are largely unknown. In this study, the photodegradation of sixteen pesticides was investigated in PPL waters sampled from North Dakota, under simulated and natural sunlight. Enhanced pesticide removal rates in the irradiated PPL water relative to the control buffer pointed to the importance of indirect photolysis pathways involving photochemically produced reactive intermediates (PPRIs). The steady-state concentrations of carbonate radical, hydroxyl radical, singlet oxygen, and triplet-excited state DOM were measured and second-order rate constants for reactions of pesticides with these PPRIs were calculated. Results from this study underscore the role of DOM as photosensitizer in limiting the persistence of pesticides in prairie wetlands through photochemical reactions.

Economic evaluation of a combined photo-Fenton/MBR process using pesticides as model pollutant. Factors affecting costs.

The aim of this paper is to carry out an economic assessment on a solar photo-Fenton/MBR combined process to treat industrial ecotoxic wastewater. This study focuses on the impact of the contamination present in wastewater, the photochemical oxidation, the use of an MBR as biological process and the plant size on operating and amortization costs. As example of ecotoxic pollutant, a mixture of five commercial pesticides commonly used in the Mediterranean area has been used, ranging from 500 mg/L to 50mg/L, expressed as dissolved organic carbon concentration. The economic evaluation shows that (i) the increase in pollution load does not always involve an increase in photo-Fenton costs because they also depend on organic matter mineralization; (ii) the use of an MBR process permits lower photochemical oxidation requirements than other biological treatments, resulting in approximately 20% photo-Fenton cost reduction for highly polluted wastewater; (iii) when pollution load decreases, the contribution of reactant consumption to the photo-Fenton process costs increase with regard to amortization costs; (iv) 30% total cost reduction can be gained treating higher daily volumes, obtaining competitive costs that vary from 1.1-1.9 €/m(3), depending on the pollution load.

Zinc(II) phthalocyanines immobilized in mesoporous silica Al-MCM-41 and their applications in photocatalytic degradation of pesticides.

In the present study the authors investigated a set of three new zinc(II) phthalocyanines (zinc(II) tetranitrophthalocyanine (ZnTNPc), zinc(II) tetra(phenyloxy)phthalocyanine (ZnTPhOPc) and the tetraiodide salt of zinc(II)tetra(N,N,N-trimethylaminoethyloxy) phthalocyaninate (ZnTTMAEOPcI)) immobilized into Al-MCM-41 prepared via ship-in-a-bottle methodology. The samples were fully characterized by diffuse reflectance-UV-vis spectroscopy (DRS-UV-vis), luminescence, thermogravimetric analysis (TG/DSC), N(2) adsorption techniques and elemental analysis. A comparative study was made on the photocatalytic performance upon irradiation within the wavelength range 320-460nm of these three systems in the degradation of pesticides fenamiphos and pentachlorophenol. ZnTNPc@Al-MCM-41 and ZnTTMAEOPcI@Al-MCM-41 were found to be the most active systems, with the best performance observed with the immobilized cationic phthalocyanine, ZnTTMAEOPcI@Al-MCM-41. This system showed high activity even after three photocatalytic cycles. LC-MS product characterization and mechanistic studies indicate that singlet oxygen ((1)O(2)), produced by excitation of these immobilized photosensitizers, is a key intermediate in the photocatalytic degradation of both pesticides.

Effect of organic species on the solar detoxification of water polluted with pesticides.

The effect of organic species on a solar-driven photo-Fenton treatment of a mixture of pesticides (methyl-oxydemethon, methidathion, carbaryl and dimethoate) has been studied in this paper. Triethoxyisododecyl alcohol, acetophenone and ethylenediaminetetraacetic acid (EDTA) have been used as examples of surfactants, solvents and complexing agents, respectively. An inhibitory effect on mineralization as well as on the elimination of the pesticides was observed in the case of the aliphatic surfactants, most probably due to the competition between the pesticides and the added organic matter for reaction with the relatively unselective hydroxyl radical. A methodology combining chemical analyses and bioassays was tested in order to explore the applicability of coupling a photo-Fenton process with a biological treatment in the presence of the surfactant. Despite the complexity of the mixture under study, a reliable monitoring of the process was accomplished; the biocompatibility of the mixture was enhanced and the optimal irradiation intensity was achieved just after complete removal of the pesticides.

Treatment of pesticide rinsate towards reuse by photosensitized Fenton-like process.

A Fenton-like process with combination of dye has been used to enhance the treatment of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran -7-yl methylcarbamate) pesticide rinsate. Results showed that as compared to Fenton-like process, this photosensitization Fenton-like process improved the degradation efficiency of carbofuran rinsate significantly. Among the conditions studied, the optimum dosage for the complete destruction of carbofuran molecular structure was found under a [H2O2]0/[Fe3+]0 ratio of 30-35 and a [Dye]0/[Fe3+]0 ratio of 2%, respectively, after an irradiance of 500 W/m2 for 20 min. As a result, the COD degradation efficiency of rinsate could be promoted from 37.1 to 61.2% and 66.0% by an addition of methylene blue (MB) and alizarin red S (ARS), respectively. Nevertheless, ARS showed a much more effective acceleration effect on the mineralization and microtoxicity reduction of carbofuran than MB. A mineralization efficiency of 57.2% and a microtoxicity reduction of 90% could be achieved with the addition of ARS. Because of its quinone structure unit, the dye ARS could play a role like hydroquinone to recycle Fe2+ from Fe3+, resulting in one more catalytic effect on the reduction of Fe3+ and thus the mineralization and microtoxicity reduction of carbofuran was greatly promoted in the presence of ARS. In addition, it was found that carbofuran molecules could be decomposed quickly to lower-molecular-weight intermediates and even mineralized by attacking of hydroxyl radicals. Carbofuran was found to be decomposed to carbofuran phenol, 3-oxo carbofuran phenol, and 3-hydroxyl carbofuran phenol initially, and then further be degraded to smaller molecules, such as NO3-, CH3COOH, (COOH)2 and CO2. Accordingly, it was believed that the Fenton-like process along with the aid of a photosensitizer, such as ARS, under an appropriate ratio could be a feasible and potential technology for the treatment of pesticide rinsate.

Phototransformation of selected organophosphorus pesticides: roles of hydroxyl and carbonate radicals.

The phototransformation of two organophosphorus pesticides, parathion and chlorpyrifos, by hydroxyl radicals and carbonate radicals in aqueous solution were studied. Addition of hydrogen peroxide increased the UV degradation rates of both pesticides and data were simulated through kinetic modeling. The second-order rate constants of parathion and chlorpyrifos with hydroxyl radical were determined to be 9.7 +/- 0.5 x 10(9) and 4.9 +/- 0.1 x 10(9) M(-1) s(-1), respectively. The presence of bi/carbonate ions reduced the pesticide degradation rates via scavenging of hydroxyl radical but the formation of carbonate radical also contributed to the degradation of the pesticides with second-order reaction rate constants of 2.8 +/- 0.2 x 10(6) and 8.8 +/- 0.4 x 10(6) M(-1) s(-1) for parathion and chlorpyrifos, respectively. The dual roles of bicarbonate ion in UV/H2O2 treatment systems, i.e., scavenging of hydroxyl radicals and formation of carbonate radicals, were examined and discussed using a simulative kinetic model. The transformation of pesticides by carbonate radicals at environmentally relevant bi/carbonate concentrations was shown to be a significant contributor to the environmental fate of the pesticides and it reshaped the general phototransformation kinetics of both pesticides in UV/H2O2 systems.

Oxidative degradation of dinitro butyl phenol (DNBP) utilizing hydrogen peroxide and solar light over a Al2O3-supported Fe(III)-5-sulfosalicylic acid (ssal) catalyst.

A novel and efficient photo-Fenton catalyst of Fe(III)-5-sulfosalicylic acid (ssal) supported on Al(2)O(3) was prepared and characterized by FT-IR and TEM-EDX technique. A detailed investigation of photocatalytic degradation of 2-sec-butyl-4,6-dinitrophenol (DNBP) using this catalyst and H(2)O(2) under solar light irradiation was carried out. The effects of reaction parameters on photodegradation performance were investigated by examining H(2)O(2) dosage, catalyst loading, solution pH, initial DNBP concentration and temperature. The optimal conditions were an initial DNBP concentration of 40 mg L(-1) at pH 2.5 and temperature 30 degrees C with catalyst loading of 1.0 g L(-1) and H(2)O(2) concentration of 5 mmol L(-1) under solar light irradiation for 100 min. Almost complete degradation of DNBP was observed with [Fe(III)-ssal]-Al(2)O(3)/H(2)O(2) process under the optimal conditions. The degradation of DNBP by photo-Fenton-type process can be divided into the initiation phase and the fast phase. The kinetics of Fenton oxidation is complex and the degradation of DNBP in the two phases both can be described by a pseudo-first-order kinetic model. No obvious decline in efficiency of the [Fe(III)-ssal]-Al(2)O(3) catalyst was observed after 5 repeated cycles indicating this catalyst is stable and reusable. A possible reaction mechanism was proposed on the basis of all the information obtained under various experimental conditions.

Photocatalytic degradation of eight pesticides in leaching water by use of ZnO under natural sunlight.

Photodegradation of eight pesticides in leaching water at pilot plant scale using the tandem ZnO/Na(2)S(2)O(8) as photosensitizer/oxidant and compound parabolic collectors under natural sunlight is reported. The pesticides, habitually used on pepper culture and belonging to different chemical groups were azoxyxtrobin, kresoxim-methyl, hexaconazole, tebuconazole, triadimenol, and pyrimethanil (fungicides), primicarb (insecticide), and propyzamide (herbicide). As expected, the influence of the semiconductor used at 150 mg L(-1) on the degradation of pesticides was very significant in all cases. Photocatalytic experiments show that the addition of photosensitizer strongly improves the elimination of pesticides in comparison with photolytic tests; significantly increasing the reaction rates. The use of Na(2)S(2)O(8) implies a significant reduction in treatment time showing a quicker reaction time than ZnO alone. On the contrary, the addition of H(2)O(2) into illuminated ZnO suspensions does not improve the rate of photooxidation. The disappearance of the pesticides followed first-order kinetics according to Langmuir-Hinshelwood model and complete degradation occurs from 60 to 120 min. The disappearance time (DT(75)), referred to the normalized illumination time (t(30 W)) was lower than 3 min in all cases.