Comparative photodegradation study of atrazine and desethylatrazine in water samples containing titanium dioxide/hydrogen peroxide and ferric chloride/hydrogen peroxide

Results are reported for a comparative photodegradation study of atrazine and desethylatrazine in water using TiO2/H2O2, FeCl3/H2O2, and photolysis. Deionized water and ground water spiked with atrazine or desethylatrazine at 36 micrograms/L were irradiated by using a xenon arc lamp and/or sunlight. After irradiation, the water samples containing the spiked pesticides were preconcentrated by using C18 solid-phase extraction disks and analyzed by gas chromatography with nitrogen-phosphorus and mass spectrometric detection. A relative percentage of 7% desethylatrazine was detected in samples removed after 20 and 4 min of sensitized photodegradation with TiO2 and Fe3+, respectively. Atrazine and desethylatrazine did not degrade when solar irradiation (in winter) and deionized water were used. Atrazine degraded faster than desethylatrazine when a xenon arc lamp or sunlight plus FeCl3 was used, with half-lives varying from 5 to 11 min and from 19 to 26 min, respectively. In other photodegradation experiments, the degradation of atrazine was slightly higher than that of desethylatrazine. This study shows that desethylatrazine has slightly higher stability than atrazine in environmental water samples; this stability accounts for the frequent detection of desethylatrazine together with atrazine in natural waters.     

Identification of Carbofuran And Methiocarb and their Transformation Products in Estuarine Waters by On-line Solid Phase Extraction Liquid Chromatography—Mass Spectrometry

Abstract

The degradation of the carbamate insecticides carbofuran and methiocarb in distilled and natural waters was determined. Degradation studies were carried out both under a xenon arc irradiation and natural sunlight at pesticide concentrations of 50–100 μg/L. 50–100 mL water sample were preconcentrated using automated online solid phase extraction (SPE) followed by liquid chromatography (LC), UV detection or post column fluorescence detection (EPA method 531.1 for carbamate insecticides). Structure identification was carried out by on-line SPE-LC-MS either with thermospray and/or high flow pneumatically assisted electrospray interfaces. Half-lives varying between 4–12.5 days for carbofuran and methiocarb were determined under natural sunlight exposure, being chemical hydrolysis the major degradation pathway. When using xenon arc lamp irradiation both pesticides degraded very rapidly with half-lives varying from 0.3–1.7 hours. The various degradation products identified were: methiocarb sulfoxide, 4-methylthio-3, 5-dimethylphenol, 3-hydroxy-7-carbofuranphenol and 2-hydroxy-3-(2-methylprop-1-enyl)-phenyl-N-methylcarbamate.     

Identification of New Photodegradation Byproducts of the Antifouling Agent Irgarol in Seawater Samples

Abstract

A photodegradation study for Irgarol was carried out in order to investigate several products of degradation formed in different environmental matrices and under different conditions. Deionized water, groundwater and seawater samples, spiked at 30–100 μg/L with Irgarol, were irradiated using a xenon are lamp and/or sunlight. Aliquots of the spiked water samples were taken at different times of irradiation and compounds were isolated from the water samples by means of solid-phase extraction (SPE) using either C₁₈ or PLRP-s cartridges. Separation and detection of the compounds was accomplished by several analytical methodologies such as liquid chromatography-diode array detection (LC-DAD), liquid chromatography-electrospray ionization/mass spectrometry (LC-ESI/MS) and gas chromatography-mass spectrometry (GC-MS). Four new byproducts, with molecular weights of 167, 197, 207 and 213, were identified in this photodegradation study. When the photolysis was carried out with xenon lamp, half-lives of Irgarol were 103.8, 125.4 and 107.5 minutes in deionized water, groundwater and seawater, respectively. In seawater samples, a 98% of degradation was observed for Irgarol, after 217 hours of solar irradiation, being the main byproduct formed that corresponding to M_w = 213. On the other hand, the use of two different sensitizers -(TiO₂/H₂O₂), (FeCI₃/H₂O₂)- was also evaluated in deionized water samples containing Irgarol. These experiments were carried out in order to evaluate the use of these two sensitizers for decontamination of polluted waters.     

Near UV-visible light induced cationic photopolymerization reactions: A three component photoinitiating system based on acridinedione/silane/iodonium salt

Acridinediones (AD) are attractive dyes exhibiting a strong absorption at about 400 nm. When used in the presence of a silane and an iodonium salt, they efficiently initiate the free radical promoted cationic photopolymerization of an epoxide under air and upon a xenon lamp, a laser diode or sunlight exposure. The mechanism analyzed by ESR and laser flash photolysis is discussed and opens a new way for the design of such three-component systems.     

Coupled-column liquid chromatography combined with postcolumn photochemical derivatization and fluorescence detection for the determination of herbicides in groundwater

This study examines the application of coupled-column LC-photochemically induced fluorimetry-fluorescence detection (LC-LC-PIF-FD), demonstrating its potential for the quantitative and selective detection of six herbicides, including propanil and the phenylureas monuron, monolinuron, chlorotoluron, diuron and neburon in groundwater samples. An AQUASIL C18 50 x 4.6 mm(2) id column coupled to an AQUASIL C18 150 x 4.6 mm(2) id column for analyte clean-up and determination were used, respectively. A simple SPE with Cl8 cartridges was carried out, yielding average recoveries between 80 and 112% (n = 6) with RSDs between 0.5 and 9%. The LODs ranged from 0.0083 to 0.0833 microg/L in the groundwater samples.     

Analysis of phenylurea herbicides from plants by GC/MS

Seven phenylurea herbicides (chlorbromuron, fluometuron, diuron, linuron, metobromuron, monolinuron, monuron) were isolated from weed plant materials by extraction with acidic aqueous solutions-the aqueous extract preconcentrated and cleaned-up by using a continuous SPE module. Elution with ethyl acetate resulted in >95% recovery of the herbicides from the LiChrolut-EN sorbent column. Separation of the seven herbicides was easily achieved working under fixed gas-chromatographic conditions and, although other peaks were also detected (corresponding to isocyanate degradation products), they showed different retention times and lower intensity than the parent compounds; in addition, as reproducible chromatograms in terms of herbicide-to-isocyanate product peak areas ratio were obtained, no derivatization was required. The analytical figures of merit of the GC/MS method in the selective ion monitoring mode are as follows: limits of detection from 0.5 to 5.0 ng ml(-1); precision (R.S.D.) approximately 7.0%; and preconcentration factor 100 (using 10 ml of sample extract). The proposed GC/MS method offers better resolution and selectivity than the conventional LC-UV method.     

Studying the photochemical fate of methyl parathion in natural waters under tropical conditions

This article discusses the degradation of methyl parathion (MP) in natural and sterilized waters. Experiments were prepared using natural waters gathered in two aquatic systems (Rio de Janeiro State, Brazil), ultra-pure water and humic water solution under different conditions (i.e. in the presence/absence of light, sterilized/no sterilize solutions). The exposition to sunlight was carried out using experimental bottles without headspace immersed in a swimming pool for temperature control. Natural waters results showed that the degradation kinetic of MP is of first order and the half-lives for lake water experiments, under direct sunlight and shade, were 4.41 and 6.89 days, respectively. The kinetic curve for MP degradation in river waters showed that there are no differences when samples were sterilized and placed (or not) under shade conditions, and the half-lives ranged from 5.37 to 2.75 days for sterilized river water/absence of sunlight and natural/presence of sunlight, respectively. Therefore, our results showed that photolysis plays, in addition to bio- and chemical degradation, an important role in the decomposition of MP in aquatic environments.     

Multiresidue Analysis of Phenylurea Herbicides in Environmental and Drinking Water by Capillary Electrophoresis

The present paper describes the application of capillary electrophoresis in the micellar mode to the separation and quantitative determination of five phenylurea herbicides, viz. monuron, linuron, diuron, isoproturon, and monolinuron, in water samples. Using uncoated fused silica capillary and phosphate-borate buffer (pH 7.0) containing SDS, the five pesticides are resolved in less than 15 min and quantitatively determined by an ultraviolet detector at 244 nm. Method optimization and validation parameters are presented. Good linearity and repeatability were observed for all the compounds studied (correlation coefficients 0.999). The feasibility of the method developed was tested by simultaneous determination of these herbicides in environmental and drinking water samples at the minimum residue levels (MRLs) (0.1 μg/L) after solid-phase extraction (SPE) preconcentration procedure.     

Thermal degradation of wood during photodegradation

In this study, wood samples were exposed to light irradiations (direct sunlight, xenon lamp, mercury vapour lamp) and thermal treatments were carried out in dry- and in humid conditions at 90°C. One part of the samples was covered by an aluminium plate during light irradiation. The samples under the aluminium plate also suffered considerable chemical changes, monitored by infrared technique and colour measurement. The sunlight produced greater colour change under the aluminium plate than the artificial light sources. During light irradiation, the carbonyl band having two maximum at 1700 and 1,746 cm(-1) increased and the peak of the aromatic skeletal vibration arising from lignin (1,510 cm(-1)) decreased together with the guaiacyl vibrations at 1,275 cm(-1). There was absorption decrease at 1,174 cm(-1) because of the ether band splitting. Under the covered surface only the ether band at 1,174 cm(-1) decreased and one carbonyl band increased with a maximum at 1,715 cm(-1). Degradation of lignin was negligible for the covered surface. Colour change generated by thermal degradation was much greater in humid condition than in dry condition.     

Aqueous photolysis of the sunscreen agent octyl-dimethyl-p-aminobenzoic acid. Formation of disinfection byproducts in chlorinated swimming pool water

The photochemical behavior of the sunscreen agent octyl-dimethyl-p-aminobenzoic acid (ODPABA) was studied in different aqueous solutions and under different conditions. ODPABA photolysis was performed under laboratory conditions using a xenon light source and under natural sunlight conditions in sea, swimming pool as well as in distilled water. The influence of dissolved organic matter (DOM) on the degradation kinetics was also studied in the presence of various concentrations of humic acids (HA). The phototransformation was shown to proceed via pseudo-first-order reaction in all cases and the reaction rates followed the order: distilled water > swimming pool water > seawater, depending mainly on the presence of dissolved organic matter that retarded the photolysis reaction. Kinetic experiments were monitored with HPLC/UV-DAD and the half-lives (t 1/2) varied between 1.6 and 39 h in simulated solar irradiation and between 27 and 39 h in natural sunlight conditions. The product distribution during illumination was strongly dependent on the constitution of the irradiated media. Irradiation of the aqueous ODPABA solutions gave rise to several transformation products that were isolated by means of solid-phase extraction (SPE) and identified using GC-MS techniques. These were formed mainly through dealkylation and hydroxylation reactions and were detected in all aqueous solutions investigated. In the case of swimming pool water some additional byproducts were isolated and were tentatively identified as chlorinated intermediates, formed by the subsequent chlorination of the parent molecule as well as other intermediates.     

Use of on-line liquid chromatography-nuclear magnetic resonance spectroscopy for the rapid investigation of flavonoids from Sorocea bomplandii

A HPLC method, using photochemically-induced fluorescence detection, is described for the separation and determination of four phenylurea herbicides including diuron, isoproturon, linuron and neburon. A post-column photoreactor, consisting of a reactor knitted around a 4 W xenon lamp, has been included between the column and the detector, in order to transform the non-fluorescent herbicides into fluorophors. The influence of mobile phase composition, flow-rate, pH, and buffer concentration has been studied. An acetonitrile–buffer solution of potassium phosphate dibasic of pH 7 and 0.01 M concentration (60:40, v/v), was selected as optimum. For the fluorimetric detection, optimal excitation/emission wavelengths 324/403, 301/433, 335/411 and 326/385 nm were selected for the determination of diuron, isoproturon, linuron and neburon, respectively. The detection limits ranged between 0.07 and 0.46 μg/ml, according to the compound.     

Biomimetic oxidation of plant protecting agents

The suitability of two in vitro oxidation systems as chemical models for the biological degradation of plant protecting agents has been investigated. As representative herbicides diclofop, fenoxaprop, isoproturon, linuron and monolinuron have been oxidised by two systems, the Fentons' reagent and the ascorbic acid oxidation system (AAOS) and the results compared to those of the known metabolic pathways of these compounds. The herbicides have been oxidised by Fentons' reagent (hydroxy radicals). The main products were isolated by preparative scale HPLC and identified with (1)H-NMR and MS. Some of the products have been identified by comparing their retention times and UV/Vis-spectra to those of standard compounds. Several products known from biological degradation are also found after chemical oxidation, however, notable differences between the two pathways have been observed, for instance in the case of diclofop. Oxidation by the AAOS leads to comparable results. Reaction rates for the oxidation with the AAOS have been studied and compared with data known from degradation studies of the herbicides in soil. Compounds which are slowly degraded in soil are oxidised more slowly in the biomimetic process than those with a fast degradation in soil.     

Study of degradation behavior of besifloxacin,characterization of its degradation products by LC–ESI–QTOF–MS and their in silico toxicity prediction

Knowledge and understanding of the stability profile of a drug is important as it affects its safety and efficacy. In the present work, besifloxacin, a new, fourth‐generation fluoroquinolone antibiotic, was subjected to different forced‐degradation conditions as per International Conference on Harmonization (ICH) guidelines such as hydrolysis (acid, base and neutral), oxidation, thermal and photolysis. The drug degraded under acidic, basic, oxidative and photolytic conditions while it was found to be stable under dry heat and neutral hydrolytic conditions. In total, five degradation products (DPs) were formed under different conditions—DP1 and DP2 (photolysis), DP3 (oxidation), DP4 (acidic), DP3 and DP5 (basic). The chromatographic separation of besifloxacin and its degradation products was achieved on a Sunfire C₁₈ (250 mm × 4.6 mm, 5 μm) column with 0.1% aqueous formic acid–acetonitrile as a mobile phase. The gradient RP‐HPLC method was developed and validated as per ICH guidelines. The degradation products were characterized with the help of LC–ESI–QTOF mass spectrometric studies and the most likely degradation pathway of the drug was proposed. In silico toxicity assessment of the drug and its degradation products was carried out, which indicated that DP3 and DP4 carry a mutagenicity alert.     

Recent developments with light-exposure apparatus and measurement of radiation of their light sources

New techniques and devices which were recently developed in order to avoid various drawbacks of current light-exposure apparatus are introduced. The spectral distribution of the open flame carbon arc approximates more closely to that of sunlight by modifications of the filter system.The life of carbon arcs was lengthened more than two fold. The long-life xenon arc lamp minimized the reduction in output of radiation.The slanted holder improved the locational variance of radiation falling on a specimen.The instrumental methods for measuring light dosage are explained.     

Outdoor and accelerated weathering tests for polypropylene and polypropylene/talc composites: A comparative study of their weathering behavior

In this study, the comparisons of degradation behavior of polypropylene(PP) and PP/talc composites were carried out with one outdoor weathering test and three accelerated weathering (xenon, metal halide and carbon arc lamps) tests, respectively. The outdoor exposure vigorously advanced these degradations with the lowest amount of UV exposure energy. It was found that the degradation rates were affected by the visible light intensity in the light sources. In the case of the existence of talc compound, the degradation was synergistically accelerated by the exposures of the sunshine, the xenon and the metal halide lamps having higher visible light intensities. In addition, the degradations of the PP and the PP/talc composites were found to be synergistically accelerated by sunlight exposure and the acid rain, too.     

Development and Validation of a Novel Stability-Indicating LC Method for the Determination of Riluzole in Bulk Drug and Tablets

A novel stability indicating LC method was developed and validated for the quantitative determination of riluzole in bulk drugs and in pharmaceutical dosage forms in the presence of its isomers, related substances and degradation products. The drug was subjected to stress conditions of hydrolysis (acid, base and neutral), oxidation, photolysis and thermal degradation. Considerable degradation was observed under base hydrolysis and oxidation. The stress samples were assayed against a qualified reference standard and the mass balance was found close to 99.5%. The developed method was validated with respect to linearity, accuracy, precision, specificity, ruggedness and robustness.     

纳米级金红石型二氧化钛与受阻胺光稳定剂协同改进ABS的抗老化性能研究

分别采用纳米级金红石型TiO2和受阻胺光稳定剂(HALS)对ABS进行改性,通过熔融共混法制备了ABS/纳米TiO2、ABS/纳米TiO2/HALS和ABS/HALS复合材料,采用GB/T16422.2~1999所述的塑料实验室光源暴露实验方法,用氙灯气候试验机对其进行28天人工加速老化,通过测定其老化过程中的无缺口和缺口试样冲击强度的变化来对其抗老化性能进行表征,同时利用光学显微镜和扫描电镜对其老化过程中的冲击断口形貌变化进行了研究.结果表明,纳米TiO2在ABS基体中分散良好,改性后的复合材料均具有较好的抗老化性能,纳米TiO2与HALS复合改性ABS对其耐候性的提高具有明显的协同作用,其老化后的抗冲击性能超过了单一使用HALS或纳米TiO2的改性效果,老化28天后纯ABS树脂试样的无缺口冲击强度保持率只有20%左右,添加2.0 wt%纳米TiO2后,老化28天后的ABS/纳米TiO2/HALS复合材料试样的保持率则提高到47.9%,为纯ABS树脂试样的2.5倍.     

Gas chromatographic method for studying the rate of photodegradation of some nitrogen-containing pesticides

Summary The photodegradation behaviour of 12 nitrogen-containing herbicides (atrazine, cyanazine, terbuthylazine, terbutryn, EPTC, buthylate, molinate, cycloate, vernolate, fenuron, chloroxuron, and methabenzthiazuron) has been examined. The compounds were degraded completely when exposed to a mercury-vapour lamp; the degradation process was followed by consecutive GC measurements. All the compounds studied had measurable photochemical activity, although actual and average degradation rates varied significantly. All the compounds except terbutryn furnished more than one major degradation product, in different ratios. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

Photodecomposition of Pigment Yellow 74, a pigment used in tattoo inks

Tattooing has become a popular recreational practice among younger adults over the past decade. Although some of the pigments used in tattooing have been described, very little is known concerning the toxicology, phototoxicology or photochemistry of these pigments. Seven yellow tattoo inks were obtained from commercial sources and their pigments extracted, identified and quantitatively analyzed. The monoazo compound Pigment Yellow 74 (PY74; CI 11741) was found to be the major pigment in several of the tattoo inks. Solutions of commercial PY74 in tetrahydrofuran (THF) were deoxygenated using argon gas, and the photochemical reaction products were determined after exposure to simulated solar light generated by a filtered 6.5 kW xenon arc lamp. Spectrophotometric and high-pressure liquid chromatography (HPLC) analyses indicated that PY74 photodecomposed to multiple products that were isolated using a combination of silica chromatography and reversed-phase HPLC. Three of the major photodecomposition products were identified by nuclear magnetic resonance and mass spectrometry as N-(2-methoxyphenyl)-3-oxobutanamide (o-acetoacetanisidide), 2-(hydroxyimine)-N-(2-methoxyphenyl)-3-oxobutanamide and N,N'-bis(2-methoxyphenyl)urea. These results demonstrate that PY74 is not photostable in THF and that photochemical lysis occurs at several sites in PY74 including the hydrazone and amide groups. The data also suggest that the use of PY74 in tattoo inks could potentially result in the formation of photolysis products, resulting in toxicity at the tattoo site after irradiation with sunlight or more intense light sources.