Chemical and photochemical transformation of fenamiphos—an organophosphorus nematicide

Fenamiphos, an organophosphorus nematicide and its hydrolysis product 4‐methylthio‐m‐cresol under dye‐sensitized photo‐oxidative conditions yielded the corresponding sulfoxide analogs. Under UV‐photolytic conditions, fenamiphos in methanol solution gave mainly the cleavage products. To obtain standards of the oxidative degradation products/metabolites in larger quantities, fenamiphos and fenamiphos phenol was chemically transformed to the corresponding sulfoxide and sulfone. Their structures were confirmed by ‘HNMR and mass spectra.     

Photodegradation of fenamiphos on the surface of clays and soils

The photodegradation of the organophosphorus fenamiphos was studied in various clay matrices: montmorillonite, kaolin and the mineral components of two soils collected from two different sites: Settat (S) and Berrechid (B). The degradation was shown to be mainly due to the direct excitation of fenamiphos and was similar for all the matrices with a two-step kinetics : a fast and a slower one. The first step rate obtained at the surface of montmorillonite was slightly lower than that determined at the surface of kaolin. The fenamiphos degradation process clearly depended on the amount of humic substances and iron(III). The latter component accelerated the disappearance of fenamiphos, while humic substances clearly inhibited the process. The degradation rate increased in the presence of water and was mainly due to the involvement of the photohydrolysis process leading to the scission of the P–O bond. The formation of the main by-products, sulfoxide, sulfone and phenol derivatives, were elucidated by HPLC/MS.     

Photodegradation of the pure and formulated alpha-cypermethrin insecticide gives different products

Alpha-cypermethrin is a broad-spectrum insecticide widely used in the treatment of rice crops, mainly commercialized as a CONTEST^® formulation. The photodegradation of alpha-cypermethrin and of the commercial formulation has not yet been systematically investigated in paddy water under natural conditions. Here, paddy water solutions of alpha-cypermethrin and CONTEST^® formulation at 5.0 mg L^?1 were irradiated under simulated sunlight for 10 days. Hydrolysis experiments were carried out on the same solutions preserved in the dark. Analysis by ultra-high-performance liquid chromatography–tandem mass spectrometry was developed for the identification of photodegradation products. Results show that degradation of pure alpha-cypermethrin and the formulation counterpart produces both common and different photodegradation products. Five out eleven photodegradation products were identified for the first time, in particular three in the alpha-cypermethrin paddy water solution and four in the formulation. Our findings underline the importance of carrying out photodegradation experiments directly on the commercial formulation, since degradation products could be different from the pure insecticide.     

Improvement of the photostability of selected substances in aqueous medium

The photodegradation of some pesticides in water has been investigated. The kinetics of the photochemical processes is discussed and the photolytic half‐life is calculated. The objective of this paper is to present some of the recent results on the kinetics and on the products of sunlight‐induced reactions of Parathion, Gardona, Diazinon, Atrazine and Phenmediphame at low concentrations in distilled water and fresh water. The quantum yield, measured at 263 nm for Phenmediphame in aerated water at 5 × 10^‐4 M and 30°C, was 1.4 × 10^‐2, and for Parathion, measured at 300 nm in aqueous solution at 3.42 M at pH 6.4 and 25 °C, was 1.5 × 10^‐3. The measured absorption spectra and the variable light intensity were used to estimate the environental phototransformation process and the persistence of these compounds in water.     

Photodegradation of Benthiocarb

The photodegradation of ¹⁴C-benthiocarb in water, on a glass surface, on soil and silica gel TLC plates was studied. the study was designed to obtain some information of its dissipation and photodegradation under various laboratory conditions. Benthiocarb degrades readily when exposed to either sunlight or UV light (254 nm). However, it is degraded much faster by UV light than by sunlight. Also, benthiocarb decomposes faster in water or on a glass surface or silica gel surface than on a soil surface. the half-life of benthiocarb exposed to UV light was: 1 hr on glass surface; 1.5 hrs in water; 2 hrs on silica gel TLC plate; 20 hrs on soil TLC plate. Benthiocarb in water, and exposed to sunlight, had a half-life of approximately 3 days. the following major photodegradation products were identified: 4-chlorobenzyl alcohol; 4-chlorobenzaldehyde; 4-chlorobenzoic acid.     

Photodegradation of Benthiocarb

The photodegradation of ¹⁴C-benthiocarb in water, on a glass surface, on soil and silica gel TLC plates was studied. the study was designed to obtain some information of its dissipation and photodegradation under various laboratory conditions. Benthiocarb degrades readily when exposed to either sunlight or UV light (254 nm). However, it is degraded much faster by UV light than by sunlight. Also, benthiocarb decomposes faster in water or on a glass surface or silica gel surface than on a soil surface. the half-life of benthiocarb exposed to UV light was: 1 hr on glass surface; 1.5 hrs in water; 2 hrs on silica gel TLC plate; 20 hrs on soil TLC plate. Benthiocarb in water, and exposed to sunlight, had a half-life of approximately 3 days. the following major photodegradation products were identified: 4-chlorobenzyl alcohol; 4-chlorobenzaldehyde; 4-chlorobenzoic acid.     

European starling nestling response to chlorpyrifos exposure in a corn agroecosystem

European starling (Sturnus vulgaris) nestlings were used as a surrogate to study the effect of chlorpyrifos application to a corn agroecosystem on songbird reproduction. Chlorpyrifos was applied in a T‐band at 1.3 kg AI/ha, and residues were measured in soil, earthworms, ground‐dwelling insects, and diet items collected from the crop of starling nestlings. Chlorpyrifos levels in soil peaked at 34.2 μg/g, 4 days post‐application, and dissipated to trace levels by 64 days post‐application. Concentrations of chlorpyrifos in earthworms and ground‐dwelling insects reached 0.9 and 0.7 ug/g, respectively. Starling nestling diet items included invertebrates from eight orders with chlorpyrifos concentrations ranging from trace levels to 10.6 μg/g in earthworms. Nestling brain and plasma cholinesterase (ChE) activity and body mass measurements were taken at 3, 8, and 13 days post‐hatch (DPH). Adult starling fecundity was also measured. Body mass differences between treatment and reference site nestlings at 3 and 13 DPH were not significant at α = 0.05. However, 8 DPH nestlings from the Treatment Site had a transient reduction in weight (p = 0.03) when compared with 8 DPH reference nestlings. There were no significant differences in brain or plasma ChE activities of 3, 8, or 13 DPH nestlings. Further, multiple measures of fecundity (i.e., clutch size, hatching percentage, and fledging percentage) indicated that chlorpyrifos application did not affect starling nestling survival to fledging, as the values from the Treatment and Reference Site were nearly identical. This screening‐level study suggests that although one age group of starling nestlings from the Treatment Site weighed less than their Reference Site counterparts, a single T‐band application of chlorpyrifos did not impair starling nesting success.     

The occurrence of disinfection by‐products in Taiwan drinking water

In this study, samples were taken from six conventional water treatment plants for disinfection by‐products analysis. Results from the analysis revealed that trihalomethanes (THMs) concentrations in all samples were below regulatory levels (100 μg/L). Although the national standard for haloacetic acids (HAA5) has not yet been promulgated in Taiwan, samples from two water plants contained HAA5 concentrations exceeding the USEPA limit (MCL of HAA5 of Stage 1, 60 μg/L). THMs and HAA5 were found to be the major disinfection by‐products in all water treatment plants. It was noted that the concentration of HAA5 in most samples was higher than that of the trihalomathanes. However, the formation potential of THM (THMFP) was found to be higher than that of HAA (HAAFP). Good correlation also was found between THMFP (or THMFP) and HAA5 (or THMs). In evaluating the performance of the treatment processes, it was found that conventional water treatment processes followed by activated carbon were effective in removing disinfection by‐products (DBPs) from source water with pre‐ozonation. The treatment processes were at their optimum performance in removing contaminants when O₃/TOC₀ was held at 0.75.     

Potential correlation between perfluorinated acids and liver morphology in East Greenland polar bears (Ursus maritimus)

In this study, residual concentrations of chlorpyrifos (CPF) were determined in feed (40) and fodder (25) samples collected from various locations of Tarai region of Uttarakhand. For extracting residues, liquid–liquid partition followed by alumina column clean up was used and the detection and quantification of residues was undertaken with the help of high-performance liquid chromatography using C18 column and diode array detector at 220?nm. Of the total 40 feed samples analyzed, 7 (17.5%) samples were found positive for CPF with the mean residual concentration of 0.058?µg?g^?1; while out of 25 fodder samples, CPF residues were detected in a single (4%) sample with residual concentration of 0.39?µg?g^?1. However, none of the feed or fodder samples contained CPF residues above the prescribed limit.     

Photolytic decomposition of uc‐54229, a Proinsecticide of the Carbamate group

Phototransformation of UC‐54229 (1) [2,3‐dihydro‐2,2‐dimethyl‐7‐benzofuranyl‐N‐(trimethylamino acetyl)‐N‐methyl carbamate chloride] was studied under UV and visible light conditions. Photoirradiation of 1 with UV‐light resulted in the formation of five degradation products which on the basis of their mass and ¹H Nmr spectral analysis were characterised as 2, 3, 4, 5 and 6. It was observed that under the influence of light, UC‐54229 was degraded to acetyl‐carbofuran which under similar conditions underwent further transformation to the actual toxicant carbofuran. The degradation products or impurities present in 100% water soluble powder formulation were identified as carbofuran phenol and triethylamine hydrochloride.     

水体和甘蓝及土壤中毒死蜱残留检测方法

研究运用不同的样品前处理方式,在装配火焰光度检测器的气相色谱(GC-FPD)上检测,建立了有机磷杀虫剂毒死蜱在水样、土壤和甘蓝中的残留测定方法.研究表明,不同样品中的毒死蜱残留采用本文中介绍的前处理方法是可行的,用石油醚盐析提取和净化水样中毒死蜱,采用丙酮振荡提取甘蓝中毒死蜱,选用索氏提取法提取土壤中毒死蜱,并经液液分配净化后,采用OV-101大口径毛细管柱(30 m×0.53 mm×1.0μm),在装配火焰光度检测器(FPD和磷滤光片)的气相色谱上测定.该分析方法下,毒死蜱的保留时间为1.74 min,线性范围在1.0×10-11—1.0×10-8g之间,其线性相关系数为0.9998,最小检出量为2.0×10-12g.在设定的较低添加浓度的条件下,毒死蜱在水样、土壤与甘蓝上的添加回收率为80%—120%,变异系数均小于5%.该分析方法灵敏、准确、操作简便,适合水样、甘蓝和土壤中低浓度毒死蜱的残留检测.     

Soil and plant biodegradation of chlorpyrifos in fields of cauliflower and brussels sprouts crops

For the protection of early and summer cauliflower and brussels sprouts crops against root fly, the insecticide chlorpyrifos was applied at planting onto soil around the stem of the plant, or in the planting line. In the soil, chlorpyrifos (1) was transformed into the insecticide metabolites oxon, 0,0‐diethyl‐0‐(3,5,6‐tri‐chloro‐2‐pyridinyl) phosphate (2), and 3,5,6‐trichloro‐2‐pyridinol (3). The soil half life time of chlorpyrifos could be 2.8 times greater (42 days relative to 15 days) when the field history as to cauliflower monoculture and insecticide treatments was short (1 year), than when it was long (8 years). Rains and season also had cumulative effects on the chlorpyrifos soil half life times. In the leaves of cabbage, chlorpyrifos and compound 3 were observed at concentrations which were higher, especially when their soil concentrations were high. Chlorpyrifos and compounds 2 and 3 however were not detected in the “flower” of cauliflower, nor in the brussels sprouts itself, the limit of sensitivity being 0.02 ppm of fresh weight.     

Dissipation of fluvalinate and characterisation of its degradation products on chickpea crop by mass spectroscopy

Fluvalinate was applied on chickpea crop at (i) 0.056, (ii) 0.112 and (iii) 0.56 kg a.i. ha^‐1 to evaluate its rate of dissipation. Two major degradation products of fluvalinate formed on the crop were identified and characterised as phenoxybenzoic acid and 2‐[2‐chloro‐4‐(trifluoromethyl)anilino]‐3‐methylbutanoic acid. They were estimated in day‐5 and day‐10 samples of chickpea crop as their methyl esters by gas liquid chromatography.     

Photodegradation of the antibiotic spiramycin studied by high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry

The degradation of spiramycin induced by ultraviolet (UV) irradiation was studied at pH 3–4, 6–7 and 8–9 using high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry. Furthermore, the influence of hydrogen peroxide and oxygen on the photodegradation was investigated. Three degradation products were observed in the presence of oxygen and four in the absence of oxygen. The degradation kinetics were monitored as mass area-time curves, analyzed and described using subsequent follow-up reaction first-order models. The m/z values of the degradation products were determined to be 160, 322 and 366, the latter representing two separate products, the sugar moieties of spiramycin. Remainders of the macrocycle or the intact lactone ring of spiramycin were not observed, since the conjugated π-electron system was assumed photoexcited and thus undergoing photodegradation and fast destruction of the ring. The kinetic of the degradation of spiramycin itself was described using a first-order model. The degradation was accelerated upon addition of hydrogen peroxide. In contrast, systematic acceleration depending on pH could not be found. The absence of oxygen did not lead to any significant acceleration. The findings are interpreted in terms of the effectiveness of advanced oxidation processes and their potential use as a fourth purification step in wastewater treatment plants.     

A chemical mechanism for dry deposition—the role of biogenic hydrocarbon (Terpene) emissions in the dry deposition of O3, SO2 and NOx in forest areas

Terpenes react quite rapidly with ambient ozone and lead via ozonides to highly oxidizing radicals and consecutive products forming aerosols. In the presence of SO₂ sulphur containing compounds, mainly as sulphate, are formed. By means of gas chromatography/mass spectrometry and by comparison with known spectra the main products of the reaction of ß‐pinene (as a model compound) with ozone and sulphur dioxide could be identified.

Reaction of terpenes with NO₃‐radicals, which build up in the atmosphere at night‐time, leads to the formation of organic nitrates that form aerosols. The kinetics as well as the products of the reaction between NO₃‐radicals and ß‐pinene have been studied by FTIR and MS.     

Aliphatic and aromatic halocarbons as potential mutagens in drinking water

Chlorinated phenols are either products of industrial chemical processes or the result of chlorination of drinking water. Often, the formation of chlorinated phenols is based upon naturally occurring phenol. The following chlorinated phenols have been selected for testing in the Ames‐test for their mutagenic activity: 3‐chlorophenol, 4‐chlorophenol, 2,3,6‐, 2,4,5‐, 2,4,6‐trichlorophenol, 4‐chloro‐2‐methylphenol and 4‐chloro‐3‐methylchlorophenol. The tester strains TA97, TA98, TA100 and TA104 were employed. All tested compounds produced mutagenic activity at least in one tester strain. The highest numbers of revertants were detected for 2,3,6‐ and 2,4,6‐trichlorophenol. But in contrast to the other substances, these two induced only frameshift mutations in presence of a metabolizing system. The evidence of their presence in drinking water and of their mutagenic activity makes them to a potential health hazard.     

甲草胺热裂解气相色谱-质谱分析

甲草胺是一种广泛用于农作物上的酰胺类除草剂.本文利用裂解气相色谱与质谱联用(Py-GC-MS)研究了甲草胺在热裂解温度200℃、400℃、600℃、800℃下的降解产物和热降解机理.实验结果表明,共有60种裂解产物被分离鉴定,随着温度的升高甲草胺显著分解,当裂解温度超过600℃时,大量的芳烃类、喹啉类、吲哚类化合物在高温裂解中产生,温度越高他们的相对含量也越高.基于对裂解产物的定性和它们含量的变化提出了甲草胺的热降解机理.     

A preliminary assessment of levels of antifouling booster biocides in harbours and marinas of the island of Gran Canaria, using SPE-HPLC

An analytical procedure was developed to allow for the study of the levels of concentration of biocides in the various different ports on the island of Gran Canaria, The Canary Islands. The analytes studied were extracted from water samples using solid-phase extraction and then determined by high-performance liquid chromatography using a diode array detector. The relative standard deviations of the developed procedure were under 12%. Recoveries over 85% and limits of detection between 0.007 and 0.4 μg/L were obtained for all the analytes. The method was applied to the analysis of sea water samples from the ports and marinas on the island of Gran Canaria.     

Environmental degradation of atrazine,linuron and fenitrothion in soil samples

The persistence of atrazine, linuron and fenitrothion in soil samples from an estuarine area (Ebro delta, Tarragona, Spain) has been studied. Soil samples from the top surface (10 cm) were collected during 1989–91, freeze‐dried, sieved through 200 μm, Soxhlet extracted with methanol, cleaned‐up with Florisil and analysed either by gas chromatography‐nitrogen phosphorus detection (GC‐NPD), in the case of atrazine and fenitrothion, or by liquid chromatography with diode array detection (LC‐DAD), for linuron. Confirmation of the samples analysed by GC‐NPD was carried out using GC‐mass spectrometric detection (MS) in the electron impact mode. The soil half lives obtained under the real environmental conditions have been calculated and the values obtained have been correlated with the physicochemical properties of each pesticide and the soil type. Degradation was affected by volatilization since temperatures in the area of study are relatively high, ca. 30°C, in the summer period. In the case of atrazine it has been shown that deethylatrazine is formed in all the samples studied..     

Contaminants in water: non-target UHPLC/MS analysis

Contamination of water resources is one of the major problems to be faced for environment preservation and sustainability. The monitoring of target compounds based on mass spectrometry and selected reaction monitoring mode is often insufficient to definitely assess the quality of surface water. Also potentially harmful non-target pollutants simultaneously present must be taken into account. Liquid chromatography coupled with tandem mass spectrometry is suitable to obtain complete information on water composition. Hybrid mass spectrometers such as triple quadrupole/linear ion trap, hybrid quadrupole/time-of-flight and linear ion trap/orbitrap analyzers should be used. Here, we review ultra-high performance liquid chromatography coupled with mass spectrometry methods developed for post-target and non-target screening analysis of water emerging contaminants, such as pesticides and their degradation products, pharmaceuticals and drug side-reaction products, surfactants and illicit drugs. The major points are the following: (1) the possibility of performing retrospective analysis only by high-resolution mass analyzer; (2) the compatibility of mass analyzer with ultra-high performance liquid chromatography; (3) the use of deconvolution software to detect unknowns; and (4) the limited availability of library database.