Determination of residues of endosulfan in human blood by a negative ion chemical ionization gas chromatographic/mass spectrometric method: impact of long-term aerial spray exposure

A new and sensitive analytical method using negative ion chemical ionization gas chromatography/mass spectrometry in selective ion monitoring (SIM) mode has been developed for the determination of residues of endosulfan in the human blood. The residues of endosulfan are extracted from whole blood samples without separating the serum by the addition of 60% sulfuric acid at 10 degrees C followed by partition with hexane + acetone (9 + 1 by volume). The total endosulfan is quantified as the sum of alpha-endosulfan, beta-endosulfan and endosulfan sulfate in SIM mode. The mass-fragment ions used for this purpose that are monitored for in SIM mode include endosulfan diol: 95, 169, 214, 313, alpha-endosulfan: 99, 242, 270, 406, beta-endosulfan: 99, 242, 270, 406, and endosulfan sulfate: 97, 353, 386. Recovery experiments were conducted at the concentration range 1.0-100 pg ml(-1). Results showed 112-98% recovery of total endosulfan from the whole blood samples. The relative standard deviation was 1.49-2.68%. The method was found to be highly sensitive in quantifying endosulfan residues down to the 0.1 pg ml(-1) level. Conversion of endosulfan to endosulfan diol was found to be less than 0.1% under the conditions used. The results were compared with published data. The applications of the analytical method for the determination of endosulfan residues in real samples was tested by analyzing 106 human blood samples collected from a population living in Padre village, Kasargode District, Kerala, India, where aerial spraying of endosulfan has been a common agricultural practice over the years. The results showed that none of the blood samples contained residues of endosulfan (alpha-endosulfan 4 beta-endosulfan + endosulfan sulfate) or endosulfan diol. The results were confirmed by the detection of the appropriate amounts in a number of these samples which had subsequently been spiked with endosulfan.     

Interconversion of stereoisomers of endosulfan on chickpea crop under field conditions

The pure individual stereoisomers of endosulfan, alpha-endosulfan and beta-endosulfan, were applied as emulsifiable concentrates to chickpea crop at the rate of 175 g a.i. ha −1 and 50 g a.i. ha −1, respectively. The dissipation rate of these isomers revealed that alpha-endosulfan interconverted to beta-endosulfan in minor quantities, while it was converted into endosulfan sulfate on chickpea leaves in significant amounts. On application, beta-endosulfan was converted to endosulfan sulfate and alpha-endosulfan in relatively smaller amounts. The study indicates that the beta stereoisomer of endosulfan is more persistent because it is resistant to interconversion and metabolic change.     

The interaction of endosulfan with the Collembolan, Proisotoma minuta (Tullberg): toxicity, the effects of sub-lethal concentrations and metabolism

An increased level of the Collembolan, Proisotoma minuta Tullberg was found in the cotton-growing areas of New South Wales, Australia. They were regularly exposed to endosulfan, a highly insecticidal compound. Toxicity, sub-lethal effects and metabolism of endosulfan were studied in P minuta that had been successfully maintained in a plaster of Paris and charcoal mixture substrate with freeze-dried yeast as a food. The 168-h LD50 values were 0.011, 0.049 and 0.055 mg liter(-1) for alpha- and beta-endosulfan and endosulfan sulfate, respectively. When P minuta were exposed to non-lethal concentrations of the endosulfans, egg production was inhibited. On recovery from the toxic effects of the endosulfans they resumed production of viable eggs. Conversion of alpha- and beta-endosulfan to endosulfan sulfate was found and the endosulfan sulfate could be further metabolized. The rate of metabolism of alpha-endosulfan was greater than that of beta-endosulfan and the product of endosulfan sulfate metabolism was not identified.     

Determination of residues of endosulfan and endosulfan sulfate on eggplant,mustard and chickpea

Extractable residues of endosulfan stereoisomers and its toxic metabolite, endosulfan sulfate, on a vegetable, an oilseed and a pulse crop were determined by gas-liquid chromatography. The study revealed that the alpha isomer degraded faster than the beta isomer. Beta-endosulfan accumulated during the first three days following the treatment. Endosulfan sulfate residues appeared a few days after application and decreased with time. The total endosulfan residues in the seeds from treated mustard ranged from 0.08 to 0.12 mg kg^?1 and were at or below the limit of determination (0.02 mg kg^?1) in chickpea seeds following harvest.     

Endosulfan residues on alfalfa hay exposed to drying by sunlight,ultraviolet light and air

Endosulfan residues on alfalfa hay exposed to drying by sunlight, ultraviolet light and air under controlled conditions were investigated using g.l.c. and t.l.c. Maximum loss of total endosulfan and related residues calculated as endosulfan occurred approximately 7 days after application and exposure on Lot 1 (dark) and 5 days on Lot II (ultraviolet light) and 6 days on Lot III (sunlight). Maximum losses of residues on Lot I, Lot II and Lot HI were 48.3, 66.7 and 81.9%, respectively. No endosulfan lactone was detected in any of the samples exposed to the different light treatments. In all Lots the endosulfan sulphate percentage of the total residue increased but most dramatically in the dark drying experiment. The endosulfan a-hydroxy ether residues increased in Lot III (sunlight) up to day 7.     

Fate of Endosulfan in Cotton Soil under Sub-tropical Conditions of Northern India

Terrestrial field studies were conducted with endosulfan during the 1989–90 Kharif season in bare cotton soil, to investigate the fate of endosulfan and its downward movement under sub-tropical conditions of northern India. Field experiments consisted of spray application of endosulfan at 875 g ha^-1 42 and 63 days after the assumed date of sowing in two separate treatments. Soil samples drawn periodically from different depths were analysed by GC-ECD (Ni⁶³) for endosulfan and its breakdown products. Dissipation of the total endosulfan residues occurred to an extent of 92–97% in the first four-week period and by about 99% in 238 days in two distinct phases in first-order kinetics. Residue half life (T_1/2) varied from 39 to 42 days. The parent compound metabolized to endosulfan-diol and endosulfan sulfate. Endosulfan-diol remained confined in the upper 5-cm layer and dissipated completely in 28 days whereas endosulfan sulfate was first detectable seven days after treatment and persisted until the end of the experiment, remaining confined in the upper 0–10 cm soil layer. The β-isomer also did not leach down beyond 10 cm depth. © 1997 SCI.     

Residues and fate of endosulfan on field-grown pepper and tomato

Endosulfan (Thiodan 3 EC), a mixture of α- and β-isomers, was sprayed on 92-day-old field-grown pepper and tomato at the recommended rate of 0·61 kg AI ha^-1. Plant tissue samples were collected at 1 h to 14 days after application and analysed to determine the content and dissipation rate of endosulfan isomers (α- and β-endosulfan) and the major metabolite, endosulfan sulfate. Analysis of samples was accomplished using gas chromatography-mass selective detection (GC-MSD). The results indicated the formation of endosulfan sulfate as a residue component on the plant tissues and also the relatively higher persistence of the β-isomer as compared to the α-isomer on pepper fruits. The initial total residues (α- and β-endosulfan isomers plus endosulfan sulfate) were higher on leaves than on fruits. On pepper fruits, the α-isomer, which is the more toxic to mammals, dissipated faster than the less toxic β-isomer. Total residues (α- and β-endosulfan isomers plus the sulfate metabolite) on tomato leaves revealed longer persistence (t_1/2 4·6 days) compared to the total residues detected on pepper leaves (t_1/2 2·0 days) 3–14 days following spraying. Persistence of the β-isomer on pepper fruits was high 3–14 days following spraying compared to on tomato fruits. This long persistence increases risk of exposure of the consumer. In addition, the longer persistence of the total residues on tomato foliage should be considered of importance for timing the safe entry of tomato harvesters due to the high mammalian toxicity of endosulfan. © 1998 Society of Chemical Industry     

Accumulation of endosulfan residues in fish and their predators after aerial spraying for the control of tsetse fly in Botswana

Residues of endosulfan insecticide (α- and β-isomers, and ‘endosulfan sulphate’) in fish and their predators were measured during and after operations to control tsetse fly in the Okavango Delta, Botswana. Six ultra-low-volume doses of endosulfan 35% e.c. (6–12 g a.i. ha^?1) were applied from the air in a period of 12 weeks over 2500 km². The concentration of residues found in living fish was up to 0.19 mg kg^?1 wet wt in caudal muscle, and usually < 0.8 mg kg^?1 wet wt in pooled viscera (maximum 2.8 mg kg^?1). These values returned to near-normal within 3 months after cessation of spraying, but residues were still detectable after 12 months. By comparison, fish killed by spraying contained a maximum residue level (whole-body) of 1.5 mg kg^?1 wet wt. The residue level in fish was approximately proportional to their fat content. Lean fish were more susceptible to poisoning than fat fish. The proportion of the ‘endosulfan sulphate’ metabolite in fish increased at least six times with respect to the parent isomers (α+β) during the period of spraying, but more advanced stages of metabolic breakdown were not monitored. Residue levels in fish predators (fish-eating birds and crocodiles) were similar to those in their prey, and the risk to them was consequently low.     

Acaricides and their residues in Spanish commercial beeswax

BACKGROUND: The purpose of this work was to determine residues of acaricides in recycled Spanish beeswax. RESULTS: Chlorfenvinphos, fluvalinate, amitraz, bromopropylate, acrinathrin, flumethrin, coumaphos, chlorpyrifos, chlordimeform, endosulfan and malathion residues were determined by GC‐µECD/NPD/MS detection. Owing to the extreme instability of amitraz, this analyte was transformed into the stable end‐metabolite 2,4‐dimethylaniline, later derivatised with heptafluorobutyric anhydride and determined by GC‐µECD/MS. Recoveries from spiked samples ranged from 86 to 108%, while quantification limits varied from 0.10 to 0.30 mg kg^?1 using GC‐µECD/NPD, and from 12 to 85 µg kg^?1 by GC‐MSD. Of a total of 197 samples analysed, only eight samples (4%) were free of residues of chlorfenvinphos (0.019–10.6 mg kg^?1), fluvalinate was present in 93.6% of samples analysed (0.027 –88.7 mg kg^?1), while coumaphos was confirmed in only five of the 134 samples analysed at concentrations of less than 195 µg kg^?1. The remaining acaricides were identified with different levels of incidence at concentrations from 12 to 231 µg kg^?1. CONCLUSIONS: Residues of acaricides were found in an extensive number of beeswax samples. The contamination with chlorfenvinphos and tau‐fluvalinate was very relevant, particularly as chlorfenvinphos is not legally authorised for use in beekeeping. The possible impacts of the main acaricides detected on larval and adult honey bees are discussed. Copyright © 2010 Society of Chemical Industry     

Fate of endosulfan in rats and toxicological considerations of apolar metabolites

[¹⁴C]Endosulfan, α or β isomers separately, was administered to rats as a single oral dose and as a dietary supplement for 14 days. No appreciable differences were observed in the fate of the two isomers. Five days after the single dose, 75% of the dose had been voided in the feces and 13% in the urine. Of the total radiocarbon consumed in the diet after 14 days, 56% had been eliminated in the feces and 8% in the urine. Bile collection studies showed that up to 47% of a single oral dose was eliminated from the liver via this route; enterohepatic circulation was not apparent. Maximum [¹⁴C]endosulfan equivalents in body tissue occurred in the kidney and liver, 3 and 1 ppm, respectively, after 14 days of feeding 5 ppm of endosulfan. Apolar metabolites in the excreta and/or tissues were a minor portion of the total residues and consisted of the sulfate, diol, α-hydroxy ether, lactone, and ether derivatives of endosulfan. The sulfate was slightly more toxic to mice than endosulfan, while the other products were less toxic. Neither endosulfan nor its metabolites were active in the Salmonella mutagenicity test. Endosulfan in the diet of rats for 28 days at 50 ppm did not induce liver oxidase enzymes, alter liver or kidney weights, or influence the rate of weight gain of the animals.     

Persistence and performance of esfenvalerate residues on broccoli

The efficacy of esfenvalerate (84 g litre-1 EC; Asana XL) at 7.0 g AI ha-1 on broccoli was tested against the flea beetle, Phyllotreta cruciferae Goeze (Chrysomelidae: Coleoptera) and the imported cabbage worm, Pieris rapae L (Pieridae: Lepidoptera) under field conditions. Insect populations were monitored before and after treatment. Periodic sweep-net collections and examination of the leaves in treated and untreated broccoli plots revealed mean reductions of P cruciferae levels of nearly 98% 1 week post-application compared with untreated plots. The residual toxicity of esfenvalerate was also effective for 2 weeks in reducing population density of P rapae by 69% on broccoli leaves. The impact of esfenvalerate on feeding damage to broccoli leaves was established by counting the number of feeding holes made by P cruciferae on spring broccoli and P rapae on fall broccoli. As the leaf area ingested increased, a linear relationship was seen between the number of holes and number of insects. Results indicated that forage destruction by the two pests was significantly reduced by esfenvalerate application. Esfenvalerate was extracted from broccoli at 1 h and 1, 3, 7, 10, and 14 days post-application for residue analysis. Residues on spring broccoli were 12.2, 5.2 and 2.9 micrograms cm-2 on the leaves and 0.13, 0.05 and 0.02 microgram g-1 on the heads at 1 h, 1 and 3 days, respectively. Only trace levels (0.001 microgram g-1) were detected in/on the heads 14 days after spraying. On the basis of half-life (T1/2) values, persistence of esfenvalerate on spring broccoli leaves (T1/2 = 1 day) was shorter than on fall broccoli (T1/2 = 1.6 days). T1/2 values were 2.1 and 3.6 days on spring and fall broccoli heads, respectively. The implications of these residue levels on re-entry times into treated fields are discussed.     

Fenvalerate residues in milk following topical treatments to dairy cows

Two mature Holstein cows were treated with 0.1g of fenvalerate each, in six consecutive topical treatments at intervals of 3 or 4 days. Neither of the diastereoisomers of fenvalerate was detected in the milk 6h after the application. After 3 days, the mean fenvalerate residue was 0.46μg litre⁻¹; by day 4, this residue had declined below the detection limit of 0.1μg litre⁻¹ for each of the diastereoisomers. Two Holstein cows were also treated with 0.5g of fenvalerate per cow in three consecutive topical treatments at intervals of 14 days. Residues in whole milk were at a maximum 6h after treatment and declined to less than 0.2μg litre⁻¹ over 21 days. Only 0.03 to 0.06% of the applied fenvalerate appeared in the milk as the intact insecticide.     

Organochlorine residues in fish, water, and sediment of American Falls Reservoir, Idaho, 1974.

Organochlorine residues of TDE, DDE, and PCBs as high as 1.96, 2.79, and 28.74 microgram/kg, respectively, have been found in sediments of American Falls Reservoir, Idaho. Residues of TDE, DDE, and dieldrin in the flesh of sport fish were as high as 52.3, 67.2, and 160.4 microgram/kg, respectively. Maximum organochlorine residue levels found in sucker taken in the commercial fishery were 1.1 mg PCBs/kg, 781.7 microgram TDE/kg, and 82.1 microgram DDE/kg.     

QuEChERS-气相色谱-串联质谱法同时测定饲草中10种农药残留

建立了同时测定饲草中敌敌畏、乙酰甲胺磷、乐果、莠去津、乙草胺、马拉硫磷、倍硫磷、毒死蜱、氯氰菊酯和溴氰菊酯10种农药残留的QuEChERS/气相色谱-串联质谱（GC-MS/MS）方法。样品经饱和氯化钠溶液浸泡10~15 min、乙腈匀浆提取1 min,上清液以无水MgSO₄、N-丙基乙二胺（PSA）、C₁₈和石墨化碳黑（GCB）（质量比30:10:10:1）为吸附剂进行基质分散萃取净化,浓缩后用乙酸乙酯定容,通过HB-5MS气相色谱柱（30 m×250 μm,0.25 μm）分离,采用串联质谱在多反应监测模式（MRM）下检测分析。结果表明:在1~200 μg/L范围内,10种农药的进样质量浓度与其对应的峰面积间呈良好的线性关系,相关系数均大于0.99,该方法检出限（LOD）为0.001 5~0.015,定量限（LOQ）为0.005~0.05 mg/kg。在0.05、0.2和1.0 mg/kg 3个添加水平下,10种农药在饲草中的平均回收率为75%~110%,相对标准偏差（RSD）为1.7%~11.6%。利用该方法对山东省100批次饲草产品中的农药残留进行检测,共检出8种农药,其中毒死蜱的检出率较高,其在青贮料和干草料中的残留量分别在0.002~0.447和0.002~3.502 mg/kg之间,其他农药的检出率则较低,在0.027~0.428 mg/kg之间。参照国内外最大允许残留限量（MRL）值,毒死蜱、乐果、乙草胺、马拉硫磷、氯氰菊酯和溴氰菊酯在饲草中的残留水平是安全的;而莠去津和倍硫磷尚未规定其在饲草中的MRL值。该方法简单、快速、灵敏、准确,能够满足大批量饲草中农药残留的检测需要。     

Excretion and residues of the herbicides benzoylprop-ethyl flamprop-isopropyl and flamprop-methyl in cows,pigs and hens

Two wild oat herbicides, benzoylprop-ethyl and flamprop-methyl were administered to lactating cows at low dose levels (0.3–3.0 mg/kg in total diet) and the excretion of total metabolites in milk, urine and faeces was measured. Total residues in tissues were also determined. Similarly a third and related herbicide flamprop-isopropyl was fed to cows, pigs and hens (at 0.5 mg/kg in total diet) and the residues were determined in excreta and tissues, including eggs. The amounts of the compounds fed were equivalent to approximately 10–300 times the total residue found in cereal treated in the field. Residues in milk in most cases were well below 0.001 mg/kg; in muscle samples <0.003 mg/kg; and in eggs, 0.0008 mg/kg, decreasing by 50% in approximately 3 days to 0.0001 mg/kg 4 days after the termination of treatment. Elimination of the herbicides from the animals was rapid in every case and this, together with the low residue levels, was attributed to very efficient metabolic de-esterification to the parent carboxylic acid metabolites (benzoylprop and flamprop). These metabolites possess physical properties ideally suited for excretion via the kidneys and bile into urine and faeces and, conversely, unsuited for transport into milk and eggs.     

Pesticide residues in beeswax samples collected from honey bee colonies (Apis mellifera L.) in France

In 2002 a field survey was initiated in French apiaries in order to monitor the health of honey bee colonies (Apis mellifera L.). Studied apiaries were evenly distributed across five sites located in continental France. Beeswax samples were collected once a year over 2 years from a total of 125 honey bee colonies. Multiresidue analyses were performed on these samples in order to identify residues of 16 insecticides and acaricides and two fungicides. Residues of 14 of the searched-for compounds were found in samples. Tau-fluvalinate, coumaphos and endosulfan residues were the most frequently occurring residues (61.9, 52.2 and 23.4% of samples respectively). Coumaphos was found in the highest average quantities (792.6 microg kg(-1)). Residues of cypermethrin, lindane and deltamethrin were found in 21.9, 4.3 and 2.4% of samples respectively. Statistical tests showed no difference between years of sampling, with the exception of the frequency of pyrethroid residues. Beeswax contamination was the result of both in-hive acaricide treatments and, to a much lesser extent, environmental pollution.     

Toxicity and metabolism of endosulfan and its effect on oxygen consumption and total nitrogen excretion of the fish Macrognathus aculeatum

Experiments were conducted with the freshwater fish Macrognathus aculeatum to study the toxicity and metabolism of endosulfan and the effect of the pesticide on the oxygen consumption and total nitrogen excretion. The 96-hr LC₅₀ value was 3.5 ± 0.2 ppb. In brain, gills, gut, liver, and kidney, endosulfan was metabolized to endosulfan sulfate, but this appears to be only an intermediary step as the nontoxic endosulfan ether was found only in the liver and kidney, the principal organs of elimination of toxicants in fish. The pesticide, both at sublethal and lethal concentrations, decreased oxygen consumption and total nitrogen excretion.     

Behaviour of endosulfan residues in peppers,cucumbers and cherry tomatoes grown in greenhouse: evaluation by decline curves

Decline of endosulfan residues in pepper, cucumber and cherry tomatoes grown in greenhouses, and the corresponding statistical parameters, were evaluated assessing the formal approaches proposed by Timme, Frehse and Laska to study the behaviour of pesticide residues in crops. In all cases, the first-order reaction function was confirmed to describe the behaviour of endosulfan residues, but functions that best fit the experimental data were first-order for cucumber, RF-first-order for pepper and RF-1·5th-order for tomato. Half-life periods of endosulfan residues determined from the first-order function were 11·1(±1·3) days (cucumber), 15·2(±3·3) days (pepper) and 20·1(±6·6) days (tomato), whereas the values obtained from the optimal functions were close to 10 days for the three plantations. © 1997 SCI     

Procedures for Analysis of Surface Spray Deposits of Captafol on Coffee Trees,Captan on Apple Trees and Endosulfan on Hops by Gas-Liquid Chromatography

The procedures involve the removal of captafol, captan or endosulfan spray deposits from the plant surfaces with solvent and their measurement by g.l.c. In contrast to residue analysis, clean-up procedures are avoided and the speed of the methods enable large numbers of samples to be processed in the monitoring of initial spray deposits and the subsequent redistribution or loss in relation to the efficiency of spray application techniques. Recoveries of captafol and captan suspension deposits from glass were greater than 96%: recoveries of emulsion deposits from plant surfaces were greater than 95% for captafol, 93% for captan and 96% for endosulfan.     

Pesticide and mercury residues in commercially grown catfish.

In 1970, 54 commercial catfish farms in Arkansas and Mississippi were sampled for pesticide and mercury residues. Pesticide residues above FDA action levels were detected in 15 percent of the fish samples. Data on residues in sediment, fish feed, and source water suggest that fish were not being contaminated from these sources. Average fish residue per county was, however, strongly correlated with the percent of total acres planted in cotton and soybeans. Results strongly suggest that cotton production was the primary source of contamination. Actual routes of movement have not been clearly defined but aerial transport seems most probable.