Application of an inclusion complex for determination of dithianon residues in water and fruits

A 3,3′-benzidine/β-cyclodextrin fluorescence derivative (BCDFD) was prepared and characterized by means of elemental analysis and ¹H NMR. An inclusion complex was formed between BCDFD and the pesticide dithianon based on the internal cavity of β-cyclodextrin (β-CD), and the binding constant (K_S ) of the inclusion complex was investigated. The inclusion complex could be applied for the determination of dithianon residues. Based on this, a sensitive method for the determination of dithianon was established. The linear dynamic range was from 0.63 to 12.5?mg?L^?1 with a correlation coefficient of 0.9927. The limit of detection for an aqueous solution of standard and the relative standard deviation (RSD) were 10.6?µg?L^?1 and 0.76%, respectively. The proposed method has been successfully applied for the determination of dithianon residues in water and fruit samples with satisfactory results, and recoveries in the range of 96.0–108% were obtained. The method is rapid, direct, economical, and sensitive for dithianon analysis.     

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.     

GC-MS-MS测定蔬菜中八种有机磷农药

用GC-MS-MS同时测定蔬菜中的甲拌磷、二嗪农、甲基对硫磷、毒死蜱、倍硫磷、喹硫磷、杀扑磷和亚胺硫磷.对各个化合物的特征离子对、碰撞电压进行了优化,并阐述了优化反应监测模式(MRM)条件的过程和方法,同时分析了各个化合物的线性范围和最低检出限.将该方法用于蔬菜样品的检测,测得加标回收率在90.4%-105.0%之间,RSD在3.2%-9.3%之间.     

Investigation of naphthalene contamination in olive oil from Greece

Abstract

Incidents of using naphthalene in olive orchards as a repellent of olive fly (Bactrocera oleae) have recently been recorded. Naphthalene, the primary ingredient of mothballs, is described to be diluted in plastic bottles and hanged on the trees releasing its characteristic odor which is supposed to repel olive fly. Since naphthalene has been characterized as possibly carcinogenic to humans and animals, it was considered essential to monitor olive oils regarding their potential contamination with this specific pollutant. To this goal, a simple, sensitive and reliable analytical method for the determination of naphthalene in olive oil has been developed. The method involves extraction with ethyl acetate: acetonitrile (1:1) and determination of naphthalene using gas chromatography triple quadrupole mass spectrometry. The method was validated in four fortification levels, 0.005, 0.01, 0.05, and 0.1?mg/kg in accordance with the EU requirements. The obtained results were acceptable as far as validation criteria are concerned, given recoveries between 71% and 87% and RSDs between 5% and 24%. The limit of determination for naphthalene was set at 0.005?mg/kg based on the lowest concentration level being validated with acceptable accuracy. The analytical technique was successfully applied to 75 olive oil samples collected from oil mills in Greece and no positive results of naphthalene were detected.     

南京市夏季青菜中有机磷农药残留量调查

１９９４年夏季调查和测定了南京市市售青菜中甲胺磷、乐果、甲基－１６０５等５种有机磷农药残留量。结果表明，夏季青菜（包括青菜秧）中有机磷农药残留量有超标现象，其中甲胺磷在青菜中的平均残留量为０．０６３ｍｇ／ｋｇ，超标率为１１．５％，其余４种有机磷农药在青菜中未检出。     

The effects of pesticides on greenhouse workers and their produced products

Pesticides are chemicals used in agriculture but are known to produce adverse effects on humans. In this study, blood activities of superoxide dismutase (SOD), catalase (CAT), aspartate transaminase (AST), alanine transaminase (ALT), gamma-glutamyl transaminase, lactate dehydrogenase (LDH), and levels of malondialdhyde (MDA) were determined in 44 greenhouse workers (24 tomato workers, 20 clove workers) and in tomato (24 samples) and clove (20 samples) products. At the end of this study, blood MDA levels and activities of ALT, AST, and LDH levels in greenhouse workers were significantly increased while SOD and CAT activity levels fell significantly. Pesticide residues were not found in agricultural worker blood. Malathion residues (average 0.8?ppm) were detected in tomatoes (8 samples) in these greenhouses. Data suggest that the health of the greenhouse workers may be adversely affected by pesticides.     

高铁酸钾对菠菜中3种有机磷农药残留降解的影响

菠菜(Spinaciao leracea L.)是我国出口的重要蔬菜品种之一,其农药残留是制约我国菠菜出口的重要"技术壁垒".在露地栽培条件下,研究了叶面喷施高铁酸钾水溶液对菠菜中有机磷农药的降解作用,并探讨了高铁酸钾对菠菜相关酶活、MDA含量及品质指标的影响.结果表明,叶面喷施不同浓度的高铁酸钾(200、400、600mg·L-1)可有效降低菠菜中敌敌畏、毒死蜱和乐果等有机磷农药的残留量.随着高铁酸钾喷施浓度的增大,菠菜中敌敌畏、毒死蜱和乐果残留量显著降低;试验浓度下以600mg·L-1高铁酸钾处理的降解效果最好,可使菠菜中敌敌畏、毒死蜱和乐果的降解率达到72.43%、87.15%和75.45%.叶面喷施高铁酸钾对菠菜过氧化物酶(POD)、过氧化氢酶(CAT)活性、MDA含量以及品质指标没有明显影响.试验表明高铁酸钾具有降解有机磷农药残留的作用,在菠菜生产中将高铁酸钾作为有机磷农药残留降解制剂是可行的.     

Imidacloprid residues in fruits,vegetables and water samples from Palestine

The aim of this work was to report on imidacloprid [IUPAC name 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] residues in some vegetables, fruits, and water samples collected from the West Bank, Palestine, in 1998 and 1999. Imidacloprid and its derivatives in the study samples were extracted by methanol/water and oxidized into 6-chloronicotinic acid and subsequently derivatized into 6-chloronicotinic acid trimethylsilyl ester before being determined by GC/MS. Imidacloprid residues were detected in more than half of the analyzed samples. The highest and lowest imidacloprid concentrations were found in eggplant (0.46 mg/kg) and green beans (0.08 mg/kg), respectively. An increase of 11–120% in imidacloprid concentration in the 1999 samples was observed when compared with those of 1998. This may suggest imidacloprid accumulation in the soil and/or increased use by local farmers. The imidacloprid residue concentrations in several crops were found to exceed the CODEX maximum residue limit.     

Residues and dissipation of the pesticide emamectin benzoate under Egyptian field condition: a case study

A simple, rapid analytical procedure for the quantification of emamectin benzoate in tomato was developed using high performance liquid chromatography with fluorescence detector (HPLC-FLD). Emamectin benzoate residues were extracted from tomato samples with n-hexane:ethyl acetate (1:1, v/v). The method involved derivatization using trifluoroacetic anhydride and 1-methylimidazole, prior to analysis by HPLC-FLD. Limit of quantification of this method was found to be 0.01 mg/kg, while limit of detection was 0.005 mg/kg. The dissipation of emamectin benzoate on tomato was studied, and half-life (t_1/2) was estimated in a field study carried out at three different locations. Emamectin benzoate was sprayed on tomato at recommended dosage. Samples of tomato were collected at 0, 1, 3, 7, 10, and 15 days after treatment. The t_1/2 of emamectin benzoate when applied at the recommended doses in tomato was approximately 2.5 days. The residue of emamectin benzoate reached below the maximal residue limit (MRL) 10 days after spraying at the tested dosage. Hence, a safe pre-harvest interval of 10 days is suggested before harvesting of tomato. This study would also be helpful for the Egypt government to establish the MRL of emamectin benzoate in tomatoes and provide guidance on the proper and safe use of this insecticide.     

Sediment quality assessment of Beasley Lake: bioaccumulation and effects of pesticides in Hyalella azteca

Beasley Lake is a Conservation Effects Assessment Program (CEAP) watershed in the intensively cultivated Mississippi Delta, USA. Lake sediment quality at three sites was evaluated in 2004 and 2008 for biological impairment and uptake (animal tissue pesticide residues) from 14 pesticides and three metabolites using Hyalella azteca (Saussure). Eleven pesticides and three metabolites were detected in sediment among the three sites in 2004 and all 17 compounds examined were detected among the three sites in 2008, with the herbicide atrazine having the greatest concentrations. Twenty-eight-day H. azteca survival and growth (mg w/w) indicated no survival effects at any site for either year, but growth impairment occurred in H. azteca exposed to sediments in 2004, whereas growth enhancement occurred in H. azteca exposed to sediments at one site in 2008. Pesticides observed in animal tissue pesticide residues occurred more frequently and in greater concentrations in 2004 compared with 2008. Thirteen pesticides were detected in animal tissue pesticide residues in 2004, with chlorpyrifos occurring in the greatest concentrations, and six pesticides were detected in 2008, with p,p′-DDT occurring in the greatest concentrations. H. azteca tissue pesticide residues of seven pesticides, two herbicides, three insecticides, one insecticide metabolite, and p,p′-DDT, were associated with growth.     

Phytotoxicity and uptake of chlorpyrifos in cabbage

Chinese cabbage, Brassica chinensis L., and cabbage, Brassica oleracea L. var. capitata, are the main daily foliar vegetables of the vast majority of the population of eastern and southern China. Cabbages are also planted and consumed widely in other countries. The insecticide and acaricide chlorpyrifos is registered in many countries. Chlorpyrifos controls a variety of insects in plants and soils, and chlorpyrifos is extensively used in the Chinese market. Food poisoning due to the presence of organophosphorus pesticide residues in vegetables has been reported in China provinces. Plant uptake of pesticide residues in air, water, and soil is a source of pesticide residues in vegetables. Here, phytotoxicity and uptake of chlorpyrifos by Chinese cabbage and cabbage were studied in the laboratory using the batch technique. From 0 to 16 days after chlorpyrifos treatment, vegetables roots, stems, leaves, and culture water samples were collected, and the residues of chlorpyrifos in culture water, plant tissues were analyzed using GC-FPD. The results demonstrate that culture solutions with chlorpyrifos had no significant inhibitory effects on vegetable plant height. However, at 1.0 mg/l, it had significant inhibitory effects on the root length and fresh weight of Chinese cabbage. Then, at 10.0 mg/l, it had only significant inhibitory effects on the root length and fresh weight of cabbage compared to the control treatment. The disappearance rates of chlorpyrifos in solutions were in sequence as: nutrition solution with Chinese cabbage, nutrition solution with cabbage, pond water, nutrition solution. The results showed also that chlorpyrifos can be taken up by roots of Chinese cabbage and cabbage from water and subsequently translocated as a function of time. Uptake dynamics of chlorpyrifos from culture solutions by the two cabbage plants were similar.     

Distribution of organo-chlorine pesticides (DDT and HCH) between plant and soil system

This paper reports a study of the distribution of organo-chlorine pesticides (DDT and HCH) between rice plants and the soil system by spraying before the heading stage at four different dosage levels--control, normal dosage (15 kg ha(-1) of 6% HCH and 7.5 kg ha(-1) of 25% DDT), double dosage and four times dosage. Soil and plant samples were taken respectively at the 1st h, 3rd, 10th, 20th, and 40th day after spraying and at the harvest time. The results indicate that less than 5% of HCH and 15% of DDT were absorbed by the surface of rice leaves for normal dosage. Most of both pesticides moved into the soil in solution after spraying. Compared with DDT, HCH was degraded and run off more easily. HCH residues in the surface soil layer (1-3 cm) were already below 6.4 microg kg(-1) at the mature stage, lower than Chinese Environmental Quality Standard for Agricultural Soils: HCH < 0.05 mg kg(-1). However DDT residues in the surface soil layer remained 172 microg kg(-1), higher than the national standard: DDT < 0.05 mg kg(-1). According to the test f OCP residues in rice seeds, it can be concluded that the OCP sprayed onto the surface of rice leaves can move into rice plants and accumulate in the seeds at the mature stage. HCH residues in rice seeds of the double and four times dosage treatments, and DDT residues in all treatments, exceeded the Chinese National Food Standard (HCH < 0.10 mg kg(-1), DDT < 0.20 mg kg(-1)).     

蜡状芽孢杆菌不同菌株降解有机磷农药的特性分析

筛选分离降解微生物解决有机磷农药残留给水体和土壤环境带来的污染问题是一项可行的生物修复技术。采用富集培养和定时取样分析有机磷农药残留的方法,分离驯化出三株能够降解有机磷农药的细菌,研究了其形态特征和生理生化特性并对其16SrDNA序列进行了分析,同时比较了三菌株对甲基对硫磷（Methyl－parathion）、毒死蜱（Chlorpyrifos）和_二唑磷（Triazophos）的降解特性。结果表明：通过富集培养得到10菌株具有降解甲基对硫磷和毒死蜱的能力,比较确定HY-1、HY-2和HY-4三菌株作为研究对象,经鉴定为蜡状芽孢杆菌（Bacilluscereus）的不同菌株,三菌株在Genbank上的登录号分别为：eu915687、eu915686和eu915688。在甲基对硫磷质量浓度为50mg·L-1时,三菌株72h的降解率分别为91．7％、87．7％与92．4％．降解率无显著性差异（P〉0．05）,当甲基对硫磷质量浓度增加到100mg·L-1时,三菌株对甲基对硫磷的降解率有所下降,其中HY-2对甲基对硫磷的降解率下降最大达23％,且和其他两菌株有显著性差异（P〈0．05o三菌株72h对100mg·L-1毒死蜱的降解率分别达到64．8％、53．7％和56．5％,在不同的毒死蜱初始质量浓度下,HY-1和HY-4两菌株对毒死蜱的降解率无显著性差异（P〉0．05）,HY-2与HY-1、HY-4两菌株有显著性差异（P〈0．05o三菌株对三唑磷的降解率均较低,其中HY-2对初始质量浓度为100mg·L-1三唑磷的降解率最高仅为20．7％,其余两菌株对三唑磷的降解率比HY-2低且无显著性差异（P〉0．05o可以得出本研究分离得到的蜡状芽孢杆菌不同菌株对有机磷农药的降解存在多态性。     

Dispersive solid phase extraction of chlorophenols using carbon-coated magnetic nanoparticles

Abstract

Carbon-coated magnetic nanoparticles were modified with cationic surfactant and used for the dispersive solid phase extraction of chlorophenols from aqueous samples. Surfactant adsorbed on the surface of the nanoparticles resulted in mixed hemimicelles for high extraction efficiency of chlorophenols. Under optimized conditions, calibration curves were linear from 0.5–20?mg L^?1 for analytes with limit of detection between 0.2 and 0.4?mg L^?1. The method was applied to extraction of chlorophenols from tap water, well water and industrial effluent. Recoveries were in the range of 94.0–99.4%, suggesting that sample matrix had little effect on the yields of extraction.     

围生期毒死蜱暴露致子代8周雄鼠睾丸组织的氧化损伤

毒死蜱是目前全世界使用和销售量最大的有机磷杀虫剂之一。为探讨围生期毒死蜱暴露致8周雄性子鼠睾丸组织的氧化损伤,选择健康Wistar妊娠母鼠于妊娠期(gestation days,GD)第6天至子鼠出生后(postnatal days,PND)21天通过灌胃染毒0、0.75、1.35和2.70 mg·kg~(-1)剂量的毒死蜱,待雄性子鼠8周龄取左侧睾丸实施组织病理学检查,右侧睾丸用以检测丙二醛(maleic dialdehyde,MDA)的含量和谷胱甘肽S转移酶(glutathione S transferases,GST)、谷胱甘肽过氧化物酶(glutathione peroxidase,GSH-Px)、总超氧化物歧化酶(total superoxide dismutase,T-SOD)的活力。结果表明,与对照组比较,随着染毒剂量的增加子鼠体重和睾丸、附睾脏器系数有下降的趋势(P0.05);而MDA呈升高趋势(P0.05)。各组T-SOD和1.35、2.70 mg·kg~(-1)剂量组GSH-Px活力的下降及2.70 mg·kg~(-1)剂量组GST活力的升高均有统计学意义(P0.05)。睾丸组织病理学检查结果可见2.70mg·kg~(-1)剂量组睾丸组织有明显的损伤,管腔中精液量减少,生精细胞脱落增多。上述研究结果提示母鼠于围生期暴露于毒死蜱,可通过氧化损伤诱导子代雄性大鼠睾丸的毒性作用。     

Microwave-assisted synthesized zinc nanoparticles attenuate cisplatin-induced testicular toxicity in mice

Abstract

The purpose of this study was to investigate the protective effects of zinc nanoparticles against cisplatin-induced testicular toxicity in mice. Zinc nanoparticles were produced by microwave-assisted synthesis using Lavandula vera extract as reducing agent. Single doses of cisplatin (7?mg/kg, intraperitoneally) and ZnSO₄ (10?mg/kg, orally), and various doses of zinc nanoparticles (10???50?mg/kg, orally) and vitamin E (100?mg/kg, interaperitoneally) were administered. The protective role of zinc nanoparticles was determined biochemically and histologically. Gradual reduction in malondialdehyde levels and elevation in glutathione levels and in the activities of superoxide dismutase and catalase upon administration of zinc nanoparticles were observed. The pathology of mice treated with cisplatin/vitamin E and cisplatin/zinc nanoparticles were apparently equal, but vitamin E treatment was more effective in lowering oxidative stress markers than zinc nanoparticles. These findings suggest that co-administration of zinc nanoparticles with cisplatin could prevent adverse effects on the male reproductive system via their potential antioxidant properties.     

Feasibility of using salivary biomarkers to assess human exposure to chlorpyrifos

The objective of this study was to determine the feasibility of using salivary biomarkers to assess chlorpyrifos exposure using data collected from laboratory controlled animal study, as well as from farmers in Thailand and Nicaragua who applied chlorpyrifos in the field. Time-matched saliva and arterial blood samples were collected from rats and adult agricultural workers, while spot saliva samples were collected from children. Specimen samples were analyzed for chlorpyrifos using a commercially available enzyme-linked immunosorbent assay. The results from both animal and farmer studies show that chlorpyrifos is excreted into saliva. Nevertheless, salivary excretion of chlorpyrifos seems to differ from other pesticides, as evidenced by the lack of correspondence of chlorpyrifos levels between saliva and plasma samples. The lower chlorpyrifos concentrations in saliva collected from rats, and from farmers and their children, may have resulted from the rapid hydrolysis of chlorpyrifos during the intracellular passive diffusion in the salivary gland. In conclusion, chlorpyrifos is excreted into saliva; however, the majority of chlorpyrifos that is excreted in saliva may have been metabolized due to base-dependent hydrolysis. Because of this finding, it was hypothesized that it would be ideal to measure its metabolite, 3,5,6-trichloropyridinol, in saliva as the biomarker for chlorpyrifos exposure.     

Determination of pesticide residues in fruits and vegetables in Islamabad market

Pesticide residues in fruits and vegetable from Islamabad market, Pakistan were determined by GLC using Perkin Elmer Autosystem equipped with 63NECD and capillary column. Dimethoate was determined in the quantity of 0.032 mg kg-1 in apple, 0.110 mg kg-1 in banana, 0.004 mg kg-1 in brinjal, 1.80 mg kg-1 in cauliflower and 0.13 mg kg-1 in arvi, fenvalerate 0.010 mg kg-1 in apple and chlorpyrifos 0.004 mg kg-1 in brinjal. The importance of these pesticide residues with reference to human health is also briefly discussed.     

Temporal dynamics of arsenic uptake and distribution: food and water risks in the Bengal basin

Abstract

Contaminated food chain is a serious contender for arsenic (As) uptake around the globe. In Nadia, West Bengal, we trace possible means of transfer of As from multiple sources reaching different trophic levels, and associated seasonal variability leading to chronic As uptake. This work considers possible sources-pathways of As transfer through food chain in rural community. Arsenic concentration in groundwater, soil, rice, and vegetable-samples collected detected in different harvest seasons of 2014 and 2016. Arsenic level in shallow groundwater samples ranged from 0.1 to 354?µg/L, with 75% of the sites above the prescribed limit by WHO (10?µg/L) during the boro harvest season. High soil As content (～20.6?mg/kg), resulted in accumulation of As in food crops. A positive correlation in As conc. with increase over period in all sites indicating gradual As accumulation in topsoil. Unpolished rice samples showed high As content (～1.75?mg/kg), polishing reduced 80% of As. Among vegetables, the plant family Poaceae with high irrigation requirements and Solanaceae retaining high moisture, have the highest levels of As. Contaminated animal fodder (Poaceae) and turf water for cattle are shown to contaminate milk (0.06 to 0.24?µg/L) and behoves strategies, practices to minimize As exposure.