江苏省茶园和农田土壤中拟除虫菊酯类农药残留与污染特征分析

于2018年4—6月采集了江苏省10个市的茶园和农田表层土壤样品,采用气相色谱-三重四级杆质谱仪分析样品中12种拟除虫菊酯类农药的质量比和组成。结果表明,江苏省茶园和农田土壤中广泛检出拟除虫菊酯类农药,总量分别为27.1~50.7,56.9~97.0 ng/g。研究区域的拟除虫菊酯类农药含量存在差异,但组成相近,均是高效氯氟氰菊酯和联苯菊酯的比例较高。与国内其他地区土壤相比,江苏省茶园和农田土壤中拟除虫菊酯含量处于中等水平。     

气相色谱法测定土壤中37种有机磷农药残留

采用气相色谱法测定土壤中37种有机磷农药,当取样量为10 g时,37种有机磷农药方法检出限为0. 002～0. 015 mg/kg,测定下限为0. 008～0. 060 mg/kg。低含量加标样品中有机磷农药的加标回收率为72. 8%～104%,相对标准偏差为4. 2%～13. 8%;中含量加标样品中有机磷农药的加标回收率为71. 5%～101%,相对标准偏差为4. 3%～13. 5%;高含量加标样品中有机磷农药的加标回收率为74. 6%～109%,相对标准偏差为6. 8%～14. 6%。该方法灵敏度高、分离效果好、重现性好,能够满足土壤中37种有机磷农药残留检测的要求。     

Impacts of pesticides in a Central California estuary

Recent and past studies have documented the prevalence of pyrethroid and organophosphate pesticides in urban and agricultural watersheds in California. While toxic concentrations of these pesticides have been found in freshwater systems, there has been little research into their impacts in marine receiving waters. Our study investigated pesticide impacts in the Santa Maria River estuary, which provides critical habitat to numerous aquatic, terrestrial, and avian species on the central California coast. Runoff from irrigated agriculture constitutes a significant portion of Santa Maria River flow during most of the year, and a number of studies have documented pesticide occurrence and biological impacts in this watershed. Our study extended into the Santa Maria watershed coastal zone and measured pesticide concentrations throughout the estuary, including the water column and sediments. Biological effects were measured at the organism and community levels. Results of this study suggest the Santa Maria River estuary is impacted by current-use pesticides. The majority of water samples were highly toxic to invertebrates (Ceriodaphnia dubia and Hyalella azteca), and chemistry evidence suggests toxicity was associated with the organophosphate pesticide chlorpyrifos, pyrethroid pesticides, or mixtures of both classes of pesticides. A high percentage of sediment samples were also toxic in this estuary, and sediment toxicity occurred when mixtures of chlorpyrifos and pyrethroid pesticides exceeded established toxicity thresholds. Based on a Relative Benthic Index, Santa Maria estuary stations where benthic macroinvertebrate communities were assessed were degraded. Impacts in the Santa Maria River estuary were likely due to the proximity of this system to Orcutt Creek, the tributary which accounts for most of the flow to the lower Santa Maria River. Water and sediment samples from Orcutt Creek were highly toxic to invertebrates due to mixtures of the same pesticides measured in the estuary. This study suggests that the same pyrethroid and organophosphate pesticides that have been shown to cause water and sediment toxicity in urban and agriculture water bodies throughout California, have the potential to affect estuarine habitats. The results establish baseline data in the Santa Maria River estuary to allow evaluation of ecosystem improvement as management initiatives to reduce pesticide runoff are implemented in this watershed.     

Pesticide residues in vegetable samples from the Andaman Islands, India

Vegetable samples of brinjal, okra, green chilli, crucifers, and cucurbits collected from farmers' field were tested for the presence of organochlorine (OC), organophosphorus (OP), and synthetic pyrethroid (SP) compounds using a gas chromatograph equipped with electron capture and flame thermionic detectors. Of the samples tested, 34.0 % were found to have pesticide residues. Among the OC compounds, α-endosulfan, β-endosulfan, and endosulfan sulfate were detected in 14.5 % of the samples with residues. These were taken from crucifer, okra, green chilli, and cucurbit samples. SP compound residues, such as α-cypermethrin, fenvalerate I, fluvalinate I, deltamethrin, and λ-cyhalothrin were detected in 32 % of the samples with residues. OP compound residues such as chlorpyrifos, profenofos, monocrotophos, triazophos, ethion, dimethoate, and acephate were found in 54 % of the samples with residues, which were taken from all vegetable samples. Of the positive samples, 15.3 % were found to contain residues exceeding the prescribed maximum residue limit. The average pesticide residue content across all the vegetable samples was 0.108 ppm, with values ranging from 0.008 to 2.099 ppm. Multiple residues of more than one compound were detected in 34.1 % of samples containing residues.     

Pesticide residues in dried table grapes from the Aegean region of Turkey

Dried grapes make the ideal low-calorie snack. The formation of gray mold during the drying of the grapes can severely decrease production. Pesticides and fungicides are applied to prevent losses due to pests and mold. Dried grapes from 99 farms in the Aegean region were sampled for pesticide residues. Of the 26 pesticides analyzed for, chlorpyrifos methyl, chlorpyrifos ethyl, deltamethrin, lambda-cyolathrin, dichlofluanid, iprodione, and procymidone were detected in the dried grapes. Only seven samples contained residues above the maximum residue limit. It is important to note that pesticide residues were only present in samples originating from vineyards using conventional farming practices.     

Assessment of Pesticide Residues in Two Arable Soils from the Semi-Arid and Subtropical Regions of China

The residues of 31 chlorinated hydrocarbons (CHCs), 25 chlorophenols (CPs), 30 organophosphorus (OP) and pyrethroid (PRT) in two arable soils from the semi-arid and subtropical regions of China were assessed. Data obtained indicate that the main compounds of CHC pesticide residues in the semi-arid soil were 4,4′-DDE (25.3 ng/g) and β-HCH (14.1 ng/g), which totally accounted to about 90% of total CHC residues detected. The total content of CHC residues detected in the subtropical soil was only 3.1 ng/g, of which approximately 50% was β-HCH. However, the total content of CP residues in both of the soils was about 11 ng/g. In the semi-arid soil, only parathion-methyl amongst the 30 compounds of OP and PRT residues was detected (32.5 ng/g), whilst malathion and parathion-methyl (8.7 and 17.7 ng/g, respectively) detected in the subtropical soil. Based on these results, it was suggested the environmental risk of pesticide residues ranked in an order as CHCs (mainly as 4,4′-DDE, β-HCH) > OP (parathion-methyl) > CPs for the semi-arid soil, and as OPs (parathion-methyl and malathion) > CPs > CHCs (β-HCH) for the subtropical soil.     

农药厂周边有机磷农药在生物体中残留的检测方法研究

测定南京某农药厂附近大米、蔬菜及肉类中11种有机磷农药含量，通过使用气相色谱/质谱联用的方法，建立GC／MS定性定量分析方法，检出限达到0．05μg／kg（肉类）和0．1μg／kg（大米和蔬菜），回收率均符合测定要求。环境样品监测结果显示，大米和蔬菜中有机磷农药的含量高于肉类中的含量，说明在大米和蔬菜表面残留的农药量要高于进入生物体体内的含量。南京蔬菜样品中有机磷农药高于常州蔬菜样品，说明农药厂对蔬菜表面残留农药量有影响。不同的有机磷农药在不同的介质中，检出情况不一样，说明不同的环境介质对有机磷农药的保留水平不一样。     

Monitoring of pesticide residues levels in fresh vegetable form Heibei Province,North China

In this study, 226 samples of seven types of domestic vegetables collected from several vegetable-growing regions in Hebei Province of China were tested for the presence of 38 different agricultural pesticides using a gas chromatograph equipped with electron capture and nitrogen phosphorus detectors. The aim of this study was to investigate the distribution of pesticides in main vegetables from Hebei Province. Results showed that, in 65.93 % of the samples, no residues were found, 31.42 % of the samples contained pesticide residues at or below the maximum residue levels (MRLs), and 2.65 % of the samples contained pesticide residues above MRL. The most frequently detected pesticides were acephate (31), followed by cyhalothrin (15), bifenthrin (8), omethoate (6), isazophos (6), dimethoate (5), chlorpyrifos (2), and malathion (1). Some (1.33 %) of the samples contained multiple residues. The results provide useful information on the current contamination status of a key agricultural area in North China, and points to the continuous monitoring and strict regulation of pesticide use on vegetables are necessary.     

深圳主要河流中农药类环境激素污染调查

调查了深圳市10条主要河流农药类环境激素的污染现状。结果表明，深圳市各河流均受到农药类环境激素的污染，共有15种农药类环境激素被检出，质量浓度为未检出-4.8μg／L。并推荐深圳市河流中优先控制的农药类环境激素为：六六六、α-氯丹、硫丹I、环氧七氯、六氯苯、氟乐灵、联苯菊酯、二硫代农药。     

Organochlorine Pesticide Residues in Wheat and Drinking Water Samples from Jaipur, Rajasthan, India

The organochlorine pesticide contamination in dietary sources has caused serious threat to the human progeny. The present study was therefore conducted to evaluate the pesticide contamination in wheat flour and drinking water from Jaipur City, Rajasthan, India using Gas Chromatograph. All the wheat and water samples were found to be contaminated with various organochlorine pesticide residues of DDT and its metabolites, HCH and its isomers, heptachlor and its expoxide and aldrin. The amount of pesticide detected in wheat flour was higher than the permissible limits prescribed by WHO/FAO. In drinking water only a few pesticides exceeded the permissible limits. Seasonal variations of pesticides residues were also observed during the study period.     

Pesticides residues in okra (non-target crop) grown close to a watermelon farm in Ghana

The study looked at the levels of pesticides in okra grown close to a watermelon farm herein referred to as a non-target crop. The watermelon received some pesticide application in the course of its cultivation, and the okra which was not meant to be sprayed was also affected by the pesticide. About 500 okra samples were collected for a period of 6 weeks and pesticides extracted with 1:1 n-hexane and dichloromethane which was analysed with Agilent 2222 GC/MS coupled with 389 auto-sampler. The results confirmed accumulation of significant levels of pesticides in the non-target crop (okra grown close to watermelon farm). Levels of organochlorine pesticides ranged from 3.10 to 7.60 μg/kg whilst the organophosphorus pesticides had levels ranging from 2.80 to 2016.80 μg/kg. The synthetic pyrethroid pesticide mean levels also ranged from 0.10 to 4.10 μg/kg and were below World Health Organization/Food and Agriculture Organization-recommended residue levels, and though not appearing to constitute a grave threat to life, their occurrence is a concern, and pre-emptive techniques must be developed to thwart the contaminations. Though the non- target crop was not treated directly with the pesticides, some level of contamination with organochlorine and organophosphorus pesticides persisted in the crops. It can be inferred that application of pesticides affected the adjoining crops, meaning that inter-cropping and mix-cropping might not be acceptable when one of the crops requires pesticide application. It is important for the farmers to be trained to ensure proper application of pesticide to minimise its impact on the health of consumers.     

Analysis of insecticides in okra and brinjal from IPM and non-IPM fields

Samples of okra and brinjal fruits, collected from non-integrated pest management (Non-IPM) and IPM fields in village Raispur, Ghaziabad District (U.P.), were analyzed for pesticide residues. The residues of chlorpyrifos in soil were 4.219 and 1.135 microg/g at harvest time in non-IPM and IPM fields of summer okra crop from initial value of 0.407 microg/g before sowing, while in brinjal crop, it was not detected in soils of any trials. During first year of study, the residues of chlorpyrifos and cypermethrin in okra fruit were observed to be 5.75 and 0.625 microg/g, respectively, for non-IPM fields; and 0.104 microg/g of chlorpyrifos for IPM trials. The pesticide residues were found to be 0.77, 1.39, 0.4 and 0.32 microg/g for cypermethrin, chlorpyrifos, monocrotophos and dimethoate, respectively, for non-IPM okra fruits in second year. For brinjal fruit, residues of cypermethrin and imidacloprid were not detected in IPM trials while it was found to be 0.28 and 0.78 microg/g for cypermethrin and chlorpyrifos respectively, for non-IPM trials.     

An analytical model for the assessment of pesticide exposure levels in soils and groundwater

The movement and degradation of pesticide residues in soils and groundwater are complex processes affected by soil physical, (bio)chemical, and hydrogeological properties, climatic conditions, and agricultural practices. This work presents a physically-based analytical model suitable for long-term predictions of pesticide concentrations in groundwater. The primary interest is to investigate the impact of soil environment, related physical and (bio)chemical processes, especially, volatilization, crop uptake, and agricultural practices on long-term vulnerability of groundwater to contamination by pesticides. The soil is separated into root and intermediate vadose zones, each with uniform properties. Transport in each soil zone is modeled on the basis of complete mixing, by spatial averaging the related point multiphase-transport partial differential equation (i.e., linear-reservoir models). Transport in the aquifer, however, is modeled by a two-dimensional advection-dispersion transport equation, considering adsorption and first-order decay rate. Vaporization in the soil is accounted for by assuming liquid-vapor phase partitioning using Henry's law, and vapor flux (volatilization) from the soil surface is modeled by diffusion through an air boundary layer. Sorption of liquid-phase solutes by crops is described by a linear relationship which is valid for first-order (passive) crop uptake. The model is applied to five pesticides (atrazine, bromacil, chlordane, heptachlor, and lindane), and the potential for pesticide contamination of groundwater is investigated for sandy and clayey soils. Simulation results show that groundwater contamination can be substantially reduced for clayey soil environments, where bio(chemical) degradation and volatilization are most efficient as natural loss pathways for the pesticides. Also, uptake by cross can be a significant mechanism for attenuating exposure levels in ground-water especially in a sandy soil environment, and for relatively persisting pesticides. Further, simulations indicate that changing agricultural practices can have a profound effect on vulnerability of groundwater to mobile and relatively persisting pesticides.     

Evaluation of ozonation technique for pesticide residue removal and its effect on ascorbic acid,cyanidin-3-glucoside,and polyphenols in apple (<Emphasis Type="Italic">Malus domesticus</Emphasis>) fruits

Ozonated water dip technique was evaluated for the detoxification of six pesticides, i.e., chlorpyrifos, cypermethrin, azoxystrobin, hexaconazole, methyl parathion, and chlorothalonil from apple fruits. Results revealed that ozonation was better than washing alone. Ozonation for 15 min decreased residues of the test pesticides in the range of from 26.91 to 73.58%, while ozonation for 30 min could remove the pesticide residues by 39.39–95.14 % compared to 19.05–72.80 % by washing. Cypermethrin was the least removed pesticide by washing as well as by ozonation. Chlorothalonil, chlorpyrifos, and azoxystrobin were removed up to 71.45–95.14 % in a 30-min ozonation period. In case of methyl parathion removal, no extra advantage could be obtained by ozonation. The HPLC analysis indicated that ozonation also affected adversely the ascorbic acid and cyanidin-3-glucoside content of apples. However, 11 polyphenols studied showed a mixed trend. Gallic acid, 3,4-dihydroxybenzoic acid, catechin, epicatechin, p-coumaric acid, quercetin-3-O-glucoside, quercetin, and kaempferol were found to decrease while syringic acid, rutin, and resveratrol were found to increase in 30-min ozonation.     

气相色谱法测定赤水河中段水体中14种有机氯农药的残留

建立了用正己烷萃取,气相色谱—电子捕获（GC—ECD）测定水体中有机氯农药痕量残留的方法。结果表明：六氯苯、α-HCH、β-HCH、γ-HCH、δ-HCH、p,p′-DDD、p,p′-DDE、p,p′-DDT、艾氏剂、狄氏剂、异狄氏剂、七氯、环氧七氯、o,p′-DDT 14种农药在14 min内有较好的分离;2个不同浓...     

The Status of Pesticide Residues in the Drinking Water Sources in Meiliangwan Bay, Taihu Lake of China

The study was carried out to assess the levels of pesticide residues in the water of Meiliangwan Bay, Taihu Lake of China. The most commonly employed organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs) and herbicide atrazine were analyzed. The water samples were collected seasonally from Meiliangwan Bay within a period of one year. The pesticides were analyzed by gas chromatography (GC) with μECD or NPD after solid-phase extraction (SPE), which was confirmed by GC with an ion trap mass spectrometry (MS). The mean concentrations were 1.98 ng/l for lindane, 0.378 ng/l for heptachlor epoxide, 0.367 ng/l for p,p′-DDE, 0.496 ng/l for p,p′-DDD, 1.06 ng/l for p,p′-DDT and 51.6 ng/l for dichlorvos, 39.0 ng/l for demeton, 346 ng/l for dimethoate, 4.12 ng/l for methyl parathion, 11.6 ng/l for malathion, 2.17 ng/l for parathion and 217 ng/l for atrazine. Generally, low concentrations of OCP were found, whereas the concentrations of the OPPs and atrazine in the water of Taihu Lake were relatively high. Heptachlor epoxide and lindane were the two most commonly encountered OCPs while dichlorvos, demeton and dimethoate were found to have much higher concentrations and occurrences than other OPPs.     

Impact assessment of pesticide residues in fish of Ganga river around Kolkata in West Bengal

An investigation was conducted from 2001 to 2005 for determining the residual concentration of five pesticides, viz., total-HCH, total-DDT, total-Endosulfan, Dimethoate and Malathion in fish samples collected from various points of the river Ganga. Fish samples were analyzed for pesticide residues using standard laboratory procedures by GC method. It was found that total-HCH concentration remains above the MRL values for maximum number of times in comparison to four other pesticides. The pesticide contamination to fish may be due to indiscriminate discharge of polluted and untreated sewage-sludge to the river. The pesticide contents in some places are alarming. Thus proper care, maintenance, treatment and disposal of sewage water and sludge are most vital and should be the prime thrust for the nation.     

31P-NMR evaluation of organophosphorus pesticides degradation through metal ion promoted hydrolysis

The degradation of some organophosphorus pesticides (OPPs) in the presence of metal ions was studied by ³¹P-NMR spectroscopy. Both ³¹P-NMR and gas chromatography/mass spectroscopy results were used in order to determine the nature of metabolites formed after degradation. The degraded organophosphorus pesticide were investigated for chlorpyrifos and phoxim in the presence of several metal ions including Hg²⁺, Cu²⁺, Cd²⁺, Ni²⁺, Pb²⁺, and Ag⁺. ³¹P-NMR results indicated Ag⁺ and Hg²⁺ ion promoted degradation of OPPs and other metal ions formed complex with OPPs and cannot degrade OPPs. We found that the degradation of chlorpyrifos and phoxim with Ag⁺ or Hg²⁺ led to the formation of O,O-diethyl-O-methyl phosphorothionate, (C₂H₅O)₂(CH₃O)PS, at metal ion/pesticide mole ratios ≤1.0 and completely decomposed at a higher mole ratio of 10. Finally, the method was successfully applied to the degradation study of a number of technical and formulated pesticides in the presence of Ag⁺ ion at a metal ion/pesticide mole ratio of 10.     

Survey on the pesticide residues in tea in south India

Tea is considered as a ‘health beverage’ due its antioxidant properties and resultant beneficial effects on human health. Such a beverage should be free from toxic elements such as pesticide residues and heavy metals. A large scale survey of teas produced in the tea factories of south India had been carried out for a period of three years from 2006 to 2008 and 912 tea samples were analysed for the residues of certain pesticides such as dicofol, ethion, quinalphos, hexaconazole, fenpropathrin, fenvalerate and propargite which are used for pest and disease control in tea in this part of the country. The analytical data proved that only less than 0.5 percentage of tea samples had residues of these pesticides. However, residues of pesticides were below their maximum limits in tea, stipulated by the European Union, Codex Alimentarius Commission of FAO/WHO and Prevention of Food Adulteration Act of Govt. of India.