Monitoring of Seasonal Vegetables for Pesticide Residues

Market samples (60) of six seasonal vegetables were monitoredduring 1996–1997 to determine the magnitude of pesticidalcontamination. The estimation of insecticide residuesrepresenting four major chemical groups i.e. organochlorine,organophosphorous, synthetic pyrethroid and carbamate, was doneby adopting a multiresidue analytical technique employingGC-ECD and GC-NPD systems with capillary columns. The testedsamples showed 100% contamination with low but measurableamounts of residues. Among the four chemical groups, theorganophosphates were dominant followed by organochlorines,synthetic pyrethroids and carbamates. About 23% of the samplesshowed contamination with organophosphorous compounds abovetheir respective MRL values. More extensive studies coveringdifferent regions of Haryana state are suggested to get a clearidea of the magnitude of vegetable contamination with pesticideresidues.     

Pesticide residues in rain water from Hisar, India

Presence of pesticide residues was studied in rain water during 2002 employing multi residue analysis method by gas liquid chromatography equipped with ECD and NPD detectors and capillary columns. The presence of pesticide residues in surface aquatic system triggered the investigation of the presence of pesticides in rain water. A total of 13 pesticides were detected in rain water samples. Among the different groups of pesticides, organochlorines were present in the range of 0.041–7.060 ppb with maximum concentration of p,p’-DDT up to 7.060 μg l⁻¹. Synthetic pyrethroids were present ranging from 0.100 to 1.000 μg l⁻¹ and organophosphates in the range of 0.050–4.000 μg l⁻¹ showing maximum contamination with cypermethrin (1.000 μg l⁻¹) and monocrotophos (4.000 μg l⁻¹) of the respective groups. Almost 80% samples showed the residues above MRL of 0.5 ppb fixed for multi residues and on the basis of single pesticide, 16–50% samples contained residues above the MRL value of 0.1 ppb.     

Dissipation of Endosulfan and Dichlorvos Residues In/On Cauliflower Curds

Dissipation behaviour of endosulfan and dichlorvos in/on cauliflower, variety Snowball-16, was studied during rabi season (Sep.–March) 2003–2004. Endosulfan and dichlorvos were sprayed @ 350 and 110g a.i. with 115 g a.i., respectively, 80 days after transplanting. Samples were taken at the interval of 0 (1h after spray), 3, 5, 7, and 10 days after spray (DAS) in triplicate and residues were estimated on GC-ECD system equipped with capillary column. The initial deposits of 3.452 and 0.295μgg⁻¹ of endosulfan and dichlorvos dissipated to 0.084 (97.56%) and 0.009 (96.95%), respectively after 10 DAS. Residues of endosulfan reached below maximum residue limit of 2μgg⁻¹ one day after spray and of dichlorvos were below MRL value of 0.5μgg⁻¹ even on 0 day. Dissipation pattern followed first order kinetics for both the insecticides with half life periods of 1.81 and 2.08 days for endosulfan and dichlorvos, respectively.     

Monitoring of Butter and Ghee (Clarified Butter Fat) for Pesticidal Contamination from Cotton Belt of Haryana, India

Butter (45) and ghee (55) samples were collected from rural and urban areas of cotton growing belt of Haryana and analysed for detecting the residues of organochlorine, synthetic pyrethroid and organophosphate insecticides. The estimation was carried out by using multi residue analytical technique employing GC-ECD and GC-NPD systems equipped with capillary columns. Butter samples were comparatively more contaminated (97%) than ghee (94%), showing more contamination with organochlorine insecticides from urban samples. About 11% samples of butter showed endosulfan residues above MRL value and 2% samples had residues of synthetic pyrethroids and organophosphates each above their respective MRL values. In ghee, residues of HCH & DDT both and of endosulfan exceeded the MRL values in 5 and 20% samples, respectively. Among organophosphates, only chlorpyriphos was detected with 9% samples showing its residue above MRL value. Irrespective of contamination levels, residues above the MRL values were more in ghee. More extensive study covering other agricultural regions/zones of Haryana has been suggested to know the overall scenario of contamination of milk products.     

Magnitude of pesticidal contamination in winter vegetables from Hisar,Haryana

Monitoring of 80 winter vegetable samples during 1997–1998 for pesticidal contamination was carried out on GC-ECD and GC-NPD systems with capillary columns following multiresidueanalytical technique. The tested samples were found 100%contaminated with low but measurable amounts of pesticideresidues. Among the four major chemical groups, residue levels oforganophosphorous insecticides were highest followed bycarbamates, synthetic pyrethroids and organochlorines. About 32%of the samples showed contamination with organophosphorous andcarbamate insecticides above their respective MRL values. On thebasis of observations made in these studies, it is suggested thatmore extensive monitoring studies covering all vegetable cropsfrom different agro-climatic regions of the state be carried outto know exact level of pesticidal contamination, which may serveas basis for future policy on chemical use.     

Monitoring of Organochlorine Pesticide Residues in Summer and Winter Vegetables from Agra, India – A case study

Analysis of summer and winter vegetable samples during 2002–2003 for pesticidal contamination was carried out on Gas Chromatograph-Electron Capture Detector with capillary columns. The contamination levels of winter vegetables (average concentration of 4.57, 6.80 and 5.47 ppb respectively for Lindane, Endosulphan and DDT) were found to be slightly higher than the summer vegetables (average concentration of 4.47, 3.14 and 2.82 ppb respectively for Lindane, Endosulphan and DDT). The concentration of these organochlorine pesticides in summer and winter vegetables were well below the established tolerances but continuous consumption of such vegetables even with moderate contamination level can accumulate in the receptor's body and may lead to chronic effects that could be fatal.     

Status of insecticide contamination of soil and water in Haryana, India

Twelve samples each of soil and ground water were collected from paddy-wheat, paddy-cotton, sugarcane fields and tube wells from same or near by fields around Hisar, Haryana, India during 2002–2003 to monitor pesticide residues. Residues were estimated by GC-ECD and GC-NPD systems equipped with capillary columns for organochlorine, synthetic pyrethroid and organophosphate insecticides. In soil, HCH (0.002–0.051 μg g⁻¹), DDT (0.001–0.066 μg g⁻¹), endosulfan (0.002–0.039 μg g⁻¹) and chlordane (0.0002–0.019 μg g⁻¹) among organochlorines, cypermethrin (0.001–0.035 μg g⁻¹) and fenvalerate (0.001–0.022 μg g⁻¹) among synthetic pyrethroids and chlorpyriphos (0.002–0.172 μg g⁻¹), malathion (0.002–0.008 μg g⁻¹), quinalphos (0.001–0.010 μg g⁻¹) among organophosphates were detected. Dominant contaminants were DDT, cypermethrin and chlorpyriphos from the respective groups. In water samples, HCH, DDT, endosulfan and cypermethrin residues were observed frequently. Only chlorpyriphos among organophosphates was detected in 10 samples. On consideration of tube well water for drinking purpose, about 80% samples were found to contain residues above the regulatory limits.     

Pesticide Residues in Bovine Milk from a Predominantly Agricultural State of Haryana, India

One hundred forty seven samples of bovine milk were collected from 14 districts of Haryana, India during December 1998–February 1999 and analysed for the presence of organochlorine pesticide (OCPs) residues. ∑HCH, ∑DDT, ∑endosulfan and aldrin were detected in 100%, 97%, 43% and 12% samples and with mean values of 0.0292, 0.0367, 0.0022 and 0.0036 μg/ml, respectively. Eight percent samples exceeded the maximum residue limit (MRL) of 0.10 mg/kg as recommended by WHO for ∑HCH, 4% samples of 0.05 mg/kg for α-HCH, 5% samples of 0.01 mg/kg for γ-HCH, 26% samples of 0.02 mg/kg for β-HCH as recommended by PFAA and 24% samples of 0.05 mg/kg as recommended by FAO for ∑DDT. Concentrations of β-HCH and p,p′-DDE were more as compared to other isomers and metabolites of HCH and DDT.     

Persistence and Dissipation of Readymix Formulations of Insecticides In/On Okra Fruits

Dissipation behaviour of ready mix polytrin C 44EC (profenophos 40% + cypermethrin 4%) and spark 36EC (triazophos 35%+.deltamethrin 1%) applied at 1 L/ha in okra crop during Kharif in year 2000 was studied at 0, 1, 3, 5 and 7 days after treatment. Dissipation on 7th day was found to be maximum (98.4%) for profenophos followed by triazophos (86.2%), cypermethrin (73.5%) and deltamethrin (55.7%). Half life (t1/2) values for the above insecticides were 1.35, 2.55, 4.11 and 7.60 days, respectively. All the insecticides followed a first order kinetics. Profenophos and triazophos followed a biphasic dissipation pattern with faster dissipation in phase I (0–1 days) and manifesting slower rate of dissipation in phase II (1–7 days).     

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.     

Persistent Organochlorine Pesticide Residues in Soil and Surface Water of Northern Indo-Gangetic Alluvial Plains

This study reports the concentration levels and distribution pattern of the organochlorine pesticide (OCPs) residues in the soil and surface water samples collected from the northern Indo-Gangetic alluvial plains. A total of 31 soil and 23 surface water samples were collected from the study region in Unnao district covering an area of 2150 km² and analyzed for aldrin, dieldrin, endrin, HCB, HCH isomers, DDT isomers/metabolites, endosulfan isomers (α and β), endosulfan sulfate, heptachlor and its metabolites, α-chlordane, γ-chlordane and methoxychlor. In both the soil and surface water samples β- and δ-isomers of HCH were detected most frequently, whereas, methoxychlor was the least detected pesticide. The results showed contamination of soil and surface water of the region with several persistent organic pesticides. The total OCPs level ranged from 0.36–104.50 ng g^–1 and 2.63–3.72 μg L^–1 in soil and surface water samples, respectively.     

毛细管气相色谱法测定烟草中有机氯农药残留

研究了烟草中六六六及滴滴涕异构体含量的气相色谱分析方法.样品以石油醚 丙酮在索氏提取器中提取,提取液以浓硫酸净化.采用DB-5弹性石英毛细管柱分离样品,GC-ECD检测农药六六六、滴滴涕的残留量.方法的线性范围为2.27×10-13～7.66×10-11g;最小检测量为1.3×10-8～3.0×10-7 μg,加标平均回收率为95.3%～103.3%,RSD为2.8%～4.5%.     

Facile and Sensitive Spectrophotometric Determination of Synthetic Pyrithroids in Their Formulations, Water and Grain Samples

A novel reagent was introduced for the facile and sensitive spectrophotometric determination of syntheitic pyrethroids in their formulations (fenvalerate, cypermethrin and decamethrin), water and grain samples. These methods were based on the hydrolysis of synthetic pyrethroids under the alkaline conditions to form respective aldehyde groups. These groups were condensation with 3-methyl-2-benzothiazolinone hydrochloride (MBTH) to yield color derivatives having λ_max at 520 nm for fenvalerate, 516 nm for cypermethrin and 512 nm for decamethrin. The proposed method could be successfully applied for the determination of synthetic pyrethroids in their formulations, water and grain samples.     

Recommendations for Monitoring of Polybrominated Diphenyl Ethers in the Canadian Environment

Polybrominated diphenyl ethers (PBDEs) have been reported in air, surface waters, suspended sediments, soil, sediment, fish, marine mammals, and bird eggs throughout Canada, from the St. Lawrence Estuary to the Strait of Georgia and the northernmost reaches of the Canadian Arctic. Canadian scientists have detected the presence of PBDEs in breast milk in every Canadian province. In fact, recent data on temporal trends strongly suggests that the concentrations of PBDEs are on the rise in the Canadian environment. These findings are similar to those reported in other nordic countries, and have prompted several countries to implement environmental monitoring programs. Among the key challenges currently facing Canada and other countries concerns how best to measure these chemicals in different matrices. In this paper, several analytical methods cited in the scientific literature for determining PBDE concentrations in different abiotic and biological matrices are reviewed. The critical criteria required for accurate determination of PBDEs in complex environmental matrices are discussed, including instrument sensitivity, reliability, potential interference's and the need for specialized instrumentation for the determination of compounds up to 975 Daltons. While a single analytical method that meets these and other criteria has not yet been perfected by scientists, GC/HRMS-based methods amenable to isotope dilution techniques warrant further refinement, and likely represent the best tools for future environmental monitoring programs.     

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.     

云南曲靖某煤化工基地及周边土壤中多环芳烃的检测研究

采用快速溶剂提取处理土壤样品,利用气相色谱质谱内标法测定土壤中多环芳烃,其检出限范围为2.01~3.68μg/kg,相对标准偏差为2.6%~14.7%,加标回收率为67.1%~119%。结果表明,此方法具有良好的灵敏度、准确度和精密度。本研究对11个不同采样点土壤进行了检测分析,并考察了土壤中多环芳烃的污染水平。     

Screening-Level Risk Assessment of Di(2-ethylhexyl)phthalate for Aquatic Organisms Using Monitoring Data in Japan

Screening-level ecological risk assessments of di(2-ethylhexyl)phthalate (DEHP) for aquatic organisms in Japan were conducted using estimated statistical values based on surface water and sediment monitoring data and effect threshold values based on a large aquatic toxicity database. An alternative method is proposed to handle monitoring data that contain nondetects including multiple detection limits and to determine the statistical values of DEHP concentrations in Japanese surface waters. The No-Observed-Effect-Concentration (NOEC_water) of DEHP for aquatic life of 77 μ g/L was determined giving equal importance to both physical effects probably caused by undissolved DEHP and to the intrinsic toxicity potentially caused by DEHP. The NOEC_sediment of 615,000 μg/kg was determined by the Equilibrium Partitioning (EqP) theory, conservatively assuming a threshold effect level in the water column as the water solubility of 3 μ g/L. The potential risks of DEHP in Japanese water environments were characterized simply by comparing the margin of exposure (MOE) with a specified uncertainty multiplier (UM). The MOE is expressed as the ratio of NOEC_water or NOEC_sediment to the expected environmental concentrations such as the 95th percentiles of the estimated DEHP concentration distributions for surface water or sediment. The results of risk characterization show that all MOE values calculated using the statistical values of DEHP concentrations in Japanese surface waters and sediments are above 10, indicating minimal risk. Although the DEHP concentrations of some surface water samples showed MOE values of less than 10, considering environmental chemistry such as bioavailable fractions and the form of existence of DEHP in a water environment, we conclude that the current levels of DEHP are of little concern to aquatic life in the majority of Japanese surface waters and sediments.     

吹扫—捕集／气相色谱法测定水中挥发性有机物

为提高样品分析效率,研究并建立了吹扫-捕集／气相色谱／氢火焰检测器联用同时测定水中1,2-二氯乙烷、苯、甲苯、氯苯、乙苯、对-二甲苯、间-二甲苯、苯乙烯、邻-二甲苯、异丙苯、1,4-二氯苯、1,2-二氯苯、硝基苯、1,3,5-三氯苯、1,2,4-三氯苯、1,2,3-三氯苯、六氯丁二烯17种挥发性有机物的分析方法。结果表明,当进样体积为25．0ml时,最低检出限为0．0034-0．1088μg/L,相对标准偏差为1．8％～6．4％,加标平均回收率为97．6％-105．8％。该方法可快速、简便、准确、高灵敏度的测定水中17种挥发性有机物,并适用于饮用水和地表水中挥发性有机物的测定。     

Spatial Analysis of Volatile Organic Compounds from a Community-Based Air Toxics Monitoring Network in Deer Park,Texas, USA

In the summer of 2003, ambient air concentrations of volatile organic compounds (VOCs) were measured at 12 sites within a 3-km radius in Deer Park, Texas near Houston. The purpose of the study was to assess local spatial influence of traffic and other urban sources and was part of a larger investigation of VOC spatial and temporal heterogeneity influences in selected areas of Houston. Seventy 2-h samples were collected using passive organic vapor monitors. Most measurements of 13 VOC species were greater than the method detection limits. Samplers were located at 10 residential sites, a regulatory air monitoring station, and a site located at the centroid of the census tract in which the regulatory station was located. For residential sites, sampler placement locations (e. g., covered porch vs. house eaves) had no effect on concentration with the exception of methyl tertiary-butyl ether (MTBE). Relatively high correlations (Pearson r > 0.8) were found between toluene, ethylbenzene, and o,m,p-xylenes suggesting petroleum-related influence. Chloroform was not correlated with these species or benzene (Pearson r < 0.35) suggesting a different source influence, possibly from process-related activities. As shown in other spatial studies, wind direction relative to source location had an effect on VOC concentrations.