Comparative assessment of pesticide residues in grain, soil, and water from IPM and non-IPM trials of basmati rice

The integrated pest management (IPM) modules of pesticide schedule on Basmati rice were validated at field experiments conducted in Northern India for consecutive 3 years (2005–2008). The pesticide residues were found below the detectable limit (<0.01–0.001 mg/kg) in soil and irrigation water samples of Kaithal region. In Dehra Dun region of Uttrakhand, the residues of carbendazim in rice grains and soil were detected below <0.01 mg/kg level. In second year experiments (2006–2007), only four non-IPM soil samples indicated the presence of chlorpyrifos and endosulfan in the range of ND <0.001 to 0.07 mg/kg, out of 45 samples analyzed. Carbendazim applied as seed treatment at Dehradun and Kaithal field trials was found below detectable limit in both IPM and non-IPM rice grains (<0.01 mg/kg) and irrigation water (0.01 μl/ml). Chlorpyrifos was detected in five water samples from Kaithal and one from Pant Nagar in the range of 0.003–0.006 μl/L, α- and β-isomer of endosulfan in the range of 0.005–0.03, and 0.005–0.02 μl/ml, respectively, in one sample from Pant Nagar and two from Kaithal, out of a total of 22 samples. In the region of Uttrakhand and Uttar Pradesh during 2007–2008, four non-IPM samples of soil indicated trace levels of endosulfan, out of 16 samples analyzed. The residues were detected below detection limit for carbendazim (<0.01 mg/kg) in soil samples of Dehradun IPM fields and for endosulfan and carbendazim (0.001–0.01 μl/L) in water samples each from IPM and non-IPM fields of Uttar Pradesh. The results of 3-year trials of IPM module indicated basmati rice as safe and economical with pesticide residue-free rice grains.     

吹扫捕集-气相色谱质谱法分析土壤和沉积物中挥发性有机物

采用吹扫捕集-气相色谱质谱法对土壤和沉积物中挥发性有机物进行分析,优化了实验条件,所有物质的相对标准偏差小于5.0％,土壤样回收率在78.2％ ～99.8％之间,沉积物样的回收率在55.2％～95.2％之间.     

快速溶剂萃取、色质联机法及气相色谱法测定土壤中多氯联苯

尝试性地建立了快速溶剂萃取、气相色谱、气质联用仪测定土壤中具有代表性的7种多氯联苯单体的测定法。方法定量线性良好、灵敏度高，回收率在75％～110％之间，相对标准偏差小于15％。用于环境实样的分析，结果满意。     

Community air monitoring for pesticides—part 2: multiresidue determination of pesticides in air by gas chromatography,gas chromatography–mass spectrometry,and liquid chromatography–mass spectrometry

Two multiresidue methods were developed to determine pesticides in air collected in California. Pesticides were trapped using XAD-4 resin and extracted with ethyl acetate. Based on an analytical method from the University of California Davis Trace Analytical Laboratory, pesticides were detected by analyzing the extract by gas chromatography–mass spectrometry (GC-MS) to determine chlorothalonil, chlorthal-dimethyl, cycloate, dicloran, dicofol, EPTC, ethalfluralin, iprodione, mefenoxam, metolachlor, PCNB, permethrin, pronamide, simazine, trifluralin, and vinclozolin. A GC with a flame photometric detector was used to determine chlorpyrifos, chlorpyrifos oxon, diazinon, diazinon oxon, dimethoate, dimethoate oxon, fonophos, fonophos oxon, malathion, malathion oxon, naled, and oxydemeton. Trapping efficiencies ranged from 78 to 92 % for low level (0.5 μg) and 37–104 % for high level (50 and 100 μg) recoveries. Little to no degradation of compounds occurred over 31 days; recoveries ranged from 78 to 113 %. In the California Department of Food and Agriculture (CDFA) method, pesticides were detected by analyzing the extract by GC-MS to determine chlorothalonil, chlorpyrifos, cypermethrin, dichlorvos, dicofol, endosulfan 1, endosulfan sulfate, oxyfluorfen, permethrin, propargite, and trifluralin. A liquid chromatograph coupled to a MS was used to determine azinphos-methyl, chloropyrifos oxon, DEF, diazinon, diazinon oxon, dimethoate, dimethoate oxon, diuron, EPTC, malathion, malathion oxon, metolachlor, molinate, norflurazon, oryzalin, phosmet, propanil, simazine and thiobencarb. Trapping efficiencies for compounds determined by the CDFA method ranged from 10 to 113, 22 to 114, and 56 to 132 % for 10, 5, and 2 μg spikes, respectively. Storage tests yielded 70–170 % recovery for up to 28 days. These multiresidue methods represent flexible, sensitive, accurate, and cost-effective ways to determine residues of various pesticides in ambient air.     

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。     

气相色谱/负离子化学电离质谱法测定地表水中硫丹及其代谢物

采用气相色谱/负离子化学电离质谱法测定地表水中的硫丹及其代谢物,用正己烷提取,外标法定量。α-硫丹、β-硫丹及硫丹硫酸酯在0.200μg/L～10.0μg/L范围内线性良好,方法检出限分别为0.010μg/L、0.008μg/L及0.010μg/L,空白加标平行测定的RSD为3.9%～4.8%,地表水样品加标回收率为85.5%～93.8%。     

Development and comparison of methods using MS scan and selective ion monitoring modes for a wide range of airborne VOCs

Adsorbent sampling with analysis by thermal desorption, gas chromatography and mass spectrometry (TD/GC/MS) offers many advantages for volatile organic compounds (VOCs) and thus is increasingly used in many applications. For environmental samples and other complex mixtures, the MS detector typically is operated in the scan mode to aid identification of co-eluting compounds. However, scan mode does not achieve the optimal sensitivity, thus compounds occurring at low concentrations may not be detected. This paper develops and evaluates the application of a more sensitive TD/GC/MS method using selective ion monitoring (SIM) that is applicable to VOC mixtures found in ambient and indoor air. Based on toxicity and prevalence, 94 VOCs (including terpenes, aromatic, halogenated and aliphatic compounds) were selected as target compounds. Two analytical methods were developed: a conventional full scan method for ions from 29 to 270 m/z; and a SIM method using 16 time windows and different ions selected for the compounds in each window. Both methods used the same Tenax GR adsorbent sampling tubes, TD and GC parameters, and target and qualifier ions. Laboratory tests determined calibrations, method detection limits (MDLs), precisions, recoveries and storage stability. Field tests compared scan and SIM mode analyses for duplicate samples of indoor air in 51 houses and outdoor air at 41 sites. Statistical analyses included the development of error/precision models. The laboratory tests showed that most compounds demonstrated excellent precision (<10% for concentrations exceeding approximately 0.5 microg m(-3)), good linearity, near identical calibrations for scan and SIM modes, a wide dynamic range (up to 1500 microg m(-3)), and negligible storage losses after 1 month (7 compounds showed moderate losses). SIM mode MDLs ranged from 0.004 to 0.27 microg m(-3), representing a modest (1.1 to 22-fold) improvement compared to scan mode. However, in field tests the SIM method detected significantly more compounds (e.g., styrene and chloroform). Error models fit most compounds and allow quantification of errors at selected percentiles. Overall, while the new SIM method is somewhat time-consuming to develop, it offers greater sensitivity and maintains the high selectivity of traditional scan methods.     

Pesticide residue analysis of soil,water, and grain of IPM basmati rice

The main aim of the present investigations was to compare the pesticide load in integrated pest management (IPM) with non-IPM crops of rice fields. The harvest samples of Basmati rice grain, soil, and irrigation water, from IPM and non-IPM field trials, at villages in northern India, were analyzed using multi-pesticide residue method. The field experiments were conducted for three consecutive years (2008–2011) for the successful validation of the modules, synthesized for Basmati rice, at these locations. Residues of tricyclazole, propiconazole, hexconazole, lambda cyhalothrin, pretilachlor chlorpyrifos, DDVP, carbendazim, and imidacloprid were analyzed from two locations, Dudhli village of Dehradun, Uttrakhand and Saboli and Aterna village of Sonepat, Haryana. The pesticide residues were observed below detectable limit (BDL) (<0.001–0.05 μg/g) in all 24 samples of rice grains and soil under IPM and non-IPM trials. Residues were below detection level (<0.001–0.05 μg/L) in irrigation water samples (2008–09). Residues of tricyclazole and carbendazim, analyzed from same locations, revealed pesticide residues as BDL (<0.001–0.05 μg/g) in all 40 samples of Basmati rice grains and soil. It was also observed as BDL (<0.001–0.05 μg/L) for 12 water samples (2009–2010). The residues of tricyclazole, propioconazole, chlorpyrifos, hexaconazole, pretilachlor, and λ-cyhalothrin were also found as BDL (<0.001–0.05 μg/g) in 40 samples of Basmati rice grains and soil and 12 water samples (<0.001–0.05 μg/L) (2010–2011).     

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.     

Occurrence of organochlorine pesticide residues in green mussel (Perna viridis L.) and water from Ennore creek, Chennai, India

Green mussel (Perna viridis) and water samples were collected from Ennore creek, Chennai by seasonal sampling and analyzed for organochlorine pesticide residues (OCPs) like dichloro-diphenyl-trichloroethane (DDT) and its metabolites, isomers of hexachlorocyclohexane (HCH) and endosulfan. These residues were analyzed by using gas chromatograph (GC) with μECD. In the present study, mussel samples showed very low concentrations of OCPs in the statistical order of DDT (5.83 ng g^???1 wet tissue) > endosulfan (2.84 ng g^???1 wet tissue) > HCH (2.34 ng g^???1 wet tissue). Concentrations of OCPs in water samples were in the statistical order of endosulfan (29.21 ng L^???1)?> HCH (17.14 ng L^???1)?> DDT (14.63 ng L^???1). To our knowledge, this is the first report on the seasonal variation of OCPs and especially the quantification of endosulfan in Ennore Creek. The present study recommends that continuous monitoring in Ennore creek is necessary to assess possible impact on human health.     

The pollution and ecological risk of endosulfan in soil of Huai’an city, China

Endosulfan, a persistent organic pollutant newly listed under the Stockholm Convention, is currently widely produced and used as a pesticide in China. Concentrations of endosulfans (including α-, β-isomers, and their metabolite endosulfan sulfate) were determined in surface soil collected from Huai’an city, where the largest endosulfan producer is located. The concentrations of Σendosulfan (sum of α-endosulfan, β-endosulfan, and endosulfan sulfate) at all sites ranged from 0.28 to 44.81?ng/g dry weight (dw), following a lognormal distribution. The geometric mean was 1.09?ng/g dw, and the geometric standard deviation was 3.02. The β-endosulfan levels were consistently greater than those of α-isomer. The concentration ratios of α-endosulfan to β-endosulfan ranged from 0.03 to 0.70, which were much lower than the commercial endosulfan mixture. This is because that α-endosulfan is more volatile and degrades faster than β-endosulfan in soil. The contour map of Σendosulfan levels in soil indicates that the factory was the point pollution source with the highest endosulfan level in its surrounding area, especially the southern area. However, the non-point agricultural sources are more important. Based on Monte Carlo simulation, the Σendosulfan inventory in soil in Huai’an is estimated to be 0.8–3.0 tons. In order to understand the potential ecological risk of endosulfan, the Monte Carlo-based hazard quotient distribution was estimated and showed that Σendosulfan posed a potentially high risk to soil organisms. To our knowledge, this study is the first that reports soil pollution and risk of endosulfan around the manufacturer in China. This study will help China’s implementation of Stockholm Convention for the reduction and elimination of endosulfan in future.     

Determination of Endosulfans in Soil/Sediment Samples from Point Mugu, Oxnard, California Using Capillary Gas Chromatography/Mass Selective Detection (GC/MSD)

The extent of contamination by endosulfans in soil samples collected from the Point Mugu watershed near Oxnard, California was determined using capillary gas chromatography/mass selective detection (GC/MSD). The study was designed to detect three organochlorinated pesticides: endosulfan , endosulfan and endosulfan sulfate. Thirteen sets of two soil samples each were taken from various sites in the region. Our results show that the endosulfan levels in these soils range from trace amounts to nearly 30 ppm, with endosulfan being the most abundant and endosulfan sulfate the least. Two sites of the study, Hueneme and Revolon and Farm and Revolon, showed high amounts of endosulfans and , with concentrations between 20 and 30 ppm. The majority of the other sites studied in this research produced concentrations of less than 10 ppm for each of the three endosulfans monitored. At five areas in particular, Pleasant Valley and Creek, Laguna and Creek, Etting and Creek, Road and Creek and Hueneme and Creek, less than 2 ppm or only trace amounts of endosulfans , and sulfate were detected.     

A method developed for determination of heptachlor and its metabolites from pork

A new method has been developed to determine heptachlor and its metabolites heptachlor-exo-epoxide and heptachlor-endo-epoxide in pork. The pork samples were extracted with acetone–n-hexane (2:8, V:V) and cleaned up by gel permeation chromatography and florisil solid-phase extraction cartridge. The extract was then determined by gas chromatography equipped with electron capture detector (GC-ECD), followed by validation using gas chromatography–mass spectrometry (GC–MS) with negative chemical ionization. Linearity of calibration curves ranged from 0.01 to 0.5 mg L^?1, with correlation coefficients of more than 0.9980 for GC-ECD and GC–MS, respectively. At spiked concentrations of 0.01, 0.05, and 0.1 mg kg^?1, the average recovery and relative standard deviation values were 87.1–102.2 and 4.0–11.3 %, respectively. The limit of quantification for each analyte was 0.01 mg kg^?1, which satisfied the current maximum residue limit permitted in pork. Our results showed that the method developed was successfully used to determine heptachlor and heptachlor epoxide residues in real pork samples.     

A rapid and sensitive analytical method for the quantification of residues of endosulfan in blood

A new sensitive analytical procedure has been developed for the determination of residues of endosulfan in human blood samples. The method involves the extraction of residues of endosulfan from blood samples by the addition of 60% sulfuric acid at 10 degrees C, liquid/liquid partitioning by using hexane and acetone mixture (9:1) and quantification by using GC-ECD. Residues of endosulfan in blood samples were quantified as the sum of alpha-endosulfan, beta-endosulfan, endosulfan sulfate and endosulfandiol. The influence of temperature during the extraction has been studied. Recovery experiments were conducted over the concentration range 1.0-50 ng ml(-1) and the relative standard deviation calculated. The method was found to be sufficiently sensitive to quantify the residue of total endosulfan up to the 1.0 ng ml(-1) level. The recovery was 92% with a calculated relative standard deviation of 1.96%. Conversion of endosulfan to endosulfandiol is found to be less than 0.5% under the defined conditions. The method was applied to the analysis of residue contents of endosulfan and its metabolites in blood samples collected from the exposed population. The data obtained has been confirmed by GC-MS-EI in selective ion monitoring (SIM) mode.     

Status and effect of pesticide residues in soils under different land uses of Andaman Islands, India

Pesticides are shown to have a great effect on soil organisms, but the effect varies with pesticide group and concentration, and is modified by soil organic carbon content and soil texture. In the humid tropical islands of Andaman, India, no systematic study was carried out on pesticide residues in soils of different land uses. The present study used the modified QuEChERS method for multiresidue extraction from soils and detection with a gas chromatograph. DDT and its various metabolites, α-endosulfan, β-endosulfan, endosulfan sulfate, aldrin, and fenvalerate, were detected from the study area. Among the different pesticide groups detected, endosulfan and DDT accounted for 41.7 % each followed by aldrin (16.7 %) and synthetic pyrethroid (8.3 %). A significantly higher concentration of pesticide residues was detected in rice–vegetable grown in the valley followed by rice–fallow and vegetable–fallow in the coastal plains. Soil microbial biomass carbon is negatively correlated with the total pesticide residues in soils, and it varied from 181.2 to 350.6 mg?kg^?1. Pesticide residues have adversely affected the soil microbial populations, more significantly the bacterial population. The Azotobacter population has decreased to the extent of 51.8 % while actinomycetes were the least affected though accounted for 32 % when compared to the soils with no residue.     

Persistence and Distribution of Endosulfan under Field Condition

Rapid increase in industrialization and agricultural activities to meet the population need has led to environmental pollution. The major revolution in agricultural production is mainly due to increased use of pesticides and fertilizers. Soil act as a major sink for majority of pesticides applied on agricultural crops. Among the organochlorines, endosulfan is the most commonly used pesticide, hence this study concentrates on the persistence and distribution behaviour of endosulfan under field conditions. The result showed that the alpha endosulfan concentrations were very minimum (0.98 mg/kg of soil) in all the four fields under study (Nazarath, Othikadu, Ekkadu and Ekkadukandigai of Thiruvallur district, Tamil Nadu). Where as beta endosulfan concentration at the time of application was 6.39 mg/kg and declined to 0.8 mg/kg on soil at 150th day. The endosulfan sulfate concentration was 11.8 mg/kg in soil at 15th day and then concentration declined to 2.2 mg/kg at 150th day. Field run-off samples showed maximum residue levels (0.024 mg/l) at the early irrigation period. While plant foliar parts showed maximum concentrations of α-endosulfan (43.4 mg/kg), β-endosulfan (40.6 mg/kg) and endosulfan sulfate (20.1 mg/kg). At harvest stage, rice grain and husk also had lower concentrations of endosulfan sulfate (2.2 and 0.09 mg/kg), respectively.     

超声波萃取- GC/MS法测定土壤中多氯联苯

建立了超声波萃取、氟罗里硅土柱净化、气相色谱/质谱联用选择离子扫描模式测定土壤样品中多氯联苯Arochlor系列的方法.方法线性良好,灵敏度高,RSD为9.5%～12.2%,加标回收率为65.0%～105%,标准土壤样品的测定结果也符合要求.     

Uptake and bioavailability of persistent organic pollutants by plants grown in contaminated soil

This paper assesses the uptake of persistent organic pollutants (POP's) into plants. In particular, uptake of alpha-endosulfan, beta-endosulfan and endosulfan sulfate from lettuce. The lettuce plants were grown on compost that had previously been contaminated at 10 and 50 microg g(-1) per POP. The soil was slurry spiked by adding the appropriate amount of POP in acetone in an approximate ratio of 1 ratio 2, w/v soil ratio solvent. The solvent was left to evaporate at ambient temperature for 24 hours. Lettuce plants were grown under artificial daylight for 12 hours a day. The influence of soil ageing on the recovery of POP's from spiked soil samples was also assessed. The average recovery of endosulfan compounds from slurry spiked soil (10, 20 and 40 microg g(-1)) was consistent (92.9 +/- 4.4% for n= 9). However, ageing of endosulfan compounds on the slurry spiked soil resulted in lower recoveries (average losses were 12.5% after 14 days ageing of slurry spiked soil). The uptake of POP's was assessed by measuring the amount of endosulfan compounds in roots and leaves from lettuce plants after 10, 20 and 33 days. In addition, control plants grown in uncontaminated soil were monitored and analysed. It was found that endosulfan compounds were present in the roots of all lettuce plants irrespective of soil spike level or age of plant. In the 33 day lettuce plants where the soil was spiked at the highest level (50 microg g(-1)) endosulfan compounds were determined in the leaves. The root to leaf ratio was found to be 3.1 for alpha-endosulfan, 46.0 for beta-endosulfan, and 24.3 for endosulfan sulfate. Spiked lettuce samples were subjected to in vitro gastrointestinal extraction to assess the bioavailability of endosulfan compounds. No detectable endosulfan compounds were determined in the gastric extracts while small quantities (range 0.06-0.12 microg g(-1)) were found in the intestinal extraction. All samples (soil and lettuce) were extracted using pressurised fluid extraction and analysed using gas chromatography with mass selective detection.     

吹扫捕集气相色谱质谱法测定土壤中挥发性有机物

建立了吹扫捕集气相色谱质谱法同时测定土壤中卤代烃类、苯系物类、氯代苯类等二十多种挥发性有机物.使用模拟土壤和实际土壤样品优化了吹扫时间、吹扫温度等参数;采用内标法绘制了校正曲线,各目标化合物5个浓度水平的响应因子的相对标准偏差均小于20%,相关系数均大于0.999;测定了方法检出限,采用2g土壤,各目标化合物方法检出限界于0.02～1.00μg/kg;对两种总有机碳含量的实际土壤样品进行了加标回收实验,回收率范围64%～123%.     

Distribution of polycyclic aromatic hydrocarbons (PAHs) and sterols in termite nest, soil, and sediment from Great Kwa River, SE Nigeria

Costal sediment samples from Great Kwa River as well as adjoining termite nest and soil samples were analyzed for quantitative determination of polycyclic aromatic hydrocarbons (PAHs) and sterols using gas chromatography–mass spectrometry (GC–MS) in order to access the possibility of transport of biologically produced PAHs/sterols from termite nest to the sediments. The total PAH concentrations (sum of parent and alkyl) for the sediments ranged between 131.96 and 139.35 ng/g dry weight (dw) while those for the nest and soil samples were in the range 9.51–9.71 and 71.85–77.26 ng/g dw, respectively. These levels of PAHs in sediments were relatively low compared to other urban/industrial Asian and American countries. No evidence of the usual biologically produced PAHs was found, thus reducing the likelihood of transport of these compounds from the nest to the sediments. The absence of parent and alkyl PAHs in central compartment of the nest may reflect the selective fern leaves feeding pattern of the dominant termite species prevalent in the vicinity of the study site. Utilization of six selected PAH ratios such as Fla/(Fla + Pyr) (0.4–0.5), Ant/(Ant + Phe) (0.25–0.90), BaA/(BaA + Chrys) (0.45–0.61), MP/P (0.05–6.81), 1,7/(1,7?+?2,6)-DMP (0.61–0.95), and LPAH/HPAH ( 2.80–3.80) allows discrimination of PAH sources for the samples to be made with a mixed source dominance observed. Examination of sterol distributions in the samples shows relatively high abundance of cholest-5-en-3β-ol in central compartment of the nest, considered here as a consequence of metabolic conversion of phyto-/fungi sterols in the tissues of the termite species. The relatively reduced levels of stanol compounds in central compartment of the nest may be associated with their utilization by the termites for growth and development.