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Sample records for organophosphorus pesticide residues

  1. Organochlorine and organophosphorus pesticide residues in raw buffalo milk from agroindustrial areas in Assiut, Egypt.

    PubMed

    Shaker, Eman M; Elsharkawy, Eman E

    2015-01-01

    Raw buffalo milk samples from the agroindustrial zone in upper Egypt were analyzed for the presence of organochlorine and organophosphorus pesticides using gas chromatography-mass spectroscopy. Five organochlorine pesticides namely, alachlor, dieldrin, hexachlorobenzene, lindane and methoxychlor and three organophosphorus pesticides chlorpyrifos, malathion, and parathion-methyl were detected in the milk samples. In 44% of the samples, the concentrations of lindane and malathion residues exceeded tolerance levels set by the European Commission (EC) in 2008. In addition, the concentrations of chlorpyrifos, methoxychlor, and hexachlorobenzene residues exceeded the 2008 EC maximum residual limits (MRLs) by 33, 66, and 88% of the examined samples, respectively. However, the levels of alachlor, dieldrin, and parathion-methyl residues were below EC MRLs. The results of this study confirm the risks of pesticide residues exposure that threaten consumer health in Egypt. Thus, we recommend that pesticide residue monitoring programs be instituted in all the developing countries.

  2. Organochlorine and organophosphorus pesticide residues in food from Egyptian local markets.

    PubMed

    Dogheim, S M; Gad Alla, S A; el-Syes, S M; Almaz, M M; Salama, E Y

    1996-01-01

    A market basket survey was conducted to monitor organochlorine and organophosphorus pesticide residues in potatoes, citrus fruits, and fish collected from local Egyptian markets. Maximum Residue Limits (MRLs) of the Codex Committee on Pesticide Residues for gamma-hexachlorocyclohexane (HCH) in potatoes were exceeded in 8 samples and for DDT in 2 samples. The aging of HCH and DDT indicated a recent use of both pesticides during the potato storage period between cultivation seasons. However, such use is illegal because HCH mixture isomers (gammaxane) and DDT have been officially prohibited from agricultural use in Egypt since 1980. The highest residue levels of fenitrothion (3.8 ppm) in potatoes may be due to its repeated use before and after harvest. No organochlorine pesticide residues were found in citrus fruits. None of the detected organophosphorus pesticides exceeded their MRLs. HCH and DDT residue limits were exceeded in 5 and 7 fish samples, respectively, collected from 12 markets throughout the country. The heptachlor MRL was violated in only one fish sample (3.9 ppm).

  3. Monitoring of organophosphorus pesticide residues in vegetables of agricultural area in Venezuela.

    PubMed

    Quintero, América; Caselles, María J; Ettiene, Gretty; de Colmenares, Nélida G; Ramírez, Tibisay; Medina, Deisy

    2008-10-01

    The purpose of this study was to determine the residues of seven pesticides organophosphorus (methamidophos, diazinon, chlorpyriphos, parathion-methyl, dimethoate, malathion and tetrachlorvinphos), in some vegetables like: potato, lettuce, tomato, onion, red pepper and green onion cultivated in José María Vargas County in Táchira State, Venezuela. The research permitted to detect that 48.0% of the samples were contaminated with some of the pesticides studied. Methamidophos was founded in the vegetables in the rank of 6.3%-65.5%. The results show that 16.7% of the samples tested have residues higher than the maximum limits permitted.

  4. Organochlorine and organophosphorus pesticide residues in fodder and milk samples along Musi river belt, India

    PubMed Central

    Kotinagu, Korrapati; Krishnaiah, Nelapati

    2015-01-01

    Aim: The present study was conducted to find the organochlorine pesticide (OCP) and organophosphorus pesticide (OPP) residues in fodder and milk samples along Musi river belt, India. Materials and Methods: Fodder and milk samples collected from the six zones of Musi river belt, Hyderabad India were analyzed by gas chromatography with electron capture detector for OCP residues and pulsated flame photometric detector for the presence of OPP residues. Results: The gas chromatographic analysis of fodder samples of Zone 5 of Musi river showed the residues of dicofol at concentration of 0.07±0.0007 (0.071-0.077). Among organophosphorus compounds, dimetheoate was present in milk samples collected from Zone 6 at a level of 0.13±0.006 (0.111-0.167). The residues of OCPs, OPPs and cyclodies were below the detection limit in the remaining fodder and milk samples collected from Musi river belt in the present study. Conclusion: The results indicate that the pesticide residues in fodder and milk samples were well below the maximum residue level (MRL) values, whereas dicofol in fodder and dimethoate in milk were slightly above the MRL values specified by EU and CODEX. PMID:27047132

  5. Organophosphorus pesticide residues in milled rice (Oryza sativa) on the Chinese market and dietary risk assessment.

    PubMed

    Chen, Chen; Li, Yun; Chen, Mingxue; Chen, Zhijun; Qian, Yongzhong

    2009-03-01

    The present study investigates the occurrence of acetylcholinesterase (AChE)-inhibiting organophosphorus (OP) pesticide residues in milled rice samples obtained form local markets in China during the period 2004-2006 and estimates their cumulative exposure. Concentrations of OP pesticides were determined by gas chromatography with flame photometric detection (GC-FPD). The results showed that 9.3% of the samples contained detectable residues of at least one of the seven target OP pesticides (chlorpyrifos, dichlorvos, omethoate, methamidophos, parathion-methyl, parathion and triazophos) mainly used for agriculture in China, with concentrations ranging 0.011-1.756 mg kg(-1). Rice consumption data was obtained from an individual food consumption survey. Relative potency factors (RPFs) for each pesticide were calculated with methamidophos as the index compound (IC), using 1- or 2-year chronic non-observed adverse effect levels (NOAEL) for AChE inhibition, mostly in rat brain, obtained from international evaluations of pesticides. Exposure to AChE-inhibiting pesticides for the population above 7 years old at P99.9 represented 52-94.5% of the acceptable daily intake (ADI) expressed as methamidophos. Estimated exposure for children aged 2-4 and 4-7 years at P99.9 were 119 and 104.3% of the ADI level, respectively. This study suggests that a yearly monitoring program for OP pesticide residues and strict implementation of the national safety standard for milled rice is necessary.

  6. Application of graphene for the SPE clean-up of organophosphorus pesticides residues from apple juices.

    PubMed

    Han, Qiang; Wang, Zonghua; Xia, Jianfei; Zhang, Xiaoqiong; Wang, Hongwu; Ding, Mingyu

    2014-01-01

    In this paper, an effective graphene-based SPE clean-up procedure coupled with GC-MS was developed for the determination of organophosphorus pesticide residues in apple juices. The apple juice samples were diluted with water and could be loaded onto the cartridge directly. Several parameters affecting the extraction efficiency were investigated, including the type of elution, washing solution, and sample pH. Under the optimized conditions, excellent limits of quantitation for the target analytes were found to be 0.15-1.18 ng/mL, and the average recoveries of the analytes at two spiked levels for real-sample analysis ranged from 69.8 to 106.2% with RSDs less than 7.3%. Furthermore, the graphene-based cartridges exhibited superior reusability for juice sample analysis. The proposed method is sensitive, simple, and cost saving, and provides a detection platform for the monitoring of pesticide residues.

  7. [Determination of 47 organophosphorus pesticide residues in drinking water by membrane extraction-gas chromatography-PFPD].

    PubMed

    Yang, Yuan; Gao, Ling; Sun, Hao; Luo, Xiaofei; Lu, Dan

    2012-03-01

    To establish a method for the rapid determination of organophosphorus pesticide residues in drinking water by membrane extraction-gas chromatography. The pesticides were extracted from 1000 ml water sample with the activation of the C18 solid disk membrane. Then the extract was eluted by ethyl acetate, dehydrated by anhydrous sodium sulfate, nitrogen at least in 1 ml, set the volume to 1 ml. The volume was 2 microl for injection by gas chromatography. The spiked recoveries were between 81.8%-122.8%, the RSD were 2.67%-24%, the detection limits of different organophosphorus pesticides were 0.006-0.35 microg/L and the LLOQ were 0.022-1.2 microg/L. The method is simple, rapid, sensitive, repeatable, reliable and suitable for determination of trace organophosphorus pesticide in water.

  8. Gas chromatography with flame photometric detection of 31 organophosphorus pesticide residues in Alpinia oxyphylla dried fruits.

    PubMed

    Zhao, Xiangsheng; Kong, Weijun; Wei, Jianhe; Yang, Meihua

    2014-11-01

    A simple, rapid and effective gas chromatography-flame photometric detection method was established for simultaneous multi-component determination of 31 organophosphorus pesticides (OPPs) residues in Alpinia oxyphylla, which is widely consumed as a traditional medicine and food in China. Sample preparation was completed in a single step without any clean-up procedure. All pesticides expressed good linear relationships between 0.004 and 1.0 μg/mL with correlation coefficients higher than 0.9973. The method gave satisfactory recoveries for most pesticides. The limits of detection varied from 1 to 10 ng/mL, and the limits of quantification (LOQs) were between 4 and 30 ng/mL. The proposed method was successfully applied to 55 commercial samples purchased from five different areas. Five pesticide residues were detected in four (7.27%) samples. The positive samples were confirmed by gas chromatography with tandem mass spectrometry (GC-MS/MS). Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. [Research on rapid and quantitative detection method for organophosphorus pesticide residue].

    PubMed

    Sun, Yuan-Xin; Chen, Bing-Tai; Yi, Sen; Sun, Ming

    2014-05-01

    The methods of physical-chemical inspection is adopted in the traditional pesticide residue detection, which require a lot of pretreatment processes, are time-consuming and complicated. In the present study, the authors take chlorpyrifos applied widely in the present agricultural field as the research object and propose a rapid and quantitative detection method for organophosphorus pesticide residues. At first, according to the chemical characteristics of chlorpyrifos and comprehensive chromogenic effect of several colorimetric reagents and secondary pollution, the pretreatment of the scheme of chromogenic reaction of chlorpyrifos with resorcin in a weak alkaline environment was determined. Secondly, by analyzing Uv-Vis spectrum data of chlorpyrifos samples whose content were between 0. 5 and 400 mg kg-1, it was confirmed that the characteristic information after the color reaction mainly was concentrated among 360 approximately 400 nm. Thirdly, the full spectrum forecasting model was established based on the partial least squares, whose correlation coefficient of calibration was 0. 999 6, correlation coefficient of prediction reached 0. 995 6, standard deviation of calibration (RMSEC) was 2. 814 7 mg kg-1, and standard deviation of verification (RMSEP) was 8. 012 4 mg kg-1. Fourthly, the wavelengths whose center wavelength is 400 nm was extracted as characteristic region to build a forecasting model, whose correlation coefficient of calibration was 0. 999 6, correlation coefficient of prediction reached 0. 999 3, standard deviation of calibration (RMSEC) was 2. 566 7 mg kg-1 , standard deviation of verification (RMSEP) was 4. 886 6 mg kg-1, respectively. At last, by analyzing the near infrared spectrum data of chlorpyrifos samples with contents between 0. 5 and 16 mg kg-1, the authors found that although the characteristics of the chromogenic functional group are not obvious, the change of absorption peaks of resorcin itself in the neighborhood of 5 200 cm

  10. The research of Organophosphorus pesticide biosensor characteristic

    NASA Astrophysics Data System (ADS)

    Peng, Yong; Luo, Xixian; Cheng, Yi

    2010-10-01

    To study the fiber-sensor film applied in detecting Organophosphorus pesticide, methyltriethoxysilane was used as precursor, which was doped by FITC- AchE. Consequently, the excellent Acetylcholinesterase biology sensitivity film was prepared. Physics characteristic of the film and sensitivity of Organophosphorus pesticide were researched. In organophosphorus pesticide residue testing, the experimental results indicated that the linear measurement range could reach 10-7{10-6 mol/L, moreover the detection limit is 10-8 mol/L. The sensor could be applied in biological / chemical research, clinical medicine, environmental protection, food inspection, biochemical preventive war field and so on.

  11. Construction of genetically engineered bacteria that degrades organophosphorus pesticide residues and can be easily detected by the fluorescence.

    PubMed

    Li, Qin; Wang, Pan; Chen, Rui; Li, Wei; Wu, Yi-Jun

    2014-01-01

    Organophosphorus compounds (OPs) are widely used in agriculture and industry and there is increased concern about their toxicological effects in the environment. Bioremediation can offer an efficient and cost-effective option for the removal of OPs. Herein, we describe the construction of a genetically engineered microorganism (GEM) that can degrade OPs and be directly detected and monitored in the environment using an enhanced green fluorescent protein (EGFP) fusion strategy. The coding regions of EGFP, a reporter protein that can fluoresce by itself, and organophosphorus hydrolase (OPH), which has a broad substrate specificity and is able to hydrolyse a number of organophosphorus pesticides, were cloned into the expression vector pET-28b. The fusion protein of EGFP-OPH was expressed in E. coli BL21 (DE3) and the protein expression reached the highest level at 11 h after isopropyl beta-D-thiogalactopyranoside induction. The fluorescence of the GEM was detected by fluorescence spectrophotometry and microscopy, and its ability to degrade OPs was determined by OPH activity assay. Those GEM that express the fusion protein (EGFP and OPH) exhibited strong fluorescence intensity and also potent hydrolase activity, which could be used to degrade organophosphorus pesticide residues in the environment and can also be directly monitored by fluorescence.

  12. [Contamination of Organophosphorus Pesticides Residue in Fresh Vegetables and Related Health Risk Assessment in Changchun, China].

    PubMed

    Yu, Rui; Liu, Jing-shuang; Wang, Qi-cun; Liu, Qiang; Wang, Yang

    2015-09-01

    This study aims to investigate the concentrations of organophosphorus pesticides (OPs) in fresh vegetables. A total of Z14 samples from seven types of vegetables were collected from the suburb in Changchun City. The OPs were analyzed by gas chromatography coupled with flame photometric detector (GC-FPD). Target hazard quotients (THQ) were applied to estimate the potential health risk to inhabitants. Results showed that OPs concentrations exceeded the Maximum Residue Limit (MRL) in more than 23. 4% samples, and were not detected in only 7. 9% samples. Detection rates of OPs was as follow in the decreased order: diazinon (82. 2%) > phorate (45. 8%) > dimethoate (29. 4%) > parathion-methyl (27. 6%) > omethoate (23. 8%) > dichlorvos (22. 9%) > fenitrothion (21%) > fenthion (18. 7%) > parathion (18. 2%) > methamidophos (17. 3%) > malathion (12. 1%). The percentages above MRL for leaves were higher than for non-leafy vegetables. The order of percentages of OPs above MRL was as follows: green onion (82. 5%) > radish (37. 5%) > red pepper (17. 2%) > Chinese vegetable (14. 3%) > cucumber (3. 2%) > eggplant (2. 9%) > tomato (0%). 49. 5% vegetables samples showed more than one OP. The average target hazard quotients (ave THQ) were all less than one and the average Hazard Index (ave HI) was 0. 462, so that inhabitants who expose average OP levels may not experience adverse health effects.

  13. Detection of residual organochlorine and organophosphorus pesticides in agricultural soil in Rio Verde region of San Luis Potosi, Mexico.

    PubMed

    Velasco, Antonio; Hernández, Sergio; Ramírez, Martha; Ortíz, Irmene

    2014-01-01

    Organochlorine pesticides were intensively used in Mexico from 1950 until their ban and restriction in 1991. However, the presence of these compounds is commonly reported in many regions of the country. The aim of the present study was to identify and quantify residual organochlorine and organophosphorus pesticides in agricultural soil in Rio Verde region, San Luis Potosi state, which has been identified as possibly polluted by pesticides. Composed samples from 24 zones covering an area of approximately 5,440 ha were analyzed. The most frequently found pesticides were p,p'-DDT followed by ,p,p'-DDE, heptachlor, endosulfan and γ-HCH whose frequency rates were 100, 91, 83 and 54%, respectively. The concentration of p,p'-DDT in the crops grown in these soils was in the following order: chili > maize > tomato > alfalfa. The results obtained in this study show that p,p'-DDT values are lower or similar to those found in other agricultural regions of Mexico. Methyl and ethyl parathion were the most frequent organophosphate pesticide detected in 100% and 62.5% of the samples with average concentrations of 25.20 and 47.48 μg kg(-1), respectively. More research is needed to establish the background levels of pesticides in agricultural soils and their potential ecological and human health effects in this region.

  14. Study on Carrier Material of Immobilization Acetylcholinesterase For Biosensor in Detectionof Organophosphorus Pesticide Residues

    NASA Astrophysics Data System (ADS)

    Sun, Xia; Wang, Xiangyou; Jia, Chuandong

    A comparison between several immobilization materials of AChE on surface of glassy carbon electrode(GCE) was presented. The immobilization methods employed crosslinking method with glutaraldehyde as a cross-linking agent and bovine serum albumin(BSA) as a protectant, AChE was immobilized on different membranes including nylon membrane, cellulose nitrate membrane and chitosan membrane respectively. The enzyme membrane was then fixed on the surface of glassy carbon electrode(GCE) with O-ring to prepare an amperometric biosensor for the detection of organophosphorus pesticides. The activity of immobilization AChE was detected by measuring the oxidation current of thiocholine, the results showed that the activity of immobilization AChE were all different with different membrane as carrier material.Compared with nylon membrane and cellulose nitrate membrane, chitosan membrane was obviously good. So chitosan membrane can be selected as immobilized AChE carrier material.

  15. Risk assessment of the cumulative acute exposure of Hungarian population to organophosphorus pesticide residues with regard to consumers of plant based foods.

    PubMed

    Zentai, Andrea; Szabó, István J; Kerekes, Kata; Ambrus, Árpád

    2016-03-01

    Based on the Hungarian pesticide residues monitoring data of the last five years and the consumption data collected within a 3-day dietary record survey in 2009 (more than 2 million pesticide residue results and almost 5000, 0-101-year-old consumers 3 non-consecutive-day personal fruit and vegetable consumption data), the cumulative acute exposure of organophosphorus pesticide residues was evaluated. The relative potency factor approach was applied, with acephate chosen as index compound. According to our conservative calculation method, applying the measured residues only, the 99.95% of the 99th percentiles of calculated daily intakes was at or below 87 μg/kgbwday, indicating that the cumulative acute exposure of the whole Hungarian population (including all age classes) to organophosphorus compounds was not a health concern.

  16. An Innovative Rapid Method for Analysis of 10 Organophosphorus Pesticide Residues in Wheat by HS-SPME-GC-FPD/MSD.

    PubMed

    Du, Xin; Ren, YongLin; Beckett, Stephen J

    2016-01-01

    The rapid detection of pesticide residues in wheat has become a top food security priority. A solvent-free headspace solid-phase microextraction (HS-SPME) has been evaluated for rapid screening of organophosphorus pesticide (OPP) residues in wheat with high sensitivity. Individual wheat samples (1.7 g), spiked with 10 OPPs, were placed in a 4 mL sealed amber glass vial and heated at 60°C for 45 min. During this time, the OPP residues were extracted with a 50 μm/30 μm divinylbenzene (DVB)/carboxen (CAR)/plasma desorption mass spectroscopy polydimethylsiloxane (PDMS) fiber from the headspace above the sample. The fiber was then removed and injected into the GC injection port at 250°C for desorption of the extracted chemicals. The multiple residues were identified by a GC mass spectrometer detector (GC-MSD) and quantified with a GC flame photometric detector (GC-FPD). Seven spiked levels of 10 OPPs on wheat were analyzed. The GC responses for a 50 μm/30 μm DVB/CAR/PDMS fiber increased with increasing spiking levels, yielding significant (R(2) > 0.98) linear regressions. The lowest LODs of the multiple pesticide standards were evaluated under the conditions of the validation study in a range of levels from 0 (control) to 100 ng of pesticide residue per g of wheat that separated on a low-polar GC capillary column (Agilent DB-35UI). The results of the HS-SPME method were compared with the QuEChERS AOAC 2007.01 method and they showed several advantages over the latter. These included improved sensitivity, selectivity, and simplicity.

  17. Analysis of six organophosphorus pesticide residues in apples and pears using cloud-point extraction coupled with HPLC-UV.

    PubMed

    Zhang, Lijin; Chen, Fang; Zhang, Wenhuan; Pan, Canping

    2014-01-01

    A cloud-point extraction (CPE) method with Triton X-114 has been developed for analysis of six organophosphorus pesticides (OPPs) in apples and pears. In this CPE procedure, the effects of the surfactant volume, mass of sodium chloride, equilibrium temperature, equilibrium time, and pH on the extraction procedure were investigated. Under the optimal CPE conditions, the analytes were enriched 20-fold and the LODs dropped to 0.44-5.20 microg/kg. Furthermore, the proposed extraction method was validated by the correlation coefficient (R2) of the calibration curve, repeatability (RSD, n = 6), and fortified recoveries, which were 0.9967-0.9993, 2.7-6.5, and 74.7-104.5%, respectively. Based on these results, it could be concluded that the proposed CPE method with Triton X-114 was suitable for the effective extraction and enrichment of OPP residues in the apple and pear samples.

  18. Monitoring of organochlorine and organophosphorus pesticide residues in water during different seasons of Tighra reservoir Gwalior, Madhya Pradesh, India.

    PubMed

    Mamta; Rao, R J; Wani, Khursheed Ahmad

    2015-11-01

    Analysis of pesticides during different seasons for pesticidal contamination in water samples of Tighra reservoir was carried out on gas chromatograph-electron capture detector with capillary columns following multiresidual analytical technique. Organochlorine pesticides, viz., hexachlorobenzene (HCB), alpha-benzene hexachloride (BHC), beta-BHC, γ-BHC, heptachlor, aldrin, alpha-endosulfan, beta-endosulfan, p,p-DDE, dieldrin, o,p-dichlorodiphenyldichloroethane (DDD), p,p-DDD, p,p-dichlorodiphenyltrichloroethane (DDT), and endrin, and organophosphorus pesticides, viz., choloropyrifos, methyl parathion, diazion, dicholorovos, ethion, malathion, and parathion, were detected in water samples during different seasons. However, the pesticide concentration varied during different seasons at different sites. The prominent reason of contamination is the use of pesticides (both organochlorine and organophosphorus) in the agricultural fields near Tighra reservoir. On the basis of our observations, more extensive monitoring studies need to be carried out, covering all wetlands of Madhya Pradesh to enforce the policies for the restricted application of pesticides in agricultural fields adjacent to wetlands.

  19. Organophosphorus and Carbamate Pesticide Residues Detected in Water Samples Collected from Paddy and Vegetable Fields of the Savar and Dhamrai Upazilas in Bangladesh

    PubMed Central

    Chowdhury, Md. Alamgir Zaman; Banik, Sanjoy; Uddin, Borhan; Moniruzzaman, Mohammed; Karim, Nurul; Gan, Siew Hua

    2012-01-01

    Several types of organophosphorous and carbamate pesticides have been used extensively by the farmers in Bangladesh during the last few decades. Twenty seven water samples collected from both paddy and vegetable fields in the Savar and Dhamrai Upazilas in Bangladesh were analyzed to determine the occurrence and distribution of organo-phosphorus (chlorpyrifos, malathion and diazinon) and carbamate (carbaryl and carbofuran) pesticide residues. A high performance liquid chromatograph instrument equipped with a photodiode array detector was used to determine the concentrations of these pesticide residues. Diazinon and carbofuran were detected in water samples collected from Savar Upazila at 0.9 μg/L and 198.7 μg/L, respectively. Malathion was also detected in a single water sample at 105.2 μg/L from Dhamrai Upazila. Carbaryl was the most common pesticide detected in Dhamrai Upazila at 14.1 and 18.1 μg/L, while another water sample from Dhamrai Upazila was contaminated with carbofuran at 105.2 μg/L. Chlorpyrifos was not detected in any sample. Overall, the pesticide residues detected were well above the maximum acceptable levels of total and individual pesticide contamination, at 0.5 and 0.1 μg/L, respectively, in water samples recommended by the European Economic Community (Directive 98/83/EC). The presence of these pesticide residues may be attributed by their intense use by the farmers living in these areas. Proper handling of these pesticides should be ensured to avoid direct or indirect exposure to these pesticides. PMID:23202689

  20. CUMULATIVE RISK ANALYSIS FOR ORGANOPHOSPHORUS PESTICIDES

    EPA Science Inventory

    Cumulative Risk Analysis for Organophosphorus Pesticides
    R. Woodrow Setzer, Jr. NHEERL MD-74, USEPA, RTP, NC 27711

    The US EPA has recently completed a risk assessment of the effects of exposure to 33 organophosphorous pesticides (OPs) through the diet, water, and resi...

  1. CUMULATIVE RISK ANALYSIS FOR ORGANOPHOSPHORUS PESTICIDES

    EPA Science Inventory

    Cumulative Risk Analysis for Organophosphorus Pesticides
    R. Woodrow Setzer, Jr. NHEERL MD-74, USEPA, RTP, NC 27711

    The US EPA has recently completed a risk assessment of the effects of exposure to 33 organophosphorous pesticides (OPs) through the diet, water, and resi...

  2. Determination of 15 organophosphorus pesticides in Italian raw milk.

    PubMed

    Gazzotti, Teresa; Sticca, Patrizia; Zironi, Elisa; Lugoboni, Barbara; Serraino, Andrea; Pagliuca, Giampiero

    2009-02-01

    A study was conducted on raw cow's milk to measure the residues of 15 organophosphorus pesticides used as dairy cattle ectoparasiticides or as insecticides in crops used for animal feed. For this purpose a previously devised method was improved and validated. The samples were collected directly from tank trucks during delivery of 3,974 tonnes of raw milk at nine Italian dairy plants. Approximately 4.4% of the 298 samples analyzed contained residues only in traces. The main pollutant was chlorpyriphos.

  3. Application of elevated temperature-dispersive liquid-liquid microextraction for determination of organophosphorus pesticides residues in aqueous samples followed by gas chromatography-flame ionization detection.

    PubMed

    Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Rezaee Aghdam, Samaneh; Nouri, Nina; Bamorrowat, Mahdi

    2016-12-01

    In the present study, an elevated temperature, dispersive, liquid-liquid microextraction/gas chromatography-flame ionization detection was investigated for the determination, pre-concentration, and extraction of six organophosphorus pesticides (malathion, phosalone, dichlorvos, diazinon, profenofos, and chlorpyrifos) residues in fruit juice and aqueous samples. A mixture of 1,2-dibromoethane (extraction solvent) and dimethyl sulfoxide (disperser solvent) was injected rapidly into the sample solution heated at an elevated temperature. Analytical parameters, including enrichment factors (1600-2075), linearity (r>0.994), limits of detection (0.82-2.72ngmL(-1)) and quantification (2.60-7.36ngmL(-1)), relative standard deviations (<7%) and extraction recoveries (64-83%), showed the high efficiency of the method developed for analysis of the target analytes. The proposed procedure was used effectively to analyse selected analytes in river water and fruit juice, and diazinon was found at ngmL(-1) concentrations in apple juice.

  4. Pesticides.

    ERIC Educational Resources Information Center

    Sherma, Joseph

    1989-01-01

    This review is devoted to methods for the determination of residues of pesticides and some related industrial chemicals. Topics include: residue methods, sampling, chromatography, organochlorine pesticides, organophosphorus pesticides, carbamate insecticides, herbicides, fungicides, pyrethrins, fumigants, and related chemicals. (MVL)

  5. Pesticides.

    ERIC Educational Resources Information Center

    Sherma, Joseph

    1989-01-01

    This review is devoted to methods for the determination of residues of pesticides and some related industrial chemicals. Topics include: residue methods, sampling, chromatography, organochlorine pesticides, organophosphorus pesticides, carbamate insecticides, herbicides, fungicides, pyrethrins, fumigants, and related chemicals. (MVL)

  6. CUMULATIVE EFFECTS OF ORGANOPHOSPHORUS OR CARBAMATE PESTICIDES.

    EPA Science Inventory

    This book chapter strives to summarize the body of literature exploring the toxic interaction of organophosphorus and carbamate pesticides in mixtures. This review represents one of the only reviews of the subject that has been published within the last 20 years. Specifically, th...

  7. Household organophosphorus pesticide use and Parkinson's disease.

    PubMed

    Narayan, Shilpa; Liew, Zeyan; Paul, Kimberly; Lee, Pei-Chen; Sinsheimer, Janet S; Bronstein, Jeff M; Ritz, Beate

    2013-10-01

    Household pesticide use is widespread in the USA. Since the 1970s, organophosphorus chemicals (OPs) have been common active ingredients in these products. Parkinson's disease (PD) has been linked to pesticide exposures but little is known about the contributions of chronic exposures to household pesticides. Here we investigate whether long-term use of household pesticides, especially those containing OPs, increases the odds of PD. In a population-based case-control study, we assessed frequency of household pesticide use for 357 cases and 807 controls, relying on the California Department of Pesticide Regulation product label database to identify ingredients in reported household pesticide products and the Pesticide Action Network pesticide database of chemical ingredients. Using logistic regression we estimated the effects of household pesticide use. Frequent use of any household pesticide increased the odds of PD by 47% [odds ratio (OR)=1.47, (95% confidence interval (CI): 1.13, 1.92)]; frequent use of products containing OPs increased the odds of PD more strongly by 71% [OR=1.71, (95% CI: 1.21, 2.41)] and frequent organothiophosphate use almost doubled the odds of PD. Sensitivity analyses showed that estimated effects were independent of other pesticide exposures (ambient and occupational) and the largest odds ratios were estimated for frequent OP users who were carriers of the 192QQ paraoxonase genetic variant related to slower detoxification of OPs. We provide evidence that household use of OP pesticides is associated with an increased risk of developing PD.

  8. Determination of organophosphorus pesticide residues in vegetables by an enzyme inhibition method using α-naphthyl acetate esterase extracted from wheat flour*

    PubMed Central

    Wang, Jun-liang; Xia, Qing; Zhang, An-ping; Hu, Xiao-yan; Lin, Chun-mian

    2012-01-01

    The widespread use of organophosphorus pesticides (OPs) poses a great threat to human health and has made the detection of OP residues in food an important task, especially in view of the fact that easy and rapid detection methods are needed. Because OPs have inhibitory effects on the activity of α-naphthyl acetate esterase (ANAE) in plants, in this work we evaluated the possibility of detecting OPs in vegetables with ANAE extracted from commercial flour. The limits of detection (LODs) obtained for methamidophos, dichlorvos, phoxim, dimethoate, and malathion in lettuce samples with crude ANAE were 0.17, 0.11, 0.11, 0.96, and 1.70 mg/kg, respectively. Based on the maximum residue limits (MRLs) for OPs in food stipulated by Chinese laws which are 0.05, 0.20, 0.05, 1.00, and 8.00 mg/kg for methamidophos, dichlorvos, phoxim, dimethoate, and malathion, respectively, the esterase inhibition method with crude ANAE had sufficient sensitivity to detect the residues of dichlorvos, dimethoate, and malathion in lettuce, but it could not be used to guarantee the safety of the same samples if methamidophos or phoxim residue was present. The sensitivity of the method was improved by the use of esterase purified by ammonium sulfate salting-out. The LODs obtained for methamidophos and phoxim with purified esterase were lower than the MRLs for these OPs in food. This is a very promising method for the detection of OP residues in vegetables using crude or purified esterase because of its cheapness, sensitivity, and convenience. PMID:22467368

  9. Chlorination of organophosphorus pesticides in natural waters.

    PubMed

    Acero, Juan L; Benítez, F Javier; Real, Francisco J; González, Manuel

    2008-05-01

    Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 degrees C and pH 7 were determined to be 110.9, 0.004 and 191.6 M(-1) s(-1) for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L(-1) was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety.

  10. Biodegradation of organophosphorus pesticides by soil bacteria

    NASA Astrophysics Data System (ADS)

    de Pasquale, C.; Fodale, R.; Lo Piccolo, L.; Palazzolo, E.; Alonzo, G.; Quatrini, P.

    2009-04-01

    A number of studies in the 1980s and 1990s showed that crop-protection products, applied to drained fields, could move downwards through the soil profile and to the groundwater. Organophosphorus insecticides (OPs) are used all over the world for crop protection, for other agricultural practices such as sheep dipping and, in aquaculture, for the control of sea lice. Ops besides showing a specific neurotoxicity and have also been related to various modern diseases, including Creutzfeldt-Jakob (CJD) and the Gulf War syndrome. Although OPs are less persistent than Organoclorine pesticides (OCs), they still constitute an environmental risks thus increasing the social concern about their levels in soils, surface waters, and ground waters. Degradation of OPs by microorganisms has been assessed for a few bacterial strains. In the present study the OPs degrading potential of indigenous soil microorganisms was investigated. Using enrichment cultures in which parathion was the only C and energy sources many bacterial strains were isolated from OPs contaminated and pristine agricultural soils characterized by different physico-chemical properties. More than 40 potential OPs degraders were isolated and grouped in operational taxonomic units (OTU) using analysis of polymorphism showed by the ribosomal internal transcribed spacer (ITS). Partial sequencing of 16S rRNA gene of representative isolates of each OTU revealed that most of them belong to Proteobacteria and Actinobacteria. All the analyzed soils showed the presence of putative OPs degraders: the highest diversity was found in organic cultivated soils, the lowest in chemically cultivated soils. Degradation of different OPs, characterized by different physical and chemical properties, was obtained by different selected representative strains using SPME GC-MS analysis on water and soil microcosms. The results showed that, after the incubation period, the amount of pesticide residues were in the range 20-80%. Some of the

  11. Compound specific isotope analysis of organophosphorus pesticides.

    PubMed

    Wu, Langping; Yao, Jun; Trebse, Polonca; Zhang, Ning; Richnow, Hans H

    2014-09-01

    Compound-specific isotope analysis (CSIA) has been established as a tool to study the environmental fate of a wide range of contaminants. In this study, CSIA was developed to analyse the stable carbon isotope signatures of the widely used organophosphorus pesticides: dichlorvos, omethoate and dimethoate. The linearity of the GC-C-IRMS system was tested for target pesticides and led to an acceptable isotope composition within the uncertainty of the instrument. In order to assess the accuracy of the developed method, the effect of the evaporation procedure on measured carbon isotope composition (δ(13)C) values was studied and showed that concentration by evaporation of solvents had no significant isotope effect. The CSIA was then applied to investigate isotope fractionation of the hydrolysis and photolysis of selected pesticides. The carbon isotope fractionation of tested pesticides was quantified by the Rayleigh model, which revealed a bulk enrichment factor (ε) of -0.2±0.1‰ for hydrolysis of dichlorvos, -1.0±0.1‰ and -3.7±1.1‰ for hydrolysis and photolysis of dimethoate respectively. This study is a first step towards the application of CSIA to trace the transport and degradation of organophosphorus pesticides in the environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. ORGANOPHOSPHORUS PESTICIDE DEGRADATION PATHWAYS DURING DRINKING WATER TREATMENT

    EPA Science Inventory

    The objective of this work was to investigate organophosphorus (OP) pesticide transformation pathways as a class in the presence of aqueous chlorine. Seven priority OP pesticides were examined for their reactivity with aqueous chlorine: chlorpyrifos (CP), parathion (PA), diazino...

  13. ORGANOPHOSPHORUS PESTICIDE DEGRADATION PATHWAYS DURING DRINKING WATER TREATMENT

    EPA Science Inventory

    The objective of this work was to investigate organophosphorus (OP) pesticide transformation pathways as a class in the presence of aqueous chlorine. Seven priority OP pesticides were examined for their reactivity with aqueous chlorine: chlorpyrifos (CP), parathion (PA), diazino...

  14. [Evaluation of QuEchERS methods for the analysis of 66 organophosphorus pesticide residues in vegetables by liquid chromatography-tandem mass spectrometry].

    PubMed

    Wang, Lianzhu; Zhou, Yu; Chen, Yong; Wang, Ruilong; Lin, Zixu; Lin, Dejuan; Zheng, Shaohui

    2012-02-01

    A comparison was made between the two versions of QuEChERS sample preparation method for the extraction of 66 organophosphorus pesticides (OPPS) in vegetables. The two QuEChERS methods were the original method without buffer published in 2003, and the AOAC Official Method 2007. 01 with acetate buffer. The adsorption behaviors of primary secondary amine (PSA) sorbent and C18 sorbent on the OPPS were studied. The method of after-extraction addition was used to evaluate matrix effects for OPPS in matrix of broccoli, tomato, green soybean, radish and shallot during liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. As a result, the QuEChERS method with acetate buffer gave higher and more consistent recoveries for some of OPPS. The PSA sorbent and C18 sorbent can adsorb dibrom, so the QuEChERS method was not suitable for the analysis of dibrom. The maximum matrix effects were in the extracts of broccoli during LC-MS/MS analysis. In this article, OPPS were extracted using the QuEChERS method with acetate buffer, and analysed by LC-MS/MS under the optimized conditions with monitoring 132 MS/MS transitions of precursor ions (two for each pesticide) in one single run. Recoveries for all but dibrom at fortification levels of 10, 40, 80 microg/kg in broccoli, tomato, green soybean, radish and shallot ranged from 55% to 122% with relative standard deviations of 1.6% - 18%. The limits of quantification (S/N > or = 10) were 0.1 - 8 microg/kg. Based on these results, the analytical method was proven to be highly efficient, robust and sensitive, and suitable for the monitoring of the maximum residue limits (MRLs) of 66 OPPS in vegetables.

  15. Analysis of eight organophosphorus pesticide residues in fresh vegetables retailed in agricultural product markets of Nanjing, China.

    PubMed

    Wang, Ligang; Liang, Yongchao; Jiang, Xin

    2008-10-01

    A method to effectively remove pigments in fresh vegetables using activated carbon followed cleanup through solid phase extraction (SPE) cartridge to further reduce matrix interference and contamination, was established to determine eight organophosphorous pesticides (OPPs) by gas chromatography (GC) with nitrogen-phosphorus detection (NPD) in this study, and it has been successfully applied for the determination of eight OPPs in various fresh vegetables with the recoveries ranging from 61.8% to 107%. To evaluate eight OPPs residue level, some fresh vegetables retailed at three agricultural product markets (APM) of Nanjing in China were detected, the results showed that phorate in Shanghai green (0.0257 microg g(-1)) and Chinese cabbage (0.0398 microg g(-1)), dimethoate in Shanghai green (0.0466-0.0810 microg g(-1)), Chinese cabbage (0.077 microg g(-1)), and spinach (0.118-0.124 microg g(-1)), methyl-parathion in Shanghai green (0.0903 microg g(-1)), Chinese cabbage (0.157 microg g(-1)), and spinach (0.0924 microg g(-1)), malathion in Shanghai green (0.0342-0.0526 microg g(-1)), chorpyrifos in spinach (0.106-0.204 microg g(-1)), and Chinese cabbage (0.149 microg g(-1)), chlorfenvinfos in carrot (0.094-0.131 microg g(-1)), were found. However, fonofos and fenthion were not detected in all the collected vegetable samples.

  16. Photodegradation of organophosphorus pesticides in honey medium.

    PubMed

    Yuan, Zhimin; Yao, Jun; Liu, Haijun; Han, Jun; Trebše, Polonca

    2014-10-01

    Honey can be polluted due to environmental pollution and misuse of beekeeping practices. In the present study, photodegradation experiments of organophosphorus pesticides (coumaphos, methyl parathion and fenitrothion) in honey medium were conducted using Atlas Suntest simulator CPS+ as a sunlight producer. Photodegradation experiments were conducted under three different intensities as 250W/m(2), 500W/m(2) and 750W/m(2) to evaluate the impact of sunlight intensity on removal of OPs in honey medium. Significant decreases of three OPs' concentrations were observed. Coumaphos showed the highest degradability, reaching a degradation percentage of 90 percent within 15min. After 1h irradiation, residual percentages of coumaphos were 6.62 percent for 250W/m(2), 3.48 percent for 500W/m(2) and 2.98 percent for 750W/m(2), respectively. Methyl parathion and fenitrothion also could be removed through photodegradation efficiently. After 1h irradiation, the residual percentages of methyl parathion and fenitrothion under 750W/m(2) sunlight irradiation were 26.89 percent and 16.70 percent, respectively. Intensity of sunlight showed a positive impact on removal of OPs in honey medium. The higher intensity, the lower residual percentage. Photodegradation of three OPs fitted well with pseudo-first order kinetics. Half-lives calculated from pseudo-first order kinetics were 17.61min (250W/m(2)), 16.67min (500W/m(2)) and 17.58min (750W/m(2)) for coumaphos, 57.62min (250W/m(2)), 34.13min (500W/m(2)) and 31.69min (750W/m(2)) for methyl parathion and 144.70min (250W/m(2)), 95.47min (500W/m(2)) and 22.57min (750W/m(2)) for fenitrothion, respectively. Most of the three OPs could dissipate in a short time under sunlight irradiation. Photodegradation could be accepted as an appropriate method for the removal of OPs in honey medium.

  17. Fluorescent chemosensors for toxic organophosphorus pesticides: a review.

    PubMed

    Obare, Sherine O; De, Chandrima; Guo, Wen; Haywood, Tajay L; Samuels, Tova A; Adams, Clara P; Masika, Noah O; Murray, Desmond H; Anderson, Ginger A; Campbell, Keith; Fletcher, Kenneth

    2010-01-01

    Many organophosphorus (OP) based compounds are highly toxic and powerful inhibitors of cholinesterases that generate serious environmental and human health concerns. Organothiophosphates with a thiophosphoryl (P=S) functional group constitute a broad class of these widely used pesticides. They are related to the more reactive phosphoryl (P=O) organophosphates, which include very lethal nerve agents and chemical warfare agents, such as, VX, Soman and Sarin. Unfortunately, widespread and frequent commercial use of OP-based compounds in agricultural lands has resulted in their presence as residues in crops, livestock, and poultry products and also led to their migration into aquifers. Thus, the design of new sensors with improved analyte selectivity and sensitivity is of paramount importance in this area. Herein, we review recent advances in the development of fluorescent chemosensors for toxic OP pesticides and related compounds. We also discuss challenges and progress towards the design of future chemosensors with dual modes for signal transduction.

  18. Fluorescent Chemosensors for Toxic Organophosphorus Pesticides: A Review

    PubMed Central

    Obare, Sherine O.; De, Chandrima; Guo, Wen; Haywood, Tajay L.; Samuels, Tova A.; Adams, Clara P.; Masika, Noah O.; Murray, Desmond H.; Anderson, Ginger A.; Campbell, Keith; Fletcher, Kenneth

    2010-01-01

    Many organophosphorus (OP) based compounds are highly toxic and powerful inhibitors of cholinesterases that generate serious environmental and human health concerns. Organothiophosphates with a thiophosphoryl (P=S) functional group constitute a broad class of these widely used pesticides. They are related to the more reactive phosphoryl (P=O) organophosphates, which include very lethal nerve agents and chemical warfare agents, such as, VX, Soman and Sarin. Unfortunately, widespread and frequent commercial use of OP-based compounds in agricultural lands has resulted in their presence as residues in crops, livestock, and poultry products and also led to their migration into aquifers. Thus, the design of new sensors with improved analyte selectivity and sensitivity is of paramount importance in this area. Herein, we review recent advances in the development of fluorescent chemosensors for toxic OP pesticides and related compounds. We also discuss challenges and progress towards the design of future chemosensors with dual modes for signal transduction. PMID:22163587

  19. Chloramination of Organophosphorus Pesticides Found in Drinking Water Sources

    EPA Science Inventory

    The degradation of commonly detected organophosphorus (OP) pesticides, in drinking water sources, was investigated under simulated chloramination conditions. Due to monochloramine autodecomposition, it is difficult to observe the direct reaction of monochloramine with each OP pe...

  20. Chloramination of Organophosphorus Pesticides Found in Drinking Water Sources

    EPA Science Inventory

    The degradation of commonly detected organophosphorus (OP) pesticides, in drinking water sources, was investigated under simulated chloramination conditions. Due to monochloramine autodecomposition, it is difficult to observe the direct reaction of monochloramine with each OP pe...

  1. Determination of organophosphorus pesticides and their major degradation product residues in food samples by HPLC-UV.

    PubMed

    Peng, Guilong; He, Qiang; Lu, Ying; Mmereki, Daniel; Zhong, Zhihui

    2016-10-01

    A simple method based on dispersive solid-phase extraction (DSPE) and dispersive liquid-liquid microextraction method based on solidification of floating organic droplets (DLLME-SFO) was developed for the extraction of chlorpyrifos (CP), chlorpyrifos-methyl (CPM), and their main degradation product 3,5,6-trichloro-2-pyridinol (TCP) in tomato and cucumber samples. The determination was carried out by high performance liquid chromatography with ultraviolet detection (HPLC-UV). In the DSPE-DLLME-SFO, the analytes were first extracted with acetone. The clean-up of the extract by DSPE was carried out by directly adding activated carbon sorbent into the extract solution, followed by shaking and filtration. Under the optimum conditions, the proposed method was sensitive and showed a good linearity within a range of 2-500 ng/g, with the correlation coefficients (r) varying from 0.9991 to 0.9996. The enrichment factors ranged from 127 to 138. The limit of detections (LODs) were in the range of 0.12-0.68 ng/g, and the relative standard deviations (RSDs) for 50 ng/g of each analytes in tomato samples were in the range of 3.25-6.26 % (n = 5). The proposed method was successfully applied for the extraction and determination of the mentioned analytes residues in tomato and cucumber samples, and satisfactory results were obtained.

  2. Maternal exposure to the mixture of organophosphorus pesticides induces reproductive dysfunction in the offspring.

    PubMed

    Yu, Yan; Yang, Aimin; Zhang, Jinghua; Hu, Senke

    2013-09-01

    Organophosphorus pesticide residues are found in many food samples due to increasing use of multiple organophosphorus pesticides (OPs) in agriculture. Toxicity of individual organophosphorus has been well-studied in previous epidemiological and laboratory investigations. This study focused on reproductive toxicity of perinatal exposure to the mixture of organophosphorus pesticides (MOPs). The MOPs consists of three most commonly used pesticides, i.e., Dichlorovos, Dimethoate, and Malathion which individually does not cause significant effects on the reproductive system at the similar concentration levels based on previous studies. Using the Sprague-Dawley rats, we established a perinatal exposure model by oral gavage and observed significant endometrial hyperplasia and thickened uterine walls in the F0 rats after administration of high doses of the MOPs. We further monitored several key developmental and behavioral indices in the F1 generation after maternal exposure to the MOPs, and observed significantly delayed physical development and weakened mental development. Moreover, we found increased weights of the reproductive organs (the uterus and the testis) and abnormal levels of key sex hormones (progestin and testosterone) in the MOPs groups. It is more important that we observed a significantly lower pregnancy rate and live birth rate in the high-dose MOPs group. These results indicate that the MOPs may be more detrimental to the maternal endometria and the reproductive functions in the offspring than individual organophosphorus. Copyright © 2011 Wiley Periodicals, Inc., a Wiley company.

  3. Enzyme-based electrochemical biosensors for determination of organophosphorus and carbamate pesticides

    SciTech Connect

    Everett, W.R.; Rechnitz, G.A.

    1999-01-01

    A mini review of enzyme-based electrochemical biosensors for inhibition analysis of organophosphorus and carbamate pesticides is presented. Discussion includes the most recent literature to present advances in detection limits, selectivity and real sample analysis. Recent reviews on the monitoring of pesticides and their residues suggest that the classical analytical techniques of gas and liquid chromatography are the most widely used methods of detection. These techniques, although very accurate in their determinations, can be quite time consuming and expensive and usually require extensive sample clean up and pro-concentration. For these and many other reasons, the classical techniques are very difficult to adapt for field use. Numerous researchers, in the past decade, have developed and made improvements on biosensors for use in pesticide analysis. This mini review will focus on recent advances made in enzyme-based electrochemical biosensors for the determinations of organophosphorus and carbamate pesticides.

  4. Organophosphorus and carbamate pesticides. Chapter 12 in Handbook of Ecotoxicology

    USGS Publications Warehouse

    Hill, Elwood F.; Hoffman, David J.; Rattner, Barnett A.; Burton, G. Allen; Cairns, John

    1995-01-01

    Organophosphorus and carbamate pesticides are used throughout the world to control a large variety of insects and other invertebrates, fungi, birds, mammals, and herbaceous plants. Over 100 different organophosphorus and carbamate chemicals are registered in the U.S. alone for use in thousands of products applied to widely diverse habitats including agricultural crops, forests, rangelands, wetlands, towns, and cities. These applications are estimated to be nearly 200 million acre-treatments (i.e., number of acres treated corrected for number of treatments) per year to control nuisance, depradating, and disease-bearing invertebrates and vertebrates, and to maintain landscape aesthetics. Except for mosquito control, most applications target terrestrial habitat. Due to drift or run-off, pesticide and degrades are inevitably detected in soils and water that are fundamental to the primary productivity of ecosystems. Thus, critical life-giving systems are frequently contaminated with organophosphorus and carbamate pesticides, however briefly, each year.

  5. Determination of Levels of Organochlorine, Organophosphorus, and Pyrethroid Pesticide Residues in Vegetables from Markets in Dar es Salaam by GC-MS

    PubMed Central

    Khamis, Farhat A.; Lugwisha, Esther H. J.

    2017-01-01

    This study investigated the levels of pesticides and metabolites in vegetables from major markets in Dar es Salaam city, Tanzania. Samples of fresh cabbage, spinach, and onions from the markets were analysed for pesticide residues. Extraction was performed using acetone followed by dichloromethane : cyclohexane mixture and the extracts were cleaned up using Florisil. The compounds were determined by gas chromatography-mass spectrometry (GC-MS). Pesticides and metabolites were detected in 72.2% of the samples. The detected pesticide residues and their highest mean concentrations were p,p′-DDT 4.00 × 10−3 mg/kg, p,p′-DDD 6.40 × 10−1 mg/kg, o,p′-DDD 1.00 × 10−2 mg/kg, α-endosulfan 6.00 × 10−1 mg/kg, β-endosulfan 2.10 × 10−1 mg/kg, chlorpyrifos 3.00 mg/kg, and cypermethrin 4.00 × 10−2 mg/kg. The most frequently detected compounds were p,p′-DDD and chlorpyrifos. The order of contamination was spinach > cabbage > onions. Generally, there were no significant variations in concentrations of pesticide residues among samples and sampling sites, which indicated similarities in contamination patterns. The concentrations of contaminants were above the maximum residue limits (MRLs) in 33.3–50% of the samples. The findings indicated risks and concerns for public health. PMID:28280510

  6. Catanionic surfactant ambient cloud point extraction and high-performance liquid chromatography for simultaneous analysis of organophosphorus pesticide residues in water and fruit juice samples.

    PubMed

    Seebunrueng, Ketsarin; Santaladchaiyakit, Yanawath; Soisungnoen, Phimpha; Srijaranai, Supalax

    2011-09-01

    A mixed anionic-cationic surfactant cloud point extraction (CPE) has been developed using sodium dodecyl sulfate (SDS) and tetrabutylammonium bromide (TBABr) for the extraction and preconcentration of organophosphorus pesticides (OPPs) at ambient temperature before analysis by high-performance liquid chromatography. The studied OPPs were azinphos-methyl, parathion-methyl, fenitrothion, diazinon, chlorpyrifos, and prothiophos. The optimum conditions of the mixed anionic-cationic CPE were 50 mmol L(-1) SDS, 100 mmol L(-1) TBABr, and 10% (w/v) NaCl. The extracted OPPs were successfully separated within 11 min using the conditions of a Waters Symmetry C8 column, a flow rate of 0.8 mL min(-1), a gradient elution of methanol and water, and detection at 210 nm. Linearity was found over the range 0.05-5 μg mL(-1), with the correlation coefficients higher than 0.996. The enrichment factor of the target analytes was in the range 6-11, which corresponds to their limits of detection from 1 to 30 ng mL(-1). High precisions (intra-day and inter-day) were obtained with relative standard deviation <1.5% (t(R)) and 10% (peak area). Accuracies (% recovery) of the different spiked OPP concentrations were 82.7-109.1% (water samples) and 80.3-113.3% (fruit juice samples). No contamination by the OPPs was observed in any studied samples.

  7. Validation and use of a fast sample preparation method and liquid chromatography-tandem mass spectrometry in analysis of ultra-trace levels of 98 organophosphorus pesticide and carbamate residues in a total diet study involving diversified food types.

    PubMed

    Chung, Stephen W C; Chan, Benny T P

    2010-07-16

    This paper reports a comprehensive sensitive multi-residue liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for detection, identification and quantitation of 73 pesticides and their related products, a total of 98 analytes, belonging to organophosphorus pesticides (OPPs) and carbamates, in foods. The proposed method makes use of a modified QuEChERS (quick, easy, cheap, effective, rigged, and safe) procedure that combines isolation of the pesticides and sample clean-up in a single step. Analysis is performed by liquid chromatography-electrospray ionization-tandem mass spectrometry operated in the multiple reaction monitoring (MRM) mode, acquiring two specific precursor-product ion transitions per target compound. Two main fragment ions for each pesticide were obtained to achieve the identification according to the SANCO guidelines 10684/2009. The method was validated with various food samples, including edible oil, meat, egg, cheese, chocolate, coffee, rice, tree nuts, citric fruits, vegetables, etc. No significant matrix effect was observed for tested pesticides, therefore, matrix-matched calibration was not necessary. Calibration curves were linear and covered from 1 to 20 microg L(-1) for all compounds studied. The average recoveries, measured at 10 microg kg(-1), were in the range 70-120% for all of the compounds tested with relative standard deviations below 20%, while a value of 10 microg kg(-1) has been established as the method limit of quantitation (MLOQ) for all target analytes. Similar trueness and precision results were also obtained for spiking at 200 microg kg(-1). Expanded uncertainty values were in the range 21-27% while the HorRat ratios were below 1. The method has been successfully applied to the analysis of 700 food samples in the course of a baseline monitoring study of OPPs and carbamates. 2010 Elsevier B.V. All rights reserved.

  8. Sorption of triazine and organophosphorus pesticides on soil and biochar

    USDA-ARS?s Scientific Manuscript database

    Although a large number of reports are available on sorption and degradation of triazine and organophosphorus pesticides in soils, systematic studies are lacking to directly compare and predict the fate of agrochemicals having different susceptibilities for hydrolysis and other degradation pathways....

  9. New insights on molecular interactions of organophosphorus pesticides with esterases.

    PubMed

    Mangas, Iris; Estevez, Jorge; Vilanova, Eugenio; França, Tanos Celmar Costa

    2017-02-01

    Organophosphorus compounds (OPs) are a large and diverse class of chemicals mainly used as pesticides and chemical weapons. People may be exposed to OPs in several occasions, which can produce several distinct neurotoxic effects depending on the dose, frequency of exposure, type of OP, and the host factors that influence susceptibility and sensitivity. These neurotoxic effects are mainly due to the interaction with enzyme targets involved in toxicological or detoxication pathways. In this work, the toxicological relevance of known OPs targets is reviewed. The main enzyme targets of OPs have been identified among the serine hydrolase protein family, some of them decades ago (e.g. AChE, BuChE, NTE and carboxylesterases), others more recently (e.g. lysophospholipase, arylformidase and KIA1363) and others which are not molecularly identified yet (e.g. phenylvalerate esterases). Members of this family are characterized by displaying serine hydrolase activity, containing a conserved serine hydrolase motif and having an alpha-beta hydrolase fold. Improvement in Xray-crystallography and in silico methods have generated new data of the interactions between OPs and esterases and have established new methods to study new inhibitors and reactivators of cholinesterases. Mass spectrometry for AChE, BChE and APH have characterized the active site serine adducts with OPs being useful to detect biomarkers of OPs exposure and inhibitory and postinhibitory reactions of esterases and OPs. The purpose of this review is focus specifically on the interaction of OP with esterases, mainly with type B-esterases, which are able to hydrolyze carboxylesters but inhibited by OPs by covalent phosphorylation on the serine or tyrosine residue in the active sites. Other related esterases in some cases with no-irreversible effect are also discussed. The understanding of the multiple molecular interactions is the basis we are proposing for a multi-target approach for understanding the

  10. Particulate matter formation from photochemical degradation of organophosphorus pesticides

    NASA Astrophysics Data System (ADS)

    Borrás, E.; Ródenas, M.; Vera, T.; Muñoz, A.

    2015-12-01

    Several experiments were performed in the European Photo-reactor - EUPHORE - for studying aerosol formation from organophosphorus pesticides such as diazinon, chlorpyrifos, chlorpyrifos-methyl and pirimiphos-methyl. The mass concentration yields obtained (Y) were in the range 5 - 44% for the photo-oxidation reactions in the presence and the absence of NOx. These results confirm the importance of studying pesticides as significant precursors of atmospheric particulate matter due to the serious risks associated to them. The studies based on the use of EUPHORE photoreactor provide useful data about atmospheric degradation processes of organophosphorus pesticides to the atmosphere. Knowledge of the specific degradation products, including the formation of secondary particulate matter, could complete the assessment of their potential impact, since the formation of those degradation products plays a significant role in the atmospheric chemistry, global climate change, radiative force, and are related to health effects.

  11. Comparison of HS-SDME with SPME and SPE for the determination of eight organochlorine and organophosphorus pesticide residues in food matrices.

    PubMed

    Kin, Chai Mee; Huat, Tan Guan

    2009-09-01

    A headspace single-drop microextraction (HS-SDME) procedure is optimized for the analysis of organochlorine and organophosphorous pesticide residues in food matrices, namely cucumbers and strawberries by gas chromatography with an electron capture detector. The parameters affecting the HS-SDME performance, such as selection of the extraction solvent, solvent drop volume, extraction time, temperature, stirring rate, and ionic strength, were studied and optimized. Extraction was achieved by exposing 1.5 microL toluene drop to the headspace of a 5 mL aqueous solution in a 15-mL vial and stirred at 800 rpm. The analytical parameters, such as linearity, correlation coefficients, precision, limits of detection (LOD), limits of quantification (LOQ), and recovery, were compared with those obtained from headspace solid-phase microextraction (HS-SPME) and solid-phase extraction. The mean recoveries for all three methods were all above 70% and below 104%. HS-SPME was the best method with the lowest LOD and LOQ values. Overall, the proposed HS-SDME method is acceptable in the analysis of pesticide residues in food matrices.

  12. Vortex-assisted low density solvent liquid-liquid microextraction and salt-induced demulsification coupled to high performance liquid chromatography for the determination of five organophosphorus pesticide residues in fruits.

    PubMed

    Seebunrueng, Ketsarin; Santaladchaiyakit, Yanawath; Srijaranai, Supalax

    2015-01-01

    A simple and rapid microextraction method, vortex-assisted low density solvent liquid-liquid microextraction and salt-induced demulsification (VLLME-SID) coupled to high performance liquid chromatography (HPLC) was developed for the determination of organophosphorus pesticide (OPP) residues in fruits. The studied OPPs were azinphos-methyl, parathion-methyl, fenitrothion, diazinon and chlorpyrifos. For VLLME-SID, a mixture of low density solvents (1-dodecanol and hexane) was used as the extraction solvent under vortex agitation for enhancing dispersion. After complete dispersion, the emulsion was formed and the OPPs were extracted into extraction solvent droplets. Then, the emulsion was quickly broken up into two clear phases after the addition of AlCl3 as a demulsifier. Centrifugation was not required in this procedure. Under the optimal conditions, high enrichment factors (180-282), low limit of detections (LODs) (0.05-1 ng mL(-1)) and good precision (RSD≤7% for retention time and peak area) were obtained. The proposed method was successfully applied to the analysis of OPP residues in fruit samples (watermelon, grape, and cantaloupe). The LODs for samples were in the range 0.0006-0.0015 mg kg(-1) which are below the established EU-MRLs (0.01-0.3 mg kg(-1)). Good recoveries were also obtained (80-104%).

  13. Biodegradation and Utilization of Organophosphorus Pesticide Malathion by Cyanobacteria

    PubMed Central

    Ibrahim, Wael M.; Karam, Mohamed A.; El-Shahat, Reda M.; Adway, Asmaa A.

    2014-01-01

    Three strains of filamentous Cyanobacteria were used to study their growth and utilization of organophosphorus pesticide malathion. A sharp decrease in the growth of the algal strains was observed by increasing the concentration of malathion. Amongst them Nostoc muscorum tolerated different concentrations and was recorded as the highest efficient strain for biodegradation (91%) of this compound. Moreover, carbohydrate and protein content of their cells overtopped the other strains especially at higher concentrations. The algal strains were further subjected to grow under P-limitation in absence and presence of malathion. Although, the algal growth under P-limitation recorded a very poor level, a massive enhanced growth and phosphorous content of cells were obtained when the P-limited medium was amended with malathion. This study clarified that N. muscorum with its capability to utilize malathion as a sole phosphorous source is considered as an inexpensive and efficient biotechnology for remediation of organophosphorus pesticide from contaminated wastewater. PMID:24864237

  14. Household organophosphorus pesticide use and Parkinson’s disease

    PubMed Central

    Narayan, Shilpa; Liew, Zeyan; Paul, Kimberly; Lee, Pei-Chen; Sinsheimer, Janet S; Bronstein, Jeff M; Ritz, Beate

    2013-01-01

    Background Household pesticide use is widespread in the USA. Since the 1970s, organophosphorus chemicals (OPs) have been common active ingredients in these products. Parkinson’s disease (PD) has been linked to pesticide exposures but little is known about the contributions of chronic exposures to household pesticides. Here we investigate whether long-term use of household pesticides, especially those containing OPs, increases the odds of PD. Methods In a population-based case-control study, we assessed frequency of household pesticide use for 357 cases and 807 controls, relying on the California Department of Pesticide Regulation product label database to identify ingredients in reported household pesticide products and the Pesticide Action Network pesticide database of chemical ingredients. Using logistic regression we estimated the effects of household pesticide use. Results Frequent use of any household pesticide increased the odds of PD by 47% [odds ratio (OR) = 1.47, (95% confidence interval (CI): 1.13, 1.92)]; frequent use of products containing OPs increased the odds of PD more strongly by 71% [OR = 1.71, (95% CI: 1.21, 2.41)] and frequent organothiophosphate use almost doubled the odds of PD. Sensitivity analyses showed that estimated effects were independent of other pesticide exposures (ambient and occupational) and the largest odds ratios were estimated for frequent OP users who were carriers of the 192QQ paraoxonase genetic variant related to slower detoxification of OPs. Conclusions We provide evidence that household use of OP pesticides is associated with an increased risk of developing PD. PMID:24057998

  15. HIGH PERFORMANCE LIQUID CHROMATOGRAPHIC SEPARATION OF THE ENANTIOMERS OF ORGANOPHOSPHORUS PESTICIDES ON POLYSACCHARIDE CHIRAL STATIONARY PHASES

    EPA Science Inventory

    High-performance liquid chromatographic separation of the individual enantiomers of 12 organophosphorus pesticides (OPs) was obtained on polysaccharide enantioselective HPLC columns using alkane-alcohol mobile phase. The OP pesticides were crotoxyphos, dialifor, fonofos, fenamiph...

  16. HPLC SEPARATION OF CHIRAL ORGANOPHOSPHORUS PESTICIDES ON POLYSACCHARIDE CHIRAL STATIONARY PHASES

    EPA Science Inventory

    High-performance liquid chromatographic separation of the individual enantiomers of 12 organophosphorus pesticides (OPs) were obtained on polysaccharide chiral HPLC columns using an alkane-alcohol mobile phase. The OP pesticides were crotoxyphos, dialifor, dyfonate, fenamiphos, ...

  17. Organophosphorus hydrolase (OpdB) of Lactobacillus brevis WCP902 from kimchi is able to degrade organophosphorus pesticides.

    PubMed

    Islam, Shah Md Asraful; Math, Renukaradhya K; Cho, Kye Man; Lim, Woo Jin; Hong, Su Young; Kim, Jong Min; Yun, Myoung Geun; Cho, Ji Joong; Yun, Han Dae

    2010-05-12

    Lactobacillus brevis WCP902 that is capable of biodegrading chlorpyrifos was isolated from kimchi. The opdB gene cloned from this strain revealed 825 bp, encoding 274 aa, and an enzyme molecular weight of about 27 kDa. OpdB contains the same Gly-X-Ser-X-Gly motif found in most bacterial and eukaryotic esterase, lipase, and serine hydrolases, yet it is a novel member of the GDSVG family of esterolytic enzymes. Its conserved serine residue, Ser82, is significantly involved with enzyme activity that may have application for removing some pesticides. Optimum organophosphorus hydrolase (OpdB) activity appeared at pH 6.0 and 35 degrees C and during degradation of chlorpyrifos, coumaphos, diazinon, methylparathion, and parathion.

  18. Prediction of acute toxicity of organophosphorus pesticides using topological indices.

    PubMed

    García-Domenech, R; Alarcón-Elbal, P; Bolas, G; Bueno-Marí, R; Chordá-Olmos, F A; Delacour, S A; Mouriño, M C; Vidal, A; Gálvez, J

    2007-01-01

    Topological indices were used in the prediction of the acute toxicity (intraperitoneal and oral LD(50)) of organophosphorus pesticides on rats. Models with six variables for the prediction of LD(50)-i.p. (r = 0.849, Q(2) = 0.613) and eight variables for LD(50)-oral (r = 0.906, Q(2) = 0.701) were selected. External group and cross-validation by use of leave-n-out tests were also performed in order to assess the stability and the prediction performance of the selected topological models.

  19. Simple, specific analysis of organophosphorus and carbamate pesticides in sediments using column extraction and gas chromatography

    USGS Publications Warehouse

    Belisle, A.A.; Swineford, D.M.

    1988-01-01

    A simple, specific procedure was developed for the analysis of organophosphorus and carbamate pesticides in sediment. The wet soil was mixed with anhydrous sodium sulfate to bind water and the residues were column extracted in acetone:methylene chloride (1:l,v/v). Coextracted water was removed by additional sodium sulfate packed below the sample mixture. The eluate was concentrated and analyzed directly by capillary gas chromatography using phosphorus and nitrogen specific detectors. Recoveries averaged 93 % for sediments extracted shortly after spiking, but decreased significantly as the samples aged.

  20. Chloramination of organophosphorus pesticides found in drinking water sources.

    PubMed

    Duirk, Stephen E; Desetto, Lisa M; Davis, Gary M; Lindell, Cristal; Cornelison, Christopher T

    2010-02-01

    The degradation of commonly detected organophosphorus (OP) pesticides, in drinking water sources, was investigated under simulated chloramination conditions. Due to monochloramine autodecomposition, it is difficult to observe the direct reaction of monochloramine with each OP pesticide. Therefore, a model was developed to examine the reaction of monochloramine (NH(2)Cl) and dichloramine (NHCl(2)) with chlorpyrifos (CP), diazinon (DZ), and malathion (MA). Monochloramine was found not to be very reactive with each OP pesticides, (k)NH(2)Cl,OP = 11-21 M(-1)h(-1). While, dichloramine (NHCl(2)) was found to be 2 orders of magnitude more reactive with each of the OP pesticides than monochloramine, (k)NHCl(2),OP = 2000-2900 M(-1)h(-1), which is still three orders of magnitude less than the hypochlorous acid reaction rate coefficient with each OP pesticide. For each pesticide, the reactivity of the three chlorinated oxidants was then found to correlate with half-wave potentials (E(1/2)) of each oxidant. With reaction rate coefficients for the three chlorinated oxidations as well as neutral and alkaline hydrolysis rate coefficients for the pesticides, the model was used to determine the dominant reaction pathways as a function of pH. At pH 6.5, OP pesticide transformation was mostly due to the reaction of hypochlorous acid and dichloramine. Above pH 8, alkaline hydrolysis or the direct reaction with monochloramine was the primary degradation pathway responsible for the transformation of OP pesticides. This demonstrates the ability of models to be used as tools to elucidate degradation pathways and parameterize critical reaction parameters when used with select yet comprehensive data sets. (c) 2009. Published by Elsevier Ltd.

  1. Novel and rapid method for determination of organophosphorus pesticide residues in edible fungus using direct gas purge microsyringe extraction coupled on-line with gas chromatography-mass spectrometry.

    PubMed

    Nan, Jingxi; Wang, Juan; Piao, Xiangfan; Yang, Cui; Wu, Xue; Quinto, Maurizio; Li, Donghao

    2015-09-01

    In this work a new analytical method for a rapid and simultaneous determination of 28 organophosphorus pesticides (OPPs) residues in edible fungus using gas purge microsyringe extraction (GP-MSE), coupled with on-line gas chromatography-mass spectrometry (GP-MSE-GC-MS) has been developed and optimized. GP-MSE, a novel gas flow liquid-phase microextraction technique, has been then fruitfully used as innovative and one-step extraction procedure, allowing a direct injection into the gas chromatograph coupled with a mass spectrometry detector (GC-MS) system without any further cleaning step. Once optimized, the GP-MSE-GC-MS analysis procedure showed reproducibility values, resolutions, linear responses, detection and quantification limits that allowed to consider this method suitable for the analysis of the 28 OPPs in real samples. Furthermore, OPP recoveries and the relative standard deviations (RSDs) ranged from 85.26% to 100.21%, and from 1.6% to 6.9%, respectively. This procedure was then used for the analysis of real samples and the obtained results were compared with those of ultrasonic extraction-solid phase extraction. Among the 28 OPPs, 14 of them were found in Lentinus edodes and Enoki mushrooms fungus samples, with a total concentrations of 112.7 and 210.7 μg kg(-1), respectively. This work demonstrated then that GP-MSE-GC-MS provided a highly efficient, solvent-saving, accurate and sensitive quantitative analysis method for a rapid determination of OPPs in edible fungus. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Pesticide residue determination in vegetables from western China applying gas chromatography with mass spectrometry.

    PubMed

    Qin, Guofu; Zou, Keting; Li, Yongbo; Chen, Yan; He, Fengrui; Ding, Guirong

    2016-09-01

    In this study,an effort has been made to evaluate the pesticide residues in vegetables from western China. Fifty-one pesticides, including organophosphorus, organochlorine, carbamate and pyrethroid, were detected in 369 commonly used vegetables by GC-MS. Concentrations of organophosphorus pesticides were detected ranging from 0.0008 to 18.8200 mg/kg, among which organophosphorus pesticide concentrations exceeded their maximum residue levels (MRLs) in five samples. Carbamate and organochlorine pesticides were determined to have concentrations in the range of 0.0012-0.7928 mg/kg. The residual concentrations of carbamate pesticides in six samples and organochlorine pesticides in four samples exceeded their MRLs. The residual concentrations of five pyrethroid pesticides were within the range of 0.0016-6.0827 mg/kg and the pyrethroid residues in two samples exceeded their MRLs. The results revealed that pesticide residues in 70.73% of the vegetables samples were not detected, while in the rest of vegetables there were one or more pesticide residues and some even exceeded their MRLs, which would threaten the health of consumers. Our work provides significant information for the food safety regulations to control the excessive use of some pesticides on those kinds of vegetables from western China. Copyright © 2016 John Wiley & Sons, Ltd.

  3. [The intermediate syndrome during organophosphorus pesticide poisoning].

    PubMed

    Benslama, A; Moutaouakkil, S; Charra, B; Menebhi, L

    2004-04-01

    Acute intoxication by organophosphate pesticides is frequent in Morocco. We report two cases of malathion poisoning complicated by intermediate syndrome. The purpose of this work is to describe distinctive features of this syndrome, it arises 48-96 h after the cholinergic crisis and it is characterized by respiratory paresis with difficulties of weaning from the assisted respiratory, deficit of proximal limbs, neck flexors, and cranial nerves. This syndrome coincides with the prolonged inhibition of the acetylcholinesterase, and is not due to the necrosis of muscular fiber's necrosis. Both clinical and electromyographic features are explained by a combined pre- and postsynaptic dysfunction of the neuromuscular transmission. The difficulty of this syndrome lies in its rarity and also its severity, because of the respiratory failure, which justifies medical supervision in intensive care unit, for at least 96 h, in expectation for the respiratory distress, all the more cholinergic syndrome is intense.

  4. Sorption of triazine and organophosphorus pesticides on soil and biochar.

    PubMed

    Uchimiya, Minori; Wartelle, Lynda H; Boddu, Veera M

    2012-03-28

    Sorption and degradation are the primary processes controlling the efficacy and runoff contamination risk of agrochemicals. Considering the longevity of biochar in agroecosystems, biochar soil amendment must be carefully evaluated on the basis of the target agrochemical and soil types to achieve agricultural (minimum impact on efficacy) and environmental (minimum runoff contamination) benefits. In this study, sorption-desorption isotherms and kinetics of triazine (deisopropylatrazine) and organophosphorus (malathion, parathion, and diazinon) pesticides were first investigated on various soil types ranging from clayey, acidic Puerto Rican forest soil (PR) to heavy metal contaminated small arms range (SAR) soils of sandy and peaty nature. On PR, malathion sorption did not reach equilibrium during the 3 week study. Comparison of solution-phase molar phosphorus and agrochemical concentrations suggested that degradation products of organophosphorus pesticides were bound on soil surfaces. The degree of sorption on different soils showed the following increasing trend: deisopropylatrazine < malathion < diazinon < parathion. While sorption of deisopropylatrazine on SAR soils was not affected by diazinon or malathion, deisopropylatrazine suppressed the sorption of diazinon and malathion. Deisopropylatrazine irreversibly sorbed on biochars, and greater sorption was observed with higher Brunauer-Emmett-Teller surface area of biochar (4.7-2061 mg g(-1)). The results suggested the utility of biochar for remediation of sites where concentrations of highly stable and mobile agrochemicals exceed the water-quality benchmarks.

  5. A thin film electro-acoustic enzyme biosensor allowing the detection of trace organophosphorus pesticides.

    PubMed

    Chen, Da; Wang, Jingjing; Xu, Yan; Zhang, Luyin

    2012-10-01

    We report an analytical method using a thin film electro-acoustic resonator for the detection of organophosphorus pesticides. The acetylcholinesterase (AChE) enzyme was immobilized on the surface of the resonator. In the presence of organophosphorus compounds, the degree of inhibitory effect of organophosphorus compounds on the AChE activity and the concentration of pesticides were detected in real time by measuring the frequency shift of the resonator. The proposed device has a remarkably low detection limit of 1.8×10(-11)M and obvious advantages such as small size, simple operation, and integrated circuit compatibility, providing a promising tool for pesticide analysis.

  6. Liquid-phase microextraction of organophosphorus pesticides using supramolecular solvent as a carrier for ferrofluid.

    PubMed

    Zohrabi, Parvin; Shamsipur, Mojtaba; Hashemi, Mahdi; Hashemi, Beshare

    2016-11-01

    A liquid-phase microextraction based on application of supramolecular solvent as a carrier for ferrofluid has been developed for the extraction and determination of three organophosphorus pesticides (OPPs). The ferrofluid was produced from combination of oleic acid coated magnetic particles and supramolecular solvent as the extractant solvent. Ferrofluid can be attracted by a magnet, and no centrifugation step was needed for phase separation. A response surface methodology (RSM) based on central composite design (CCD) was used for efficient optimization of the main variables in the extraction procedure. Under the optimum experimental conditions, the calibration curves found to be linear in the range of 0.5-400µgL(-1) with correlation coefficients ranging from 0.9967 to 0.9984. The intra-day and inter-day precision (RSD %) for 100 and 200µgL(-1) of each pesticides were in the range of 2.0-5.3% and 2.6-5.7%, respectively. The limit of detection (S/N=3), ranged from 0.1 to 0.35μgL(-1). The proposed method was successfully applied to the extraction and determination of organophosphorus pesticide residues in water and fruit juice samples.

  7. Highly sensitive detection of organophosphorus pesticides by acetylcholinesterase-coated thin film bulk acoustic resonator mass-loading sensor.

    PubMed

    Chen, Da; Wang, Jingjing; Xu, Yan; Li, Dehua; Zhang, Luyin; Li, Zhaoxin

    2013-03-15

    An acetylcholinesterase-coated thin film bulk acoustic resonator has been developed for the detection of organophosphorus pesticides. The thin film bulk acoustic resonator acts as a robust mass-sensitive transducer for bio-sensing. This device works in thickness shear mode with a resonance at 1.97 GHz. The detection is based on the inhibitory effects of organophosphorus compounds on the enzymatic activity of the acetylcholinesterase immobilized on one of the faces of the acoustic resonator. The enzyme reaction in the substrate solution and the inhibitory effect is observed are real time by measuring the frequency shift. The presence of organophosphorus pesticides can be detected from the diminution of the frequency shift compared with the levels found in their absence. The device exhibits linear responses, good reproducibility, simple operation, portability and a low detection limit of 5.3×10(-11) M for paraoxon. The detection results of organophosphorus pesticide residues in practical samples show that the proposed sensor has the feasibility and sensing accuracy comparable to gas chromatography.

  8. Development of a heterologous enzyme-linked immunosorbent assay for organophosphorus pesticides with phage-borne peptide.

    PubMed

    Hua, Xiude; Liu, Xiaofeng; Shi, Haiyan; Wang, Yanru; Kim, Hee Joo; Gee, Shirley J; Wang, Minghua; Liu, Fengquan; Hammock, Bruce D

    2014-01-01

    An enzyme-linked immunosorbent assay (ELISA) was developed to detect organophosphorus pesticides using a phage-borne peptide that was isolated from a cyclic 8-residue peptide phage library. The IC50 values of the phage ELISA ranged from 1.4 to 92.1 μg L(-1) for eight organophosphorus pesticides (parathion-methyl, parathion, fenitrothion, cyanophos, EPN, paraoxon-methyl, paraoxon, fenitrooxon). The sensitivity was improved 120- and 2-fold compared to conventional homologous and heterologous ELISA, respectively. The selectivity of the phage ELISA was evaluated by measuring its cross-reactivity with 23 organophosphorus pesticides, among which eight were the main cross-reactants. The spike recoveries were between 66.1% and 101.6% for the detection of single pesticide residues of parathion-methyl, parathion and fenitrothion in Chinese cabbage, apple and greengrocery, and all of the coefficient of variation were less than or equal to 15.9%. Moreover, the phage ELISA results were validated by gas chromatography. The results indicate that isolating phage-borne peptides from phage display libraries is an alternative method for the development of a heterologous immunoassay and that the developed assay has a lower limit of detection than the chemically synthesized competitor assay.

  9. SELECTED PESTICIDE RESIDUES AND METABOLITES IN URINE FROM A SURVEY OF THE U.S. GENERAL POPULATION

    EPA Science Inventory

    Residues of toxic chemicals in human tissues and fluids can be important indicators of exposure. Urine collected from a subsample of the second National Health and Nutrition Examination Survey was analyzed for organochlorine, organophosphorus, and chlorophenoxy pesticides or the...

  10. Determination of Carbamate and Organophosphorus Pesticides in Vegetable Samples and the Efficiency of Gamma-Radiation in Their Removal

    PubMed Central

    Chowdhury, Muhammed Alamgir Zaman; Jahan, Iffat; Karim, Nurul; Alam, Mohammad Khorshed; Rahman, Mohammad Abdur; Moniruzzaman, Mohammed; Gan, Siew Hua; Fakhruddin, Abu Naieum Muhammad

    2014-01-01

    In the present study, the residual pesticide levels were determined in eggplants (Solanum melongena) (n = 16), purchased from four different markets in Dhaka, Bangladesh. The carbamate and organophosphorus pesticide residual levels were determined by high performance liquid chromatography (HPLC), and the efficiency of gamma radiation on pesticide removal in three different types of vegetables was also studied. Many (50%) of the samples contained pesticides, and three samples had residual levels above the maximum residue levels determined by the World Health Organisation. Three carbamates (carbaryl, carbofuran, and pirimicarb) and six organophosphates (phenthoate, diazinon, parathion, dimethoate, phosphamidon, and pirimiphos-methyl) were detected in eggplant samples; the highest carbofuran level detected was 1.86 mg/kg, while phenthoate was detected at 0.311 mg/kg. Gamma radiation decreased pesticide levels proportionately with increasing radiation doses. Diazinon, chlorpyrifos, and phosphamidon were reduced by 40–48%, 35–43%, and 30–45%, respectively, when a radiation strength of 0.5 kGy was utilized. However, when the radiation dose was increased to 1.0 kGy, the levels of the pesticides were reduced to 85–90%, 80–91%, and 90–95%, respectively. In summary, our study revealed that pesticide residues are present at high amounts in vegetable samples and that gamma radiation at 1.0 kGy can remove 80–95% of some pesticides. PMID:24711991

  11. Determination of carbamate and organophosphorus pesticides in vegetable samples and the efficiency of gamma-radiation in their removal.

    PubMed

    Chowdhury, Muhammed Alamgir Zaman; Jahan, Iffat; Karim, Nurul; Alam, Mohammad Khorshed; Abdur Rahman, Mohammad; Moniruzzaman, Mohammed; Gan, Siew Hua; Fakhruddin, Abu Naieum Muhammad

    2014-01-01

    In the present study, the residual pesticide levels were determined in eggplants (Solanum melongena) (n = 16), purchased from four different markets in Dhaka, Bangladesh. The carbamate and organophosphorus pesticide residual levels were determined by high performance liquid chromatography (HPLC), and the efficiency of gamma radiation on pesticide removal in three different types of vegetables was also studied. Many (50%) of the samples contained pesticides, and three samples had residual levels above the maximum residue levels determined by the World Health Organisation. Three carbamates (carbaryl, carbofuran, and pirimicarb) and six organophosphates (phenthoate, diazinon, parathion, dimethoate, phosphamidon, and pirimiphos-methyl) were detected in eggplant samples; the highest carbofuran level detected was 1.86 mg/kg, while phenthoate was detected at 0.311 mg/kg. Gamma radiation decreased pesticide levels proportionately with increasing radiation doses. Diazinon, chlorpyrifos, and phosphamidon were reduced by 40-48%, 35-43%, and 30-45%, respectively, when a radiation strength of 0.5 kGy was utilized. However, when the radiation dose was increased to 1.0 kGy, the levels of the pesticides were reduced to 85-90%, 80-91%, and 90-95%, respectively. In summary, our study revealed that pesticide residues are present at high amounts in vegetable samples and that gamma radiation at 1.0 kGy can remove 80-95% of some pesticides.

  12. A nano-silver enzyme electrode for organophosphorus pesticide detection.

    PubMed

    Zheng, Qiqi; Yu, Yonghua; Fan, Kai; Ji, Feng; Wu, Jian; Ying, Yibin

    2016-08-01

    A nano-silver electrode immobilizing acetylcholinesterase (AChE) for the detection of organophosphorus (OPPs) pesticides is reported. Scanning electron microscopy (SEM) was used to characterize the surface structure of two kinds of electrodes fabricated with different sizes of silver powders and the interface between chitosan layer and nano-silver powder layer. Cyclic voltammetry was carried out to characterize the response of silver/chitosan electrode in the absence and in the presence of thiocholine (TCh). It was also used to evaluate the insulativity of the chitosan layer. An amperometric method was performed to measure the response of the electrode to TCh, which is the product of the enzymatic reaction for detecting organophosphorus pesticides indirectly. Although there are many kinds of nanoparticles, silver was chosen for its internal advantage in detecting TCh at low potential without further modification. The result shows nano-silver powder has better performance than usual silver powder, and the limit of detection of paraoxon is 4 ppb under optimized conditions. One percent (w/v) chitosan solution was used as binder for the immobilization of nano-silver powder and AChE, which made it possible for independent electrode fabrication at room temperature, whereas 3% (w/v) chitosan solution was used as insulating compound for controlling the electrode area. Unlike traditional organic insulating ink, chitosan is safe and environmentally friendly, and it is used as insulating material for the first time. The flexible nano-silver/AChE/chitosan electrode was evaluated in Chinese chives and cabbage, and the recoveries of standard addition were 105.11 and 96.41%, respectively. Owing to the antibacterial property of nano-silver and the biocompatibility, safety, and biodegradability of chitosan, the proposed method is safe, facile, environmentally friendly, and has great potential in organophosphorus pesticide detection for food safety. Graphical Abstract Current

  13. MOVEMENT AND DEPOSITION OF TWO ORGANOPHOSPHORUS PESTICIDES WITHIN A RESIDENCE AFTER INTERIOR AND EXTERIOR APPLICATIONS

    EPA Science Inventory

    Post-application temporal and spatial distributions of two organophosphorus pesticides, diazinon and chlorpyrifos, were monitored after homeowner applications for indoor and outdoor insect control. Samples were taken before and up to 12 days after treatments in the family room...

  14. MOVEMENT AND DEPOSITION OF TWO ORGANOPHOSPHORUS PESTICIDES WITHIN A RESIDENCE AFTER INTERIOR AND EXTERIOR APPLICATIONS

    EPA Science Inventory

    Post-application temporal and spatial distributions of two organophosphorus pesticides, diazinon and chlorpyrifos, were monitored after homeowner applications for indoor and outdoor insect control. Samples were taken before and up to 12 days after treatments in the family room...

  15. UPTAKE AND PHYTOTRANSFORMATION OF ORGANOPHOSPHORUS PESTICIDES BY AXENICALLY CULTIVATED AQUATIC PLANTS

    EPA Science Inventory

    The uptake and phytotransformation of organophosphorus (OP) pesticides (malathion, demeton-S-methyl, and crufomate) was investigated in vitro using the axenically aquatic cultivated plants parrot feather (Myriophyllum aquaticum), duckweed (Spirodela oligorrhiza L.), and elodea (E...

  16. UPTAKE AND PHYTOTRANSFORMATION OF ORGANOPHOSPHORUS PESTICIDES BY AXENICALLY CULTIVATED AQUATIC PLANTS

    EPA Science Inventory

    The uptake and phytotransformation of organophosphorus (OP) pesticides (malathion, demeton-S-methyl, and crufomate) was investigated in vitro using the axenically aquatic cultivated plants parrot feather (Myriophyllum aquaticum), duckweed (Spirodela oligorrhiza L.), and elodea (E...

  17. Modulation of immune response by organophosphorus pesticides: fishes as a potential model in immunotoxicology.

    PubMed

    Díaz-Resendiz, K J G; Toledo-Ibarra, G A; Girón-Pérez, M I

    2015-01-01

    Immune response is modulated by different substances that are present in the environment. Nevertheless, some of these may cause an immunotoxic effect. In this paper, the effect of organophosphorus pesticides (frequent substances spilled in aquatic ecosystems) on the immune system of fishes and in immunotoxicology is reviewed. Furthermore, some cellular and molecular mechanisms that might be involved in immunoregulation mechanisms of organophosphorus pesticides are discussed.

  18. Modulation of Immune Response by Organophosphorus Pesticides: Fishes as a Potential Model in Immunotoxicology

    PubMed Central

    Díaz-Resendiz, K. J. G.; Toledo-Ibarra, G. A.; Girón-Pérez, M. I.

    2015-01-01

    Immune response is modulated by different substances that are present in the environment. Nevertheless, some of these may cause an immunotoxic effect. In this paper, the effect of organophosphorus pesticides (frequent substances spilled in aquatic ecosystems) on the immune system of fishes and in immunotoxicology is reviewed. Furthermore, some cellular and molecular mechanisms that might be involved in immunoregulation mechanisms of organophosphorus pesticides are discussed. PMID:25973431

  19. Rapid biodegradation of organophosphorus pesticides by Stenotrophomonas sp. G1.

    PubMed

    Deng, Shuyan; Chen, Yao; Wang, Daosheng; Shi, Taozhong; Wu, Xiangwei; Ma, Xin; Li, Xiangqiong; Hua, Rimao; Tang, Xinyun; Li, Qing X

    2015-10-30

    Organophosphorus insecticides have been widely used, which are highly poisonous and cause serious concerns over food safety and environmental pollution. A bacterial strain being capable of degrading O,O-dialkyl phosphorothioate and O,O-dialkyl phosphate insecticides, designated as G1, was isolated from sludge collected at the drain outlet of a chlorpyrifos manufacture plant. Physiological and biochemical characteristics and 16S rDNA gene sequence analysis suggested that strain G1 belongs to the genus Stenotrophomonas. At an initial concentration of 50 mg/L, strain G1 degraded 100% of methyl parathion, methyl paraoxon, diazinon, and phoxim, 95% of parathion, 63% of chlorpyrifos, 38% of profenofos, and 34% of triazophos in 24 h. Orthogonal experiments showed that the optimum conditions were an inoculum volume of 20% (v/v), a substrate concentration of 50 mg/L, and an incubation temperature in 40 °C. p-Nitrophenol was detected as the metabolite of methyl parathion, for which intracellular methyl parathion hydrolase was responsible. Strain G1 can efficiently degrade eight organophosphorus pesticides (OPs) and is a very excellent candidate for applications in OP pollution remediation.

  20. Medical treatment of acute poisoning with organophosphorus and carbamate pesticides.

    PubMed

    Jokanović, Milan

    2009-10-28

    Organophosphorus compounds (OPs) are used as pesticides and developed as warfare nerve agents such as tabun, soman, sarin, VX and others. Exposure to even small amounts of an OP can be fatal and death is usually caused by respiratory failure. The mechanism of OP poisoning involves inhibition of acetylcholinesterase (AChE) leading to inactivation of the enzyme which has an important role in neurotransmission. AChE inhibition results in the accumulation of acetylcholine at cholinergic receptor sites, producing continuous stimulation of cholinergic fibers throughout the nervous systems. During more than five decades, pyridinium oximes have been developed as therapeutic agents used in the medical treatment of poisoning with OP. They act by reactivation of AChE inhibited by OP. However, they differ in their activity in poisoning with pesticides and warfare nerve agents and there is still no universal broad-spectrum oxime capable of protecting against all known OP. In spite of enormous efforts devoted to development of new pyridinium oximes as potential antidotes against poisoning with OP only four compounds so far have found its application in human medicine. Presently, a combination of an antimuscarinic agent, e.g. atropine, AChE reactivator such as one of the recommended pyridinium oximes (pralidoxime, trimedoxime, obidoxime and HI-6) and diazepam are used for the treatment of OP poisoning in humans. In this article the available data related to medical treatment of poisoning with OP pesticides are reviewed and the current recommendations are presented.

  1. Multidimensional Profiling Platforms Reveal Metabolic Dysregulation caused by Organophosphorus Pesticides

    PubMed Central

    Medina-Cleghorn, Daniel; Heslin, Ann; Morris, Patrick J.; Mulvihill, Melinda M.; Nomura, Daniel K.

    2014-01-01

    We are environmentally exposed to countless synthetic chemicals on a daily basis with an increasing number of these chemical exposures linked to adverse health effects. However, our understanding of the (patho)physiological effects of these chemicals remains poorly understood, due in-part to a general lack of effort to systematically and comprehensively identify the direct interactions of environmental chemicals with biological macromolecules in mammalian systems in vivo. Here, we have used functional chemoproteomic and metabolomic platforms to broadly identify direct enzyme targets that are inhibited by widely used organophosphorus (OP) pesticides in vivo in mice and to determine metabolic alterations that are caused by these chemicals. We find that these pesticides directly inhibit over 20 serine hydrolases in vivo leading to widespread disruptions in lipid metabolism. Through identifying direct biological targets of OP pesticides, we show heretofore unrecognized modes of toxicity that may be associated with these agents and underscore the utility of utilizing multidimensional profiling approaches to obtain a more complete understanding of toxicities associated with environmental chemicals. PMID:24205821

  2. The Fate of Organophosphorus Pesticides during Camellia Oil Production.

    PubMed

    Liu, Yihua; Mo, Runhong; Zhong, Donglian; Shen, Danyu; Ni, Zhanglin; Tang, Fubin

    2015-08-01

    The purpose of this study was to investigate the fate of organophosphorus pesticides (OPs) during camellia oil production process, from camellia fruit to the final oil product. The results showed that the OPs were mainly distributed in the peel of camellia fruit, basically above 40% after the pesticide application of 7 d (P < 0.05). A small amount of OPs could enter into the seed and convert to crude camellia oil, with the concentration of 19.5 to 548.2 mg/L. In addition, metabolites of OPs (25.7 to 768.9 mg/L) could be detected in the crude camellia oil. Moreover, the refining process (degumming, deacidfying, bleaching) had a significant effect on the removal of OPs from the crude camellia oil (P < 0.05), and the effect was related to the octanol-water partition constant (LogP) of pesticide. The larger the LogP, the more stable the OPs were during refining process. The final refined camellia oil was found to have no detectable levels of OPs metabolite.

  3. [Terahertz spectroscopic investigation of organophosphorus pesticide parathion-methyl].

    PubMed

    Yan, Zhi-Gang; Zheng, Song; Xie, Qiang-Jun; Zhou, Ze-Kui

    2009-10-01

    The present paper reports the theoretical and experimental vibrational spectra of organophosphorus pesticide parathion-methyl in the frequency range from 0.2 to 2.0 THz respectively. Under the room temperature and nitrogen conditions, the absorption peaks were found at 0.65, 1.33, 1.81 and 1.91 THz, and the average refractive index was 1.39 based on the terahertz time-domain spectroscopy (THz-TDS). In parallel with the experimental study, density functional theory (DFT) was applied to obtain the structure and vibrational frequencies of parathion-methyl in the terahertz region. The calculated results are in reasonable agreement with the experimental data. The absorption features are caused by the collective vibrational and torsional modes, and the different absorption peaks correspond to different vibrational modes.

  4. Thermal stability of organophosphorus pesticide triazophos and its relevance in the assessment of risk to the consumer of triazophos residues in food.

    PubMed

    Holden, A J; Chen, L; Shaw, I C

    2001-01-01

    The degradation of triazophos in aqueous solutions was monitored at 205 and 254 nm after separation using high-performance liquid chromatography. An ODS column was used with a mobile phase of 60% acetonitrile and 0.04% phosphoric acid at a flow rate of 1.4 cm(3) min(-)(1). When dissolved in distilled water, approximately 30% of the original triazophos was detected. The effect of heating time and temperature on a 0.5 mg dm(-3) standard was investigated. Over a 150 min period at 100 degrees C the peak area detected for the standard decreased by 58.67 +/- 6.19 and 65.03 +/- 4.61% when measured at 254 and 205 nm, respectively. The precision of the absorbance detected at 205 and 254 nm was 3.54 +/- 2.8 and 3.86 +/- 3.9%, respectively. There was a significant difference (P = 0.10) between the precision of the results obtained at each wavelength. The t(calcd) value was -2.236 and the t(crit) value was 1.94. The most sensitive wavelength was 205 nm. A 54% difference in the gradients of the calibration graphs obtained at each wavelength was observed. The results suggest that approximately 72% of triazophos is degraded during a 20 min cooking period at 100 degrees C, due to ambient and elevated temperature hydrolysis. Therefore, the dose to the consumer of triazophos residues in cooked food is likely to be approximately 72% lower than in the raw food, with a concomitant reduction in toxicological risk.

  5. Presence of organophosphorus pesticide oxygen analogs in air samples

    NASA Astrophysics Data System (ADS)

    Armstrong, Jenna L.; Fenske, Richard A.; Yost, Michael G.; Galvin, Kit; Tchong-French, Maria; Yu, Jianbo

    2013-02-01

    A number of recent toxicity studies have highlighted the increased potency of oxygen analogs (oxons) of several organophosphorus (OP) pesticides. These findings were a major concern after environmental oxons were identified in environmental samples from air and surfaces following agricultural spray applications in California and Washington State. This paper reports on the validity of oxygen analog measurements in air samples for the OP pesticide, chlorpyrifos. Controlled environmental and laboratory experiments were used to examine artificial formation of chlorpyrifos-oxon using OSHA Versatile Sampling (OVS) tubes as recommended by NIOSH method 5600. Additionally, we compared expected chlorpyrifos-oxon attributable to artificial transformation to observed chlorpyrifos-oxon in field samples from a 2008 Washington State Department of Health air monitoring study using non-parametric statistical methods. The amount of artificially transformed oxon was then modeled to determine the amount of oxon present in the environment. Toxicity equivalency factors (TEFs) for chlorpyrifos-oxon were used to calculate chlorpyrifos-equivalent air concentrations. The results demonstrate that the NIOSH-recommended sampling matrix (OVS tubes with XAD-2 resin) was found to artificially transform up to 30% of chlorpyrifos to chlorpyrifos-oxon, with higher percentages at lower concentrations (<30 ng m-3) typical of ambient or residential levels. Overall, the 2008 study data had significantly greater oxon than expected by artificial transformation, but the exact amount of environmental oxon in air remains difficult to quantify with the current sampling method. Failure to conduct laboratory analysis for chlorpyrifos-oxon may result in underestimation of total pesticide concentration when using XAD-2 resin matrices for occupational or residential sampling. Alternative methods that can accurately measure both OP pesticides and their oxygen analogs should be used for air sampling, and a toxicity

  6. New experimental Oximes in the management of organophosphorus pesticides poisoning.

    PubMed

    Barelli, A; Soave, P M; Del Vicario, M; Barelli, R

    2011-12-01

    Organophosphorus compounds (OPCs) are widely used in agriculture as pesticides and occasionally in industrial settings. They have also been developed as warfare nerve agents. OPCs poisoning from intentional, accidental, and occupational exposure is a major public health problem, especially across the rural developing world. The main toxic mechanism of OPCs is the inhibition of the enzymes acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE), resulting in accumulation of acetylcholine (ACh) at the synapse with cholinergic crisis and possible death. Exposure to even small amounts of an OPC can be fatal and death is usually caused by respiratory failure. Standard treatment involves the administration of intravenous atropine and an oxime to counteract acetylcholinesterase inhibition at the synapse, but the usefulness of oximes is still debated. During more than five decades, pyridinium oximes have been developed as therapeutic agents used in the medical treatment of poisoning with OPCs. They act by reactivation of AChE inhibited by OPCs. However, their activity in poisonings with pesticides and warfare nerve agents is different, and there is still no universal oxime sufficiently effective against all known OPCs. The aim of this article was to review the most recent findings in this field and compare the protection conferred by the new K-oximes and sugar oximes with the effect of the four recommended pyridinium oximes (pralidoxime, obidoxime, trimedoxime, and HI-6), in the search for a broad-spectrum AChE reactivator.

  7. Detection of Organophosphorus Pesticides with Colorimetry and Computer Image Analysis.

    PubMed

    Li, Yanjie; Hou, Changjun; Lei, Jincan; Deng, Bo; Huang, Jing; Yang, Mei

    2016-01-01

    Organophosphorus pesticides (OPs) represent a very important class of pesticides that are widely used in agriculture because of their relatively high-performance and moderate environmental persistence, hence the sensitive and specific detection of OPs is highly significant. Based on the inhibitory effect of acetylcholinesterase (AChE) induced by inhibitors, including OPs and carbamates, a colorimetric analysis was used for detection of OPs with computer image analysis of color density in CMYK (cyan, magenta, yellow and black) color space and non-linear modeling. The results showed that there was a gradually weakened trend of yellow intensity with the increase of the concentration of dichlorvos. The quantitative analysis of dichlorvos was achieved by Artificial Neural Network (ANN) modeling, and the results showed that the established model had a good predictive ability between training sets and predictive sets. Real cabbage samples containing dichlorvos were detected by colorimetry and gas chromatography (GC), respectively. The results showed that there was no significant difference between colorimetry and GC (P > 0.05). The experiments of accuracy, precision and repeatability revealed good performance for detection of OPs. AChE can also be inhibited by carbamates, and therefore this method has potential applications in real samples for OPs and carbamates because of high selectivity and sensitivity.

  8. Recovery of cholinesterase activity in mallard ducklings administered organophosphorus pesticides

    USGS Publications Warehouse

    Fleming, W.J.; Bradbury, S.P.

    1981-01-01

    Oral doses of the organophosphorus pesticides acephate, dicrotophos, fensulfothion, fonofos, malathion, and parathion were administered to mallard ducklings (Anas platyrhynchos), and brain and plasma cholinesterase (ChE) activities were determined for up to 77 d after dosing. In vivo recovery of brain ChE activity to within 2 standard deviations of the mean activity of undosed birds occurred within 8 d, after being depressed an average of 25-58% at 24 h after dosing. In vivo recovery of plasma ChE appeared as fast as or faster than that of brain, but the pattern of recovery was more erratic and therefore statistical comparison with brain ChE recovery was not attempted. In vitro tests indicated that the potential for dephosphorylation to contribute to in vivo recovery of inhibited brain ChE differed among chemical treatments. Some ducklings died as a result of organophosphate dosing. In an experiment in which ducklings within each treatment group received the same dose (mg/kg), the brain ChE activity in birds that died was less than that in birds that survived. Brain ChE activities in ducklings that died were significantly different among pesticide treatments: fensulfothion > parathion> acephate > malathion (p < 0.05).

  9. DEVELOPMENT OF RISK ASSESSMENT TECHNIQUES FOR SOIL BIOAVAILABILITY AND BIOACCUMULATION OF AN ORGANOPHOSPHORUS PESTICIDE

    EPA Science Inventory

    There is increased concern about the effects of organophosphorus (OP) pesticides on human and animal health. This class of chemicals has been shown to affect the immune function of macrophages and lymphocytes. Malathion, an OP compound, is one of the most widely used pesticides...

  10. DEVELOPMENT OF RISK ASSESSMENT TECHNIQUES FOR SOIL BIOAVAILABILITY AND BIOACCUMULATION OF AN ORGANOPHOSPHORUS PESTICIDE

    EPA Science Inventory

    There is increased concern about the effects of organophosphorus (OP) pesticides on human and animal health. This class of chemicals has been shown to affect the immune function of macrophages and lymphocytes. Malathion, an OP compound, is one of the most widely used pesticides...

  11. Comparative Toxicological Study between Exposed and Non-Exposed Farmers to Organophosphorus Pesticides

    PubMed Central

    Taghavian, Fariba; Vaezi, Gholamhassan; Abdollahi, Mohammad; Malekirad, Ali Akbar

    2016-01-01

    Objective The purpose of this work was to compare DNA damage, acetylcholinesterase (AChE) activity, inflammatory markers and clinical symptoms in farmers exposed to organophosphorus pesticides to individuals that had no pesticide exposure. Materials and Methods We conducted a cross-sectional survey with a total of 134 people. The subject group consisted of 67 farmers who were exposed to organophosphorus pesticides. The control group consisted of 67 people without any contact with pesticides matched with the subject group in terms of age, gender, and didactics. Oxidative DNA damage, the activities of AChE, interleukin-6 (IL6), IL10 and C-reactive protein (CRP) in serum were measured and clinical examinations conducted in order to register all clinical signs. Results Compared with the control group, substantial gains were observed in the farmers’ levels of oxidative DNA damage, IL10 and CRP. There was significantly less AChE activity in farmers exposed to organophosphorus pesticides. The levels of IL6 in both groups did not significantly differ. Conclusion The outcomes show that exposure to organophosphorus pesticides may cause DNA oxidative damage, inhibit AChE activity and increase the serum levels of inflammatory markers. Using biological materials instead of chemical pesticides and encouraging the use of safety equipment by farmers are some solutions to the adverse effects of exposure to organophosphorous pesticides. PMID:27054123

  12. Development of an Enzyme Linked Immunosorbent Assay and an Immunochromatographic Assay for Detection of Organophosphorus Pesticides in Different Agricultural Products

    PubMed Central

    Hua, Xiude; Yang, Jifei; Wang, Limin; Fang, Qingkui; Zhang, Gaiping; Liu, Fengquan

    2012-01-01

    Objective Organophosphorus (OP) pesticides are considered hazardous substances because of their high toxicity to nontarget species and their persistence in the environment and agricultural products. Therefore, it is important to develop a rapid, sensitive, and economical method for detecting OP pesticides and their residues in food and the environment. Methods A broad, selective monoclonal antibody (MAb) for organophosphorus pesticides was produced. Based on the MAb, an enzyme linked immunosorbent assay (ELISA) and an immunochromatography assay (ICA) for detecting OP pesticides in different agricultural products were developed using a binding inhibition format on microtiter plates and a membrane strip, respectively. Results Under the optimized conditions, the IC50 values of the ELISA ranged from 3.7 to 162.2 ng mL–1 for the 8 OP pesticides. The matrix interferences of Apple, Chinese cabbage, and greengrocery were removed by 40-fold dilution, the recoveries from spiked samples ranged from 79.1% to 118.1%. The IC50 values of ICA for the 8 OP pesticides ranged from 11.8 to 470.4 ng mL−1. The matrix interference was removed from the Chinese cabbage and Apple samples with 5-fold dilution, and the interference was removed from the greengrocery samples with 20-fold dilution. The recoveries from the spiked samples ranged between 70.6 and 131.9%. The established ELISA and ICA were specific selectivity for the 8 OP pesticides. Conclusions The established ELISA is a sensitive screening method for the detection of OP pesticides, but the ELISA detection method depends on a laboratory platform and requires a relative long assay time and several steps operation. The established ICA is very useful as a screening method for the quantitative, semi-quantitative or qualitative detection of OP pesticides in agricultural products, and it has advantages over ELISA methods with regard to factors such as the testing procedure, testing time, and matrix interferences, among others. PMID

  13. Preparation of Electrochemical Biosensor for Detection of Organophosphorus Pesticides

    PubMed Central

    Gothwal, Ashish; Beniwal, Puneet; Dhull, Vikas

    2014-01-01

    Polyvinyl chloride (PVC) can be used to develop reaction beaker which acts as electrochemical cell for the measurement of OP pesticides. Being chemically inert, corrosion resistant, and easy in molding to various shapes and size, PVC can be used for the immobilization of enzyme. Organophosphorus hydrolase was immobilized covalently onto the chemically activated inner surface of PVC beaker by using glutaraldehyde as a coupling agent. The carbon nanotubes paste working electrode was constructed for amperometric measurement at a potential of +0.8 V. The biosensor showed optimum response at pH 8.0 with incubation temperature of 40°C. K m and I max for substrate (methyl parathion) were 322.58 µM and 1.1 µA, respectively. Evaluation study showed a correlation of 0.985, which was in agreement with the standard method. The OPH biosensor lost 50% of its initial activity after its regular use for 25 times over a period of 50 days when stored in 0.1 M sodium phosphate buffer, pH 8.0 at 4°C. No interference was observed by interfering species. PMID:25667593

  14. BIODEGRADATION OF ORGANOPHOSPHORUS PESTICIDES BY SURFACE-EXPRESSED ORGANOPHOSPHORUS HYDROLASE. (R823663)

    EPA Science Inventory

    Organophosphorus hydrolase (OPH) was displayed and anchored onto the surface of
    Escherichia coli using an Lpp-OmpA fusion system. Production of the fusion proteins in membrane
    fractions was verified by immunoblotting with OmpA antisera. inclusion of the organophosphorus
    ...

  15. BIODEGRADATION OF ORGANOPHOSPHORUS PESTICIDES BY SURFACE-EXPRESSED ORGANOPHOSPHORUS HYDROLASE. (R823663)

    EPA Science Inventory

    Organophosphorus hydrolase (OPH) was displayed and anchored onto the surface of
    Escherichia coli using an Lpp-OmpA fusion system. Production of the fusion proteins in membrane
    fractions was verified by immunoblotting with OmpA antisera. inclusion of the organophosphorus
    ...

  16. In vivo tracing of organophosphorus pesticides in cabbage (Brassica parachinensis) and aloe (Barbadensis).

    PubMed

    Qiu, Junlang; Chen, Guosheng; Zhou, Hong; Xu, Jianqiao; Wang, Fuxin; Zhu, Fang; Ouyang, Gangfeng

    2016-04-15

    In vivo solid-phase microextraction (SPME) sampling method coupled with gas chromatography-mass spectrometry (GC-MS) analysis was employed to trace the uptake and elimination of organophosphorus pesticides (OPPs) in two kinds of edible plants, cabbage (Brassica parachinensis) and aloe (Barbadensis). The metabolism of fenthion in aloe was also investigated by the liquid chromatography tandem mass spectrometry analysis (LC-MS/MS) to understand the fate of OPPs in living plants better. Transpiration stream concentration factor (TSCF) and depuration rate constants of the OPPs in living plants were obtained therein. The health risk of the OPPs treated aloe was estimated by the maximum residue limit (MRL) approach, and it revealed that the OPPs were rather safe for their fast degradable property. However, peak concentration of fenthion-sulfoxide was found to exceed the MRL and was higher than that of the parent fenthion, which indicated the potential risk of pesticide metabolites. This study highlighted the application of in vivo SPME for contaminant tracing in different living edible plants. The in vivo tracing method is very convenient and can provide more data to evaluate the risk of different pesticides, which are very important for the safety of agriculture production.

  17. Organophosphorus pesticide mixture removal from environmental matrices by a soil Streptomyces mixed culture.

    PubMed

    Briceño, Gabriela; Vergara, Karen; Schalchli, Heidi; Palma, Graciela; Tortella, Gonzalo; Fuentes, María Soledad; Diez, María Cristina

    2017-07-26

    The current study aimed to evaluate the removal of a pesticide mixture composed of the insecticides chlorpyrifos (CP) and diazinon (DZ) from liquid medium, soil and a biobed biomixture by a Streptomyces mixed culture. Liquid medium contaminated with 100 mg L(-1) CP plus DZ was inoculated with the Streptomyces mixed culture. Results indicated that microorganisms increased their biomass and that the inoculum was viable. The inoculum was able to remove the pesticide mixture with a removal rate of 0.036 and 0.015 h(-1) and a half-life of 19 and 46 h(-1) for CP and DZ, respectively. The sterilized soil and biobed biomixture inoculated with the mixed culture showed that Streptomyces was able to colonize the substrates, exhibiting an increase in population determined by quantitative polymerase chain reaction (q-PCR), enzymatic activity dehydrogenase (DHA) and acid phosphatase (APP). In both the soil and biomixture, limited CP removal was observed (6-14%), while DZ exhibited a removal rate of 0.024 and 0.060 day(-1) and a half-life of 29 and 11 days, respectively. Removal of the organophosphorus pesticide (OP) mixture composed of CP and DZ from different environmental matrices by Streptomyces spp. is reported here for the first time. The decontamination strategy using a Streptomyces mixed culture could represent a promising alternative to eliminate CP and DZ residues from liquids as well as to eliminate DZ from soil and biobed biomixtures.

  18. Development of apple certified reference material for quantification of organophosphorus and pyrethroid pesticides.

    PubMed

    Otake, Takamitsu; Yarita, Takashi; Aoyagi, Yoshie; Kuroda, Youko; Numata, Masahiko; Iwata, Hitoshi; Watai, Masatoshi; Mitsuda, Hitoshi; Fujikawa, Takashi; Ota, Hidekazu

    2013-06-01

    An apple certified reference material for the analysis of pesticide residues was issued by the National Metrology Institute of Japan. Organophosphorus and pyrethroid pesticides were sprayed on apples, and these were used as raw materials of certified reference material. The harvested apples were cut into small pieces, freeze-dried, pulverized, sieved, placed into 200 brown glass bottles (3g each), and sterilized by γ-irradiation. Stability and homogeneity assessment was performed, and the relative uncertainties due to instability (for an expiry date of 32 months) and inhomogeneity were 10.3-25.0% and 4.0-6.8%, respectively. The characterization was carried out using multiple analytical methods to ensure the reliability of analytical results; the values of target pesticides were obtained by isotope dilution mass spectrometry. Certified values were 2.28 ± 0.82 mg/kg for diazinon, 3.14 ± 0.79 mg/kg for fenitrothion, 1.55 ± 0.81 mg/kg for cypermethrin, and 2.81 ± 0.70 mg/kg for permethrin. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. Multiresidue determination of organophosphorus pesticides in solid waste environmental samples by gas chromatography.

    PubMed

    Wu, Shijian; Zhang, Huanyan; Chen, Beibei; Liu, Ming; Shen, Yanjun; Sha, Qichao; Zhi, Yuee; Zhou, Pei

    2014-01-01

    The method for the determination of 12 organophosphorus pesticides in solid waste was established. The organophosphorus pesticides were analyzed by Soxhlet extraction or accelerated solvent extraction (ASE)-SPE cartridge-flame photometric detector (FPD), and leaching solution by rotary oscillation-positive pressure filtration-liquid-liquid extraction-SPE cartridge-FPD. The differences of extraction efficiencies between Soxhlet and ASE were compared. Solvent of Soxhlet extraction, purification and recovery of organophosphorus pesticides in leaching conditions were also studied. The recoveries were 54.2-119.8%, and the average recovery was 87.7%. The RSD was 1.89-9.10% (n = 6), the average RSD was 6.88%, and the detection limit was 0.27-0.69 μg/kg.

  20. Detoxification of organophosphorus pesticides and nerve agents through RSDL: efficacy evaluation by (31)P NMR spectroscopy.

    PubMed

    Elsinghorst, Paul W; Worek, Franz; Koller, Marianne

    2015-03-04

    Intoxication by organophosphorus compounds, especially by pesticides, poses a considerable risk to the affected individual. Countermeasures involve both medical intervention by means of antidotes as well as external decontamination to reduce the risk of dermal absorption. One of the few decontamination options available is Reactive Skin Decontamination Lotion (RSDL), which was originally developed for military use. Here, we present a (31)P NMR spectroscopy based methodology to evaluate the detoxification efficacy of RSDL with respect to a series of organophosphorus pesticides and nerve agents. Kinetic analysis of the obtained NMR data provided degradation half-lives proving that RSDL is also reasonably effective against organophosphorus pesticides. Unexpected observations of different RSDL degradation patterns are presented in view of its reported oximate-catalyzed mechanism of action.

  1. Pesticidal residues in animal tissues

    USGS Publications Warehouse

    DeWitt, J.B.; Menzie, C.M.; Adomaitis, V.A.; Reichel, W.L.

    1960-01-01

    Tests with penned starlings, rats, pheasants, and ducks indicated that each species differs in sensitivity to the various pesticides. Residues in tissues are proportional to the degree of exposure during area treatment and they are also found in animals shot six or more months after treatment. The presence of more than 20-30 ppm of DDT, 20 ppm of chlordan, and 6-20 ppm of heptachlor epoxide in quail tissues indicated that the birds had ingested lethal dosages of the pesticides.

  2. The occurrence and risk assessment of five organophosphorus pesticides in river water from Shangyu, China.

    PubMed

    Chen, Hao; Zhu, Jianqiang; Li, Zhe; Chen, An; Zhang, Quan

    2016-11-01

    Organophosphorus pesticides (OPs), which are some of the most extensively used pesticides, have drawn much attention in recent years owing to their ubiquity as well as the potential ecological and health risks they pose to aquatic organisms and even to humans. In this study, we investigated the residue of five OPs in 49 river cross sections in Shangyu, Zhejiang province, China, a rainy region with relatively developed agriculture. Correlations analysis, principal component analysis, and cluster analysis were conducted. The results showed that dichlorvos exhibited the highest concentrations (0.01 to 5.63 μg/L) among the OPs in most monitoring sites. Weak positive correlations were found between methyl parathion and dichlorvos as well as malathion and dimethoate. The principal component analysis and cluster analysis indicated a correlation among these river cross sections. We then calculated the hazard index (HI) to estimate the potential adverse health effects. The mean HI presented no risk to adults but showed potential health risks to children, with values of 0.285, 0.228, and 0.166 for dichlorvos, methyl parathion, and dimethoate, respectively. Our study will help elucidate the potential risks of OPs and their residues in the rivers of Shangyu in the Zhejiang province in China and will be beneficial for managing water quality and will provide valuable suggestions to local policy makers. Graphical abstract Comparison of the ∑5OPs concentrations among 49 river cross sections.

  3. Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean.

    PubMed

    Yarita, Takashi; Aoyagi, Yoshie; Otake, Takamitsu

    2012-01-01

    The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40- 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.

  4. Organic Diets Significantly Lower Children’s Dietary Exposure to Organophosphorus Pesticides

    PubMed Central

    Lu, Chensheng; Toepel, Kathryn; Irish, Rene; Fenske, Richard A.; Barr, Dana B.; Bravo, Roberto

    2006-01-01

    We used a novel study design to measure dietary organophosphorus pesticide exposure in a group of 23 elementary school-age children through urinary biomonitoring. We substituted most of children’s conventional diets with organic food items for 5 consecutive days and collected two spot daily urine samples, first-morning and before-bedtime voids, throughout the 15-day study period. We found that the median urinary concentrations of the specific metabolites for malathion and chlorpyrifos decreased to the nondetect levels immediately after the introduction of organic diets and remained nondetectable until the conventional diets were reintroduced. The median concentrations for other organophosphorus pesticide metabolites were also lower in the organic diet consumption days; however, the detection of those metabolites was not frequent enough to show any statistical significance. In conclusion, we were able to demonstrate that an organic diet provides a dramatic and immediate protective effect against exposures to organophosphorus pesticides that are commonly used in agricultural production. We also concluded that these children were most likely exposed to these organophosphorus pesticides exclusively through their diet. To our knowledge, this is the first study to employ a longitudinal design with a dietary intervention to assess children’s exposure to pesticides. It provides new and persuasive evidence of the effectiveness of this intervention. PMID:16451864

  5. Recent approaches to improving selectivity and sensitivity of enzyme-based biosensors for organophosphorus pesticides: A review.

    PubMed

    Songa, Everlyne A; Okonkwo, Jonathan O

    2016-08-01

    Pesticide determination has attracted great attention due to the fact that they exhibit high acute toxicity and can cause long-term damage to the environment and human lives even at trace levels. Although classical analytical methods (including gas chromatography, high performance liquid chromatography, capillary electrophoresis and mass spectrometry) have been effectively used for analysis of pesticides in contaminated samples, they present certain limitations such as time-consuming sample preparation, complexity, and the requirement of expensive instrumentation and highly skilled personnel. For these reasons, there is an expanding need for analytical methods able to provide simple, rapid, sensitive, selective, low cost and reliable detection of pesticides at trace levels. Over the past decades, acetylcholinesterase (AChE) biosensors have emerged as simple, rapid and ultra-sensitive tools for toxicity detection of pesticides in the environment and food. These biosensors have the potential to complement or replace the classical analytical methods by simplifying or eliminating sample preparation and making field-testing easier and faster with significant decrease in cost per analysis. With the recent engineering of more sensitive AChE enzymes, the development of more reliable immobilization matrices and the progress in the area of microelectronics, AChE biosensors could become competitive for multi-analyte screening and soon be used for the development of portable instrumentation for rapid toxicity testing of samples. The enzymes organophosphorus hydrolase (OPH) and organophosphorus acid anhydrolase (OPAA) have also shown considerable potential in OP biosensor applications and they have been used for direct detection of OPs. This review presents the recent advances in the fabrication of enzyme biosensors for organophosphorus pesticides (OPs) and their possible applications for toxicity monitoring of organophosphorus pesticide residues in real samples. The focus will

  6. Pesticide residues in olive oil.

    PubMed

    Lentza-Rizos, C; Avramides, E J

    1995-01-01

    The attacks of pests and diseases and the presence of weeds make it necessary to apply pesticides to olive trees to ensure crop protection. Residues of these compounds may remain and contaminate the oil produced. For the analysis of pesticide residues in olive oil, the most common methods are multiresidue methods for fatty substrates, based on partitioning between hexane or light petroleum and acetonitrile. Recently, other methods have been applied, such as ready-to-use, disposable minicolumns or direct injection of oil into a capillary gas chromatograph equipped with a precolumn with an oil recovery tank. Although several pesticides are registered in oil-producing countries for use on olive trees, available literature on the level and fate of residues is very limited. However, it is clear that fat-soluble pesticides tend to concentrate in the oil, both after full coverage and bait spraying, and their use close to harvest should therefore be avoided. Because it is sometimes necessary to use such pesticides late in autumn because of their effectiveness in cases of severe attack, residue trials should be carried out to determine the residue concentration in oil and to set a reasonable preharvest safety interval. Data produced by such trials would permit the establishment of MRLs (tolerances) in olive oil to cover cases where the residues, although relatively high, are not of toxicological significance for consumers (risk assessment). Such is the case with corn oil and the fat-soluble insecticide methyl pirimiphos, registered in the U.S. for use on corn. The U.S. EPA tolerance for methyl pirimiphos in corn is 8 mg/kg, whereas it is 11 times higher (88 mg/kg) for corn oil because it is known to concentrate in the oil. Similar provisions for olive oil, based on data from residue trials according to Good Agricultural Practice, the long-term toxicity of each pesticide as expressed by its ADI for man, and olive oil consumption patterns, would facilitate international trade

  7. Assessing the Developmental Neurotoxicity of 27 Organophosphorus Pesticides Using a Zebrafish Behavioral Assay

    EPA Science Inventory

    Assessing the Developmental Neurotoxicity of 27 Organophosphorus Pesticides Using a Zebrafish Behavioral Assay, Waalkes, M., Hunter, D.L., Jarema, K., Mundy, W., and S. Padilla. The U.S. Environmental Protection Agency is evaluating methods to screen and prioritize organophosphor...

  8. Assessing the Developmental Neurotoxicity of 27 Organophosphorus Pesticides Using a Zebrafish Behavioral Assay

    EPA Science Inventory

    Assessing the Developmental Neurotoxicity of 27 Organophosphorus Pesticides Using a Zebrafish Behavioral Assay, Waalkes, M., Hunter, D.L., Jarema, K., Mundy, W., and S. Padilla. The U.S. Environmental Protection Agency is evaluating methods to screen and prioritize organophosphor...

  9. Monoclonal antibody-based broad-specificity immunoassay for monitoring organophosphorus pesticides in environmental water samples

    USDA-ARS?s Scientific Manuscript database

    The extensive use of organophosphorus pesticides (OPs) in agriculture and domestic settings can result in widespread water contamination. The development of easy-to-use and rapid-screening immunoassay methods in a class-selective manner is a topic of considerable environmental interest. In this wo...

  10. EFFECTS OF TEMPERATURE AND SOLVENT COMPOSITION ON THE CHIRALCEL OJ SEPARATION OF CHIRAL ORGANOPHOSPHORUS PESTICIDES

    EPA Science Inventory

    The separation of the enantiomers of twelve organophosphorus pesticides (OPs) was investigated on the CHIRALCEL?OJ column to determine whether the mobile phase composition, flow rate and column temperature could be optimized to yield at least partial separation of the enantiomers...

  11. Airborne concentrations of organophosphorus pesticides in Korean pesticide manufacturing/formulation workplaces.

    PubMed

    Han, Don-Hee

    2011-01-01

    Pesticide manufacturing/formulation workers rather than farmers or applicators or people living with them are primarily exposed to organophosphorus pesticides (OPs). However, airborne concentrations in the workplace have rarely been determined. A total of 121 air samples (personal or area sampling) were collected at 4 factories where chlorpyrifos, EPN, parathion, and phorate, were manufactured/formulated from March through July, 2007-2008. Samples were collected by the National Institute for Occupational Safety and Health (NIOSH) method and were analyzed by GC-MS. The geometric mean (GM) level of airborne chlorpyrifos was 0.17 mg/m(3), 85% Korean Occupational Exposure Limit (KOEL) of 0.2 mg/m(3), and at 95% confidence, airborne concentrations exceeded the KOEL 58.8% of the time or less, indicating that this concentration level was unacceptable according to exposure assessment using a LogNorm2(®). However, compared with levels of TLV and/or PEL and/or WEL, the GM concentration levels of other OPs were remarkably low (range, 0.1-15.0%) and that these levels of concentrations to the other OPs were acceptable. The levels of airborne concentrations of OPs depended on isolation of the process; in other words, the levels depended on the extent to which the process was automated. The reason that the airborne concentration levels, except for those of chlorpyrifos, were very much lower than expected may be attributable to the fact that there was not exposed to 100% toxic active ingredients in pesticide formulation workplaces because of the use of supplemental agents or additives to produce complete pesticides. This study is limited since there were seldom or neither any data of previous studies to be compared with the study results nor dermal exposure data. The results were used to revise KOELs for OPs in 2010.

  12. Screening organophosphorus nerve agent degradation products in pesticide mixtures by GC-ICPMS.

    PubMed

    Richardson, Douglas D; Caruso, Joseph A

    2007-10-01

    Gas chromatography inductively coupled plasma mass spectrometry (GC-ICPMS) was utilized for the analysis of four organophosphorus nerve agent degradation products in the presence of mixtures of common organophosphorus pesticides. The first degradation products of sarin (isopropyl methylphosphonic acid, GB acid), cyclosarin (cyclohexyl methylphosphonic acid, GF acid), and soman (pinacolyl methylphosphonic acid) as well as their common final hydrolysis product methyl phosphonic acid were utilized throughout these experiments. Due to the non-volatile nature of these alkyl phosphonic acid degradation products, derivatization was performed to generate the volatile tert-butyl dimethylsilyl species. Degraded organophosphorus pesticide standards were obtained for acephate, chlorpyrifos, dichlorvos, ethion, and parathion ethyl. Mixtures consisting of three pesticides in the presence of a single nerve agent degradation product were prepared. GC-ICPMS allowed for the separation and detection of all four degradation products in the presence of pesticide mixtures in just over 12 minutes. This is the first study analyzing pesticides as interfering species for analysis of nerve agent degradation products by GC-ICPMS.

  13. Computational interaction analysis of organophosphorus pesticides with different metabolic proteins in humans

    PubMed Central

    Sharma, Amit Kumar; Gaur, Karuna; Tiwari, Rajeev Kumar; Gaur, Mulayam Singh

    2011-01-01

    Pesticides have the potential to leave harmful effects on humans, animals, other living organisms, and the environment. Several human metabolic proteins inhibited after exposure to organophosphorus pesticides absorbed through the skin, inhalation, eyes and oral mucosa, are most important targets for this interaction study. The crystal structure of five different proteins, PDBIDs: 3LII, 3NXU, 4GTU, 2XJ1 and 1YXA in Homo sapiens (H. sapiens), interact with organophosphorus pesticides at the molecular level. The 3-D structures were found to be of good quality and validated through PROCHECK, ERRAT and ProSA servers. The results show that the binding energy is maximum -45.21 relative units of cytochrome P450 protein with phosmet pesticide. In terms of H-bonding, methyl parathion and parathion with acetylcholinesterase protein, parathion, methylparathion and phosmet with protein kinase C show the highest interaction. We conclude that these organophosphorus pesticides are more toxic and inhibit enzymatic activity by interrupting the metabolic pathways in H. sapiens. PMID:23554709

  14. Upconversion nanoparticle-based fluorescence resonance energy transfer assay for organophosphorus pesticides.

    PubMed

    Long, Qian; Li, Haitao; Zhang, Youyu; Yao, Shouzhuo

    2015-06-15

    This paper reports a novel nanosensor for organophosphorus pesticides based on the fluorescence resonance energy transfer (FRET) between NaYF4:Yb,Er upconversion nanoparticles (UCNPs) and gold nanoparticles (AuNPs). The detection mechanism is based on the facts that AuNPs quench the fluorescence of UCNPs and organophosphorus pesticides (OPs) inhibit the activity of acetylcholinesterase (AChE) which catalyzes the hydrolysis of acetylthiocholine (ATC) into thiocholine. Under the optimized conditions, the logarithm of the pesticides concentration was proportional to the inhibition efficiency. The detection limits of parathion-methyl, monocrotophos and dimethoate reached 0.67, 23, and 67 ng/L, respectively. Meanwhile, the biosensor shows good sensitivity, stability, and could be successfully applied to detection of OPs in real food samples, suggesting the biosensor has potentially extensive application clinic diagnoses assays.

  15. Application of brain cholinesterase reactivation to differentiate between organophosphorus and carbamate pesticide exposure in wild birds

    USGS Publications Warehouse

    Smith, W.R.; Thomas, N.J.; Hulse, C.

    1995-01-01

    Brain cholinesterase activity was measured to evaluate pesticide exposure in wild birds. Thermal reactivation of brain cholinesterase was used to differentiate between carbamate and organophosphorus pesticide exposure. Brain cholinesterase activity was compared with gas chromatography and mass spectrometry of stomach contents. Pesticides were identified and confirmed in 86 of 102 incidents of mortality from 29 states within the USA from 1986 through 1991. Thermal reactivation of cholinesterase activity was used to correctly predict carbamates in 22 incidents and organophosphates in 59 incidents. Agreement (P < 0.001) between predictions based on cholinesterase activities and GC/MS results was significant.

  16. Application of brain cholinesterase reactivation to differentiate between organophosphorus and carbamate pesticide exposure in wild birds

    USGS Publications Warehouse

    Smith, M.R.; Thomas, N.J.; Hulse, C.

    1995-01-01

    Brain cholinesterase activity was measured to evaluate pesticide exposure in wild birds. Thermal reactivation of brain cholinesterase was used to differentiate between carbamate and organophosphorus pesticide exposure. Brain cholinesterase activity was compared with gas chromatography and mass spectrometry of stomach contents. Pesticides were identified and confirmed in 86 of 102 incidents of mortality from 29 states within the USA from 1986 through 1991. Thermal reactivation of cholinesterase activity was used to correctly predict carbamates in 22 incidents and organophosphates in 59 incidents. Agreement (P < 0.001) between predictions based on cholinesterase activities and GC/MS results was significant.

  17. ORGANOPHOSPHORUS HYDROLASE-BASED ASSAY FOR ORGANOPHOSPHATE PESTICIDES

    EPA Science Inventory

    We report a rapid and versatile Organophosphorus hydrolase (OPH)-based method for measurement of organophosphates. This assay is based on a substrate-dependent change in pH at the local vicinity of the enzyme. The pH change is monitored using fluorescein isothiocyanate (FITC), ...

  18. ORGANOPHOSPHORUS HYDROLASE-BASED ASSAY FOR ORGANOPHOSPHATE PESTICIDES

    EPA Science Inventory

    We report a rapid and versatile Organophosphorus hydrolase (OPH)-based method for measurement of organophosphates. This assay is based on a substrate-dependent change in pH at the local vicinity of the enzyme. The pH change is monitored using fluorescein isothiocyanate (FITC), ...

  19. Integrated microwave processing system for the extraction of organophosphorus pesticides in fresh vegetables.

    PubMed

    Wu, Lijie; Song, Ying; Hu, Mingzhu; Xu, Xu; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

    2015-03-01

    A simple and efficient integrated microwave processing system (IMPS) was firstly assembled and validated for the extraction of organophosphorus pesticides in fresh vegetables. Two processes under microwave irradiation, dynamic microwave-assisted extraction (DMAE) and microwave-accelerated solvent elution (MASE), were integrated for simplifying the pretreatment of the sample. Extraction, separation, enrichment and elution were finished in a simple step. The organophosphorus pesticides were extracted from the fresh vegetables into hexane with DMAE, and then the extract was directly introduced into the enrichment column packed with active carbon fiber (ACF). Subsequently, the organophosphorus pesticides trapped on the ACF were eluted with ethyl acetate under microwave irradiation. No further filtration or cleanup was required before analysis of the eluate by gas chromatography-mass spectrometry. Some experimental parameters affecting extraction efficiency were investigated and optimized, such as microwave output power, kind and volume of extraction solvent, extraction time, amount of sorbent, elution microwave power, kind and volume of elution solvent, elution solvent flow rate. Under the optimized conditions, the recoveries were in the range of 71.5-105.2%, and the relative standard deviations were lower than 11.6%. The experiment results prove that the present method is a simple and effective sample preparation method for the determination of pesticides in solid samples.

  20. Organophosphorus pesticide-induced butyrylcholinesterase inhibition and potentiation of succinylcholine toxicity in mice.

    PubMed

    Sparks, S E; Quistad, G B; Casida, J E

    1999-01-01

    Succinylcholine is the most important rapid-acting depolarizing muscle relaxant during anesthesia. Its desirable short duration of action is controlled by butyrylcholinesterase, the detoxifying enzyme. There are two reported cases of prolonged paralysis from succinylcholine in patients poisoned with the organophosphorus insecticides parathion and chlorpyrifos. The present study examines the possibility that other organophosphorus and methylcarbamate pesticides might also prolong succinylcholine action by inhibiting butyrylcholinesterase using mice treated intraperitoneally as a model and relating inhibition of blood serum hydrolysis of butyrylthiocholine to potentiated toxicity (mouse mortality). The organophosphorus plant defoliant tribufos (4 h pretreatment, 160 mg/kg) and organophosphorus plant growth regulator ethephon (1 h pretreatment, 200 mg/kg) potentiate the toxicity of succinylcholine by seven- and fourfold, respectively. Some other pesticides or analogs are more potent sensitizers for succinylcholine toxicity with threshold levels of 0.5, 1.0, 1.7, 8, 10, and 67 mg/kg for phenyl saligenin cyclic phosphonate, profenofos, methamidophos, tribufos, chlorpyrifos, and ethephon, respectively. Enhanced mortality from succinylcholine is generally observed when serum butyrylcholinesterase is inhibited 55-94%. Mivacurium, a related nondepolarizing muscle relaxant also detoxified by butyrylcholinesterase, is likewise potentiated by at least threefold on 4 hour pretreatment with tribufos (25 mg/kg) or profenofos (10 mg/kg).

  1. Partitioning of organophosphorus pesticides into phosphatidylcholine small unilamellar vesicles studied by second-derivative spectrophotometry.

    PubMed

    Takegami, Shigehiko; Kitamura, Keisuke; Ohsugi, Mayuko; Ito, Aya; Kitade, Tatsuya

    2015-06-15

    In order to quantitatively examine the lipophilicity of the widely used organophosphorus pesticides (OPs) chlorfenvinphos (CFVP), chlorpyrifos-methyl (CPFM), diazinon (DZN), fenitrothion (FNT), fenthion (FT), isofenphos (IFP), profenofos (PFF) and pyraclofos (PCF), their partition coefficient (Kp) values between phosphatidylcholine (PC) small unilamellar vesicles (SUVs) and water (liposome-water system) were determined by second-derivative spectrophotometry. The second-derivative spectra of these OPs in the presence of PC SUV showed a bathochromic shift according to the increase in PC concentration and distinct derivative isosbestic points, demonstrating the complete elimination of the residual background signal effects that were observed in the absorption spectra. The Kp values were calculated from the second-derivative intensity change induced by addition of PC SUV and obtained with a good precision of R.S.D. below 10%. The Kp values were in the order of CPFM>FT>PFF>PCF>IFP>CFVP>FNT⩾DZN and did not show a linear correlation relationship with the reported partition coefficients obtained using an n-octanol-water system (R(2)=0.530). Also, the results quantitatively clarified the effect of chemical-group substitution in OPs on their lipophilicity. Since the partition coefficient for the liposome-water system is more effective for modeling the quantitative structure-activity relationship than that for the n-octanol-water system, the obtained results are toxicologically important for estimating the accumulation of these OPs in human cell membranes.

  2. Partitioning of organophosphorus pesticides into phosphatidylcholine small unilamellar vesicles studied by second-derivative spectrophotometry

    NASA Astrophysics Data System (ADS)

    Takegami, Shigehiko; Kitamura, Keisuke; Ohsugi, Mayuko; Ito, Aya; Kitade, Tatsuya

    2015-06-01

    In order to quantitatively examine the lipophilicity of the widely used organophosphorus pesticides (OPs) chlorfenvinphos (CFVP), chlorpyrifos-methyl (CPFM), diazinon (DZN), fenitrothion (FNT), fenthion (FT), isofenphos (IFP), profenofos (PFF) and pyraclofos (PCF), their partition coefficient (Kp) values between phosphatidylcholine (PC) small unilamellar vesicles (SUVs) and water (liposome-water system) were determined by second-derivative spectrophotometry. The second-derivative spectra of these OPs in the presence of PC SUV showed a bathochromic shift according to the increase in PC concentration and distinct derivative isosbestic points, demonstrating the complete elimination of the residual background signal effects that were observed in the absorption spectra. The Kp values were calculated from the second-derivative intensity change induced by addition of PC SUV and obtained with a good precision of R.S.D. below 10%. The Kp values were in the order of CPFM > FT > PFF > PCF > IFP > CFVP > FNT ⩾ DZN and did not show a linear correlation relationship with the reported partition coefficients obtained using an n-octanol-water system (R2 = 0.530). Also, the results quantitatively clarified the effect of chemical-group substitution in OPs on their lipophilicity. Since the partition coefficient for the liposome-water system is more effective for modeling the quantitative structure-activity relationship than that for the n-octanol-water system, the obtained results are toxicologically important for estimating the accumulation of these OPs in human cell membranes.

  3. Organophosphorus and Organochlorine Pesticides Bioaccumulation by Eichhornia crassipes in Irrigation Canals in an Urban Agricultural System.

    PubMed

    Mercado-Borrayo, B M; Cram Heydrich, Silke; Pérez, Irma Rosas; Hernández Quiroz, Manuel; De León Hill, Claudia Ponce

    2015-01-01

    A natural wetland in Mexico City Metropolitan Area is one of the main suppliers of crops and flowers, and in consequence its canals hold a high concentration of organochlorine (OC) and organophosphorus (OP) pesticides. There is also an extensive population of water hyacinth (Eichhornia crassipes), which is considered a plague; but literature suggests water hyacinth may be used as a phytoremediator. This study demonstrates bioaccumulation difference for the OC in vivo suggesting their bioaccumulation is ruled by their log K(ow), while all the OP showed bioaccumulation regardless of their log K(ow). The higher bioaccumulation factors (BAF) of the accumulated OC pesticides cannot be explained by their log K(ow), suggesting that the OC pesticides may also be transported passively into the plant. Translocation ratios showed that water hyacinth is an accumulating plant with phytoremediation potential for all organophosphorus pesticides studied and some organochlorine pesticides. An equation for free water surface wetlands with floating macrophytes, commonly used for the construction of water-cleaning wetlands, showed removal of the pesticides by the wetland with room for improvement with appropriate management.

  4. Poisoning of raptors with organophosphorus and carbamate pesticides with emphasis on Canada, U.S. and U.K.

    USGS Publications Warehouse

    Mineau, P.; Fletcher, M.R.; Glaser, L.C.; Thomas, N.J.; Brassard, C.; Wilson, L.K.; Elliott, J.E.; Lyon, L.A.; Henny, C.J.; Bollinger, T.; Porter, S.L.

    1999-01-01

    We reviewed cases of raptor mortality resulting from cholinesterase-inhibiting pesticides. We compiled records from the U.S., U.K. and Canada for the period 1985-95 (520 incidents) and surveyed the relevant literature to identify the main routes of exposure and those products that led to the greatest number of poisoning cases. A high proportion of cases in the U.K. resulted from abusive uses of pesticides (willful poisoning). The proportion was smaller in North America where problems with labeled uses of pesticides were as frequent as abuse cases. Poisoning resulting from labeled use was possible with a large number of granular pesticides and some seed treatments through secondary poisoning or through the ingestion of contaminated invertebrates, notably earthworms. With the more toxic products, residue levels in freshly-sprayed insects were high enough to cause mortality. The use of organophosphorus products as avicides and for the topical treatment of livestock appeared to be common routes of intoxication. The use of insecticides in dormant oils also gave rise to exposure that can be lethal or which can debilitate birds and increase their vulnerability. A few pesticides of high toxicity were responsible for the bulk of poisoning cases. Based on limited information, raptors appeared to be more sensitive than other bird species to organophosphorus and carbamate pesticides. Some of the more significant risk factors that resulted in raptor poisonings were: insectivory and vermivory; opportunistic taking of debilitated prey; scavenging, especially if the gastrointestinal tracts are consumed; presence in agricultural areas; perceived status as pest species; and flocking or other gregarious behavior at some part of their life cycle. Lethal or sublethal poisoning should always be considered in the diagnosis of dead or debilitated raptors even when another diagnosis (e.g., electrocution, car or building strike) is apparent. Many cases of poisoning are not currently

  5. Zirconium(IV) functionalized magnetic nanocomposites for extraction of organophosphorus pesticides from environmental water samples.

    PubMed

    Jiang, Li; Huang, Tengjun; Feng, Shun; Wang, Jide

    2016-07-22

    The widespread use of organophosphate pesticides (OPPs) in agriculture leads to residue accumulation in the environment which is dangerous to human health and disrupts the ecological balance. In this work, one nanocomposite immobilized zirconium (Zr, IV) was prepared and used as the affinity probes to quickly and selectively extract organophosphorus pesticides (OPPs) from water samples. The Fe3O4-ethylenediamine tetraacetic acid (EDTA)@Zr(IV) nanocomposites (NPs) were prepared by simply mixing Zr(IV) ions with Fe3O4-EDTA NPs synthesized by one-pot chemical co-precipitation method. The immobilized Zr(IV) ions were further utilized to capture OPPs based on their high affinity for the phosphate moiety in OPPs. Coupled with GC-MS, four OPPs were used as models to demonstrate the feasibility of this approach. Under the optimum conditions, the limits of detection for target OPPs were in the range of 0.10-10.30ngmL(-1) with relative standard deviations (RSDs) of 0.61-4.40% (n=3), respectively. The linear ranges were over three orders of magnitudes (correlation coefficients, R(2)>0.9995). The Fe3O4-EDTA@Zr(IV) NPs were successfully applied to extract OPPs samples with recoveries of 86.95-112.60% and RSDs of 1.20-10.42% (n=3) from two spiked real water. By the proposed method, the matrix interference could be effectively eliminated. We hope our finding can provide a promising alternative for the fast extraction of OPPs from complex real samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. OpdA, a bacterial organophosphorus hydrolase, prevents lethality in rats after poisoning with highly toxic organophosphorus pesticides

    PubMed Central

    Bird, Steven B.; Sutherland, Tara D.; Gresham, Chip; Oakeshott, John; Scott, Colin; Eddleston, Michael

    2008-01-01

    Organophosphorus (OP) pesticides poison more than 3,000,000 people every year in the developing world, mostly through intentional self-poisoning. Advances in medical therapy for OP poisoning have lagged, and current treatment is not highly effective with mortality of up to 40% in even the most advanced Western medical facilities. Administration of a broadly active bacterial OP hydrolase to patients in order to hydrolyze OPs in circulation might allow current therapies to be more effective. The objective of this work was to evaluate the efficacy of a new recombinant bacterial OP hydrolase (OpdA), cloned from Agrobacterium radiobacter, in rat models of two chemically distinct but highly toxic and rapidly acting OP pesticides: dichlorvos and parathion. Without OpdA treatment, median time to death in rats poisoned with 3 × LD50 of dichlorvos or parathion was 6 minutes and 25.5 minutes, respectively. Administration of a single dose of OpdA immediately after dichlorvos resulted in 100% survival at 24 hours, with no additional antidotal therapy. After parathion poisoning, OpdA alone caused only a delay to death. However, an additional two doses of OpdA resulted in 62.5% survival at 24 hours after parathion poisoning. In combination with pralidoxime therapy, a single dose of OpdA increased survival to 75% after parathion poisoning. Our results demonstrate that OpdA is able to improve survival after poisoning by two chemically distinct and highly toxic OP pesticides. PMID:18378376

  7. Effect of some organophosphorus pesticides on oxygen consumption of shrimp, Litopenaeus vannamei.

    PubMed

    Galindo Reyes, José Guillermo; Dalla-Venezia, Luisella; Lazcano Alvarez, Maria Guadalupe

    2002-06-01

    Oxygen consumption was measured in adult specimens of Litopenaeus vannamei shrimps from a coastal lagoon of Sinaloa, Mexico, during exposure to sublethal concentrations of the organophosphorus pesticides, Diazinon, Folidol, and Gusathion. Each individual was used as a control of itself, to avoid differences between treatments being masked by individual variability. In all three treatments with pesticides, respiration rate, measured by a polarographic electrode, was significantly lower than in controls. This may, at least partly, explain the decrease in shrimp production observed in recent years in the coastal lagoons of Sinaloa. (c) 2002 Elsevier Science (USA).

  8. Pesticide Residues in Food: Your Daily Dose.

    ERIC Educational Resources Information Center

    Mott, Lawrie

    1985-01-01

    Extensive use of pesticides during food production has created concerns for certain involuntary risks. Examines these concerns: government role in control and monitoring pesticide use, proposals for reform, and how consumer awareness might be an effective pressure for finding remedies. A table listing produce and pesticide residues is included.…

  9. Pesticide Residues in Food: Your Daily Dose.

    ERIC Educational Resources Information Center

    Mott, Lawrie

    1985-01-01

    Extensive use of pesticides during food production has created concerns for certain involuntary risks. Examines these concerns: government role in control and monitoring pesticide use, proposals for reform, and how consumer awareness might be an effective pressure for finding remedies. A table listing produce and pesticide residues is included.…

  10. PESTICIDE RESIDUE RECOVERIES FROM SURFACE WIPES

    EPA Science Inventory

    Human exposure is a consequence of pesticide use indoors with a primary source resulting from residue deposition on household surfaces. Accurate measurements of surface residues is essential for estimating exposure from different routes. Various procedures have been developed ...

  11. PESTICIDE RESIDUE RECOVERIES FROM SURFACE WIPES

    EPA Science Inventory

    Human exposure is a consequence of pesticide use indoors with a primary source resulting from residue deposition on household surfaces. Accurate measurements of surface residues is essential for estimating exposure from different routes. Various procedures have been developed ...

  12. Rapid detection of pesticide residue in apple based on Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Yongyu; Sun, Yunyun; Peng, Yankun; Dhakal, Sagar; Chao, Kuanglin; Liu, Qiaoqiao

    2012-05-01

    The potential of Raman spectroscopy in the analysis of low concentration organic contaminants on apples' surface was evidenced in this study. Chlorpyrifos, an organophosphorus pesticide, was used as a probe for this purpose. The characteristic peaks of fingerprints of pesticide on an aluminum substrate and apple fruit cuticle without pesticide residue were acquired first. Then a concentration range of chlorpyrifos (commercial products at 40%) solutions were made using deionised and distilled water. Single 100 μL droplets of the chlorpyrifos solutions were placed gently on apple fruit cuticles and left to dry before analysis. Through comparative analysis of the Raman spectra data collected, 341, 632 and 1237cm-1 were identified to detect the chlorpyrifos pesticide residue on apple surface. Based on the relationship between the Raman intensity of the most prominent peak at around 632cm-1 and the pesticide concentrations, the limit of detection of ordinary Raman spectrum for chlorpyrifos was estimated to be 48ppm.

  13. [Survey of pesticide residues in imported spices and herbs (1997.4-2011.3)].

    PubMed

    Kobayashi, Maki; Ohtsuka, Kenji; Tamura, Yasuhiro; Tomizawa, Sanae; Kinoshita, Teruaki; Kamijo, Kyoko; Iwakoshi, Keiko; Sato, Chizuko; Nagayama, Toshihiro; Takano, Ichiro

    2013-01-01

    A survey of pesticide residues in 313 samples of imported spices and herbs on the Tokyo market from April 1997 to March 2011 was carried out. Thirty-seven kinds of pesticides, including organophosphorus, organochlorine, pyrethroid, carbamate and others, were detected between levels of trace (below 0.01 ppm) and 3.3 ppm from 64 samples. The rate of detection was highest in peel (100%) followed by stem (66.7%), fruit (34.5%), bark (33.3%), flower (31.3%) and leaf (14.7%). No residues were detected in root, seed or whole grass. Organochlorine pesticides were detected in all plant parts. The insecticides were detected in products from all production areas, suggesting that their use is common. Residue levels of these pesticides were calculated as less than 1% of their ADI values, based on the daily intake of spices and herbs. Therefore, these spices and herbs should be safe when consumed in customary amounts.

  14. Detection of toxic heavy metals and pesticide residue in herbal plants which are commonly used in the herbal formulations.

    PubMed

    Rao, Mruthyumjaya Meda; Kumarmeena, Ajay; Galib

    2011-10-01

    Herbal formulations are getting popular throughout the world and commercialized extensively for various medicinal properties. WHO has emphasized the need for quality assurance of herbal products, including testing of heavy metals and pesticides residues. In view of WHO guidelines, single herbal drugs used in herbal formulations were collected from local market, for testing heavy metals and persistent pesticides residue. Therefore, in the present case, we have examined few local samples of certain herbs viz. Emblica officinalis, Terminalia chebula, Terminalia belerica, and Withania somnifera. The present studies were selected for estimation of four heavy metals namely Arsenic, Cadmium, Lead, and Mercury. Apart from these, pesticide residue Viz. Organochlorine pesticides, Organophosphorus pesticides, and Pyrethroids were analyzed in the four samples of single crude drugs. Heavy metals and pesticide residue were found below detection limits in all the samples.

  15. Determination of Organophosphate Pesticides at a Carbon Nanotube/Organophosphorus Hydrolase Electrochemical Biosensor

    SciTech Connect

    Deo, R P.; Wang, Joseph; Block, I; Mulchandani, Ashok; Joshi, K; Trojanowicz, M; Scholz, F; Chen, Wilfred; Lin, Yuehe

    2005-02-08

    An amperometric biosensor for organophosphorus (OP) pesticides based on a carbon-nanotube (CNT) modified transducer and an organophosphorus hydrolase (OPH) biocatalyst is described. A bilayer approach with the OPH layer atop of the CNT film was used for preparing the CNT/OPH biosensor. The CNT layer leads to a greatly improved anodic detection of the enzymatically-generated p-nitrophenol product, including higher sensitivity and stability. The sensor performance was optimized with respect to the surface modification and operating conditions. Under the optimal conditions the biosensor was used to measure as low as 0.15 {micro}M paraoxon and 0.8 {micro}M methyl parathion with sensitivities of 25 and 6 nA/{micro}M, respectively.

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

    PubMed

    Essumang, D K; Asare, E A; Dodoo, D K

    2013-09-01

    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.

  17. N-acetylcysteine in Acute Organophosphorus Pesticide Poisoning: A Randomized, Clinical Trial.

    PubMed

    El-Ebiary, Ahmad A; Elsharkawy, Rasha E; Soliman, Nema A; Soliman, Mohammed A; Hashem, Ahmed A

    2016-08-01

    Organophosphorus poisoning is a major global health problem with hundreds of thousands of deaths each year. Research interest in N-acetylcysteine has grown among increasing evidence of the role of oxidative stress in organophosphorus poisoning. We aimed to assess the safety and efficacy of N-acetylcysteine as an adjuvant treatment in patients with acute organophosphorus poisoning. This was a randomized, controlled, parallel-group trial on 30 patients suffering from acute organophosphorus poisoning, who were admitted to the Poison Control Center of Tanta University Emergency Hospital, Tanta, Egypt, between April and September 2014. Interventions included oral N-acetylcysteine (600 mg three times daily for 3 days) as an added treatment to the conventional measures versus only the conventional treatment. Outcome measures included mortality, total dose of atropine administered, duration of hospitalization and the need for ICU admission and/or mechanical ventilation. A total of 46 patients were screened and 30 were randomized. No significant difference was found between both groups regarding demographic characteristics and the nature or severity of baseline clinical manifestations. No major adverse effects to N-acetylcysteine therapy were reported. Malondialdehyde significantly decreased and reduced glutathione significantly increased only in the NAC-treated patients. The patients on NAC therapy required less atropine doses than those who received only the conventional treatment; however, the length of hospital stay showed no significant difference between both groups. The study concluded that the use of N-acetylcysteine as an added treatment was apparently safe, and it reduced atropine requirements in patients with acute organophosphorus pesticide poisoning.

  18. Phototransformation of selected organophosphorus pesticides: Roles of hydroxyl and carbonate radicals

    PubMed Central

    Wu, Changlong

    2013-01-01

    The phototransformation of two organophosphorus pesticides, parathion and chlorpyrifos, by hydroxyl radicals and carbonate radicals in aqueous solution were studied. The second-order rate constants of parathion and chlorpyrifos with hydroxyl radical were determined to be 9.7 ± 0.5 × 109 and 4.9 ± 0.1 × 109 M−1 s−1, respectively. Addition of hydrogen peroxide increased the UV degradation rates of both pesticides and data were simulated through kinetic modeling. The presence of bicarbonate ions reduced the pesticide degradation rates via scavenging of hydroxyl radical but the formation of carbonate radical during the hydroxyl radical scavenging also contributed to the degradation of the pesticides with second-order reaction rate constants of 2.8 ± 0.2 × 106 and 8.8 ± 0.4 × 106 M−1s−1 for parathion and chlorpyrifos, respectively. The dual roles of bicarbonate ion in UV/H2O2 treatment systems, i.e., scavenging of hydroxyl radicals and formation of carbonate radicals, were examined and discussed using a simulative kinetic model. The transformation of pesticides by carbonate radicals at environmentally relevant bi/carbonate concentrations was shown to be a significant contributor to the environmental fate of the pesticides and it reshaped the general phototransformation kinetics of both pesticides in UV/H2O2 systems. PMID:20537677

  19. Simultaneous determination of three organophosphorus pesticides in different food commodities by gas chromatography with mass spectrometry.

    PubMed

    Vijaya Bhaskar Reddy, Ambavaram; Yusop, Zulkifli; Jaafar, Jafariah; Bin Aris, Azmi; Abdul Majid, Zaiton; Umar, Khalid; Talib, Juhaizah

    2016-06-01

    A sensitive and selective gas chromatography with mass spectrometry method was developed for the simultaneous determination of three organophosphorus pesticides, namely, chlorpyrifos, malathion, and diazinon in three different food commodities (milk, apples, and drinking water) employing solid-phase extraction for sample pretreatment. Pesticide extraction from different sample matrices was carried out on Chromabond C18 cartridges using 3.0 mL of methanol and 3.0 mL of a mixture of dichloromethane/acetonitrile (1:1 v/v) as the eluting solvent. Analysis was carried out by gas chromatography coupled with mass spectrometry using selected-ion monitoring mode. Good linear relationships were obtained in the range of 0.1-50 μg/L for chlorpyrifos, and 0.05-50 μg/L for both malathion and diazinon pesticides. Good repeatability and recoveries were obtained in the range of 78.54-86.73% for three pesticides under the optimized experimental conditions. The limit of detection ranged from 0.02 to 0.03 μg/L, and the limit of quantification ranged from 0.05 to 0.1 μg/L for all three pesticides. Finally, the developed method was successfully applied for the determination of three targeted pesticides in milk, apples, and drinking water samples each in triplicate. No pesticide was found in apple and milk samples, but chlorpyrifos was found in one drinking water sample below the quantification level.

  20. Analysis of organophosphorus pesticides in whole blood by GC-MS-μECD with forensic purposes.

    PubMed

    Valente, Nuno I P; Tarelho, Sónia; Castro, André L; Silvestre, Armando; Teixeira, Helena M

    2015-07-01

    In the present work, two multi-residue methods for the determination of ten organophosphorus pesticides (OPs), namely chlorfenvinphos, chlorpyrifos, diazinon, dimethoate, fenthion, malathion, parathion, phosalone, pirimiphos-methyl and quinalphos, in post-mortem whole blood samples are presented. The adopted procedure uses GC-MS for screening and quantitation, and GC-μECD (electron capture detector) for compound confirmation. Three different Solid Phase Extraction (SPE) procedures for OPs with Oasis(®) hydrophilic lipophilic balanced (HLB) and Sep-Pak(®) C18 cartridges were tested, and followed by GC-μECD and GC-MS analysis. The Sep-Pak(®) C18 cartridges extraction procedure was selected since it generated analytical signals 5 times higher than those obtained with the two different Oasis(®) HLB cartridges extraction procedures. The method has shown to be selective for the isolation of selected OPs as well as to the chosen internal standard (ethion) in postmortem blood samples. Calibration curves between 50 and 5000 ng/mL were prepared using weighted linear regression models (1/x(2)). It was not possible to establish a working range for fenthion by GC-μECD due to the lower sensitivity of the detector to this compound, whereas for pirimiphos-methyl it was set between 500 and 5000 ng/mL. The limit of quantitation was established at 50 ng/mL for all analytes, except for pirimiphos-methyl by GC-μECD analysis (500 ng/mL). The average extraction efficiency ranged from 72 to 102%. The developed methods were considered robust and fit for the purpose, and had already been adopted in the laboratory routine analysis.

  1. Determination of carbamates and organophosphorus pesticides by SDME-GC in natural water.

    PubMed

    López-Blanco, Carmen; Gómez-Alvarez, Sonia; Rey-Garrote, María; Cancho-Grande, Beatriz; Simal-Gándara, Jesús

    2005-10-01

    Water contamination due to the wide variety of pesticides used in agriculture practices is a global environmental pollution problem. Analytical methods with low quantification limits are necessary. The application of a new extraction technique, solvent drop microextraction (SDME), followed by gas chromatography with a nitrogen-phosphorus detector, was assessed for determining carbamates and organophosphorus pesticides in natural water. Experimental parameters which control the performance of SDME such as selection of microextraction solvent, optimization of organic drop volume, effects of sample stirring, salt addition, and, finally, sorption time profiles were studied. Once SDME was optimized, analytical parameters such as linearity (r 2>0.99), precision (<13%), and detection limits (0.2 to 5 microg/L), plus matrix effects were evaluated (no matrix effects were found). SDME is a dynamic technique able to extract pesticides from water in 14 min; the use of organic solvents and water samples for SDME is negligible compared to other extraction techniques.

  2. Clinical analysis of penehyclidine hydrochloride combined with hemoperfusion in the treatment of acute severe organophosphorus pesticide poisoning.

    PubMed

    Liang, M J; Zhang, Y

    2015-05-11

    This study aimed to observe the clinical curative effect of penehyclidine hydrochloride (PHC) combined with hemoperfusion in treating acute severe organophosphorus pesticide poisoning. We randomly divided 61 patients with severe organophosphorus pesticide poisoning into an experimental group (N = 31) and a control group (N = 30), and we compared the coma-recovery time, mechanical ventilation time, healing time, hospital expenses, and mortality between the two groups. The coma-recovery time, mechanical ventilation time, and healing time were lower in the experimental group than in the control group (P < 0.05), while the hospitalization expenses were higher in the experimental group than in the control group (P < 0.01); moreover, no significant difference was observed in the mortality rate between the two groups. Thus, PHC combined with hemoperfusion exerts a better therapeutic effect in acute severe organophosphorus pesticide poisoning than PHC alone.

  3. Probabilistic acute risk assessment of cumulative exposure to organophosphorus and carbamate pesticides from dietary vegetables and fruits in Shanghai populations.

    PubMed

    Li, Fan; Yuan, Yaqun; Meng, Pai; Wu, Min; Li, Shuguang; Chen, Bo

    2017-02-03

    Organophosphorus pesticides (OPs) and carbamate pesticides (CPs) are among the most widely used pesticides in China, playing a major role in protecting agricultural commodities. In this study, we determined the cumulative acute exposure to OPs and CPs of Shanghai residents from vegetables and fruits (VFs). The food consumption data were obtained from the Shanghai Food Consumption Survey (SHFCS) of 2012-14 including a total of 1973 participants aged 2-90 years. The pesticide residue data were obtained from the Shanghai monitoring programme during 2008-11 with 34 organophosphates and 11 carbamates analysed in a total of 5335 samples of VFs. A probabilistic approach was performed as recommended by the EFSA, using the optimistic model with non-detects set as zero and with processing factors (PFs) being used and the pessimistic model with non-detects replaced by limit of detection (LOD) and without PFs. We used the relative potency factor (RPF) method to normalise the various pesticides to the index compound (IC) of methamidophos and chlorpyrifos separately. Only in the pessimistic model using methamidophos as the IC was there was small risk of exposure exceeding the ARfD (3 µg kg(-)(1) bw day(-)(1)) in the populations of preschool children (0.029%), school-age children (0.022%) and adults (0.002%). There were no risk of exposure exceeding the ARfD of methamidophos in the optimistic model and of chlorpyrifos (100 µg kg(-)(1) bw day(-)(1)) in both optimistic and pessimistic models in all three populations. Considering the Chinese habits of overwhelmingly eating processed food (vegetables being cooked, and fruits being washed or peeled), we conclude that little acute risk was found for the exposure to VF-sourced OPs and CPs in Shanghai.

  4. Identification and quantification of pesticide residues in water samples of Dhamrai Upazila, Bangladesh

    NASA Astrophysics Data System (ADS)

    Hasanuzzaman, M.; Rahman, M. A.; Salam, M. A.

    2016-10-01

    Being agricultural country, different types of pesticides are widely used in Bangladesh to prevent the crop losses due to pest attack which are ultimately drain to the water bodies. The present study was conducted to identify and quantify the organochlorine (DDT, DDE and DDD), organophosphorus (malathion, diazinon and chloropyrifos) and carbamate (carbaryl) residues in water samples of different sources from Dhamrai upazila of Bangladesh using high performance liquid chromatography (HPLC) equipped with ultra violate (UV) detector. Thirty water samples from fish pond, cultivated land and tube-well were collected in winter season to analyze the pesticide residues. Among the organophosphorus pesticides, malathion was present in seven water samples ranging from 42.58 to 922.8 μg/L, whereas diazinon was detected in water sample-8 (WS-8) and the concentration was 31.5 μg/L. None of the tested water samples was found to be contaminated with chlorpyrifos, carbaryl or DDT and its metabolites (DDE and DDD). Except for a tube-well water sample, concentrations of the detected residues are above the acceptable limit for human body as assigned by different organizations. To avoid the possible health hazards, the indiscriminate application of pesticides should be restricted and various substitute products like bio-pesticide should be introduced in a broad scale as soon as possible.

  5. Organophosphorus pesticides detection using broad-specific single-stranded DNA based fluorescence polarization aptamer assay.

    PubMed

    Zhang, Cunzheng; Wang, Li; Tu, Zhui; Sun, Xing; He, Qinghua; Lei, Zhaojing; Xu, Chongxin; Liu, Yuan; Zhang, Xiao; Yang, Jingyi; Liu, Xianjin; Xu, Yang

    2014-05-15

    An approach is developed to detect the organophosphorus pesticides via competitive binding to a recombinant broad-specificity DNA aptamer with a molecular beacon (MB), the binding of the MB to the aptamer results in the activation of a fluorescent signal, which can be measured for pesticide quantification. Aptamers selected via the Systematic Evolution of Ligands by Exponential Enrichment (SELEX) were structurally modified and truncated to narrow down the binding region of the target, which indicated that loops of the aptamer contributed different functions for different chemical recognition. Thereafter, a variant fused by two different minimum functional structures, was clarified with broad specificity and increased affinity. Further molecular docking and molecular dynamics simulations was conducted to understand the molecular interaction between DNA structure and chemicals. 3D modeling revealed a hot spot area formed by 3 binding sites, forces including hydrogen bonds and van der Waals interactions appear to play a significant role in enabling and stabilizing the binding of chemicals. Finally, an engineered aptamer based approach for the detection of organophosphorus pesticides was successfully applied in a test using a real sample, the limit of quantification (LOQ) for phorate, profenofos, isocarbophos, and omethoate reached 19.2, 13.4, 17.2, and 23.4 nM (0.005 mg L(-1)), respectively.

  6. [Preparation of samples for proficiency testing of pesticide residue analysis in processed foods].

    PubMed

    Okihashi, Masahiro; Osakada, Masakazu; Uchida, Kotaro; Nagayoshi, Haruna; Yamaguchi, Takahiro; Kakimoto, Kensaku; Nakayama, Yukiko; Obana, Hirotaka

    2010-01-01

    To conduct proficiency testing for the analysis of pesticide residues in processed foods, fortified samples of retort curry and pancake were examined. In the case of retort curry, heating and mixing were necessary at the time of preparation to provide a homogenous analytical sample. A mixture of 4 carbamates and 11 organophosphorus pesticides was spiked and 14 of them showed consistent results in the samples. In the case of pancake, 10 kinds of pesticides were added to the pastry. The prepared pastry was them cooked. The relative concentrations of most of the pesticides in the pancake were not affected and all the pesticides showed consistent results in the samples. These results showed that the two tested samples were suitable for proficiency testing.

  7. Pesticide and plasticizer residues in citrus essential oils from different countries.

    PubMed

    Di Bella, Giuseppa; Lo Turco, Vincenzo; Rando, Rossana; Arena, Gabriella; Pollicino, Donatella; Luppino, Rosario Rocco; Dugo, Giacomo

    2010-08-01

    Residue analyses are very important in the quality control of citrus essential oils. Organophosphorus and organochlorine pesticides, phosphorated plasticizers and chloroparaffins contamination were investigated by HRGC with FPD and ECD detectors in 120 citrus essential oils produced in Italy and in 70 from other countries in the crop year 2006-2007. Results showed that the largest pesticide quantities were found in oils from Brazil and Spain. The presence of such residues might be the result of an improper use of pesticide in citrus growing or of previous contamination of the extractors. However, the pesticide levels showed a measurable decrease in relation to past production years. The absence of phosporated plasticizers and chloroparaffins can be the result of either improvement of the procedures used during the production cycle or in the storage of the essential oils compared with previous years.

  8. Monitoring of pesticide residues in human milk, soil, water, and food samples collected from Kafr El-Zayat Governorate.

    PubMed

    Dogheim, S M; Mohamed el-Z; Gad Alla, S A; el-Saied, S; Emel, S Y; Mohsen, A M; Fahmy, S M

    1996-01-01

    Pesticide residues in human milk and environmental samples from Kafr El-Zayat Governorate in Egypt were analyzed. This governorate is located near one of the biggest pesticide factories in Egypt. Organochlorine and organophosphorus pesticides were monitored, including those that have been prohibited from use in Egypt. Human milk samples (31 samples) from Kafr El-Zayat were compared with 11 samples collected from Cairo. Data were compared with results from studies performed in 1987 and 1990. The present study showed that aldrin and dieldrin, heptachlor and heptachlor epoxide, and endrin residues have been eliminated from human milk. Estimated daily intakes (EDIs) of DDT complex and gamma-HCH by breast-fed infants in Kafr El-Zayat were 85.96 and 3.1% of the respective acceptable daily intakes (ADIs). beta-HCH residues showed an increasing pattern, especially in human milk samples from Cairo. DDT complex and HCH isomers in orange, spinach, lettuce, potatoes, and clover samples ranged from undetectable to very low concentrations. Higher levels of DDT and HCH were detected, but aldrin, dieldrin, endrin, and the heptachlors were not detected in food of animal origin. Residues in fish samples were below maximum residue limits established by some developed countries. Those in animal milk samples approached the extraneous residue limits of the Codex Committee on Pesticide Residues. HCH residues in soil were negligible, but DDT residues in soil were somewhat higher. Among water samples, groundwater samples had the highest residues of HCHs and DDTs, followed by Nile River water and then tap water. However, the organochlorine pesticide residues were found at concentrations below the maximum allowable limits set by the World Health Organization for drinking water. Among 12 organophosphorus pesticides monitored as parent compounds, dimethoate, malathion, methamidophos, and chlorpyrifos residues were detected in low concentrations in soil samples from a pesticide factory. No

  9. Predictors of Detected Organophosphorus Pesticides Among Orang Asli Children Living in Malaysia.

    PubMed

    Mat Sutris, Juliana; Md Isa, Zaleha; Sumeri, Siti Arfah; Ghazi, Hasanain Faisal

    Increasing use of pesticides in agriculture to control pest may result in permanent damage to the environment and consequently cause harmful health problems especially among infant and children. Due to pesticide's natural toxicity and its widespread use, it causes a serious threat to public health especially to this vulnerable group. The purpose of this study was to determine the organophosphorus pesticide urinary metabolite levels and its predictors among Orang Asli children of the Mah Meri tribe living in an agricultural island in Kuala Langat, Selangor. Data collection was carried out at an island in Kuala Langat, Selangor, where a total of 180 Orang Asli children of the Mah Meri tribe voluntarily participated in the study. Data were collected via a validated, modified questionnaire. Urinary organophosphate metabolites, namely dimethylphosphate, diethylphosphate, dimethylthiophosphate, dimethyldithiophosphate, diethylthiophosphate, and diethyldithiophosphate were measured to assess organophosphate pesticide exposure in children. Eighty-four (46.7%) of the respondents were positive for urine dialkyl phosphate metabolites. In multivariable analysis, children who frequently consumed apples had 4 times higher risk of pesticide detection than those who consumed apple less frequently. In addition, those who frequently ate cucumbers had 4 times higher risk for pesticide detection than those who ate cucumbers less frequently. Children with a father whose occupation involved high exposure to pesticides (agriculture) had 3 times higher risk of pesticide detection than those with a father in a low-risk occupation (nonagriculture). Almost half of the children (46.7%) in the study area tested positive for urinary dialkyl phosphate metabolite levels. Most of the metabolite levels were equal to or higher than that reported in other previous studies. Major factors associated with pesticide detection in children in this study were frequent intake of apple and cucumber and

  10. Albumin binding as a potential biomarker of exposure to moderately low levels of organophosphorus pesticides.

    PubMed

    Tarhoni, Mabruka H; Lister, Timothy; Ray, David E; Carter, Wayne G

    2008-06-01

    We have evaluated the potential of plasma albumin to provide a sensitive biomarker of exposure to commonly used organophosphorus pesticides in order to complement the widely used measure of acetylcholinesterase (AChE) inhibition. Rat or human plasma albumin binding by tritiated-diisopropylfluorophosphate ((3)H-DFP) was quantified by retention of albumin on glass microfibre filters. Preincubation with unlabelled pesticide in vitro or dosing of F344 rats with pesticide in vivo resulted in a reduction in subsequent albumin radiolabelling with (3)H-DFP, the decrease in which was used to quantify pesticide binding. At pesticide exposures producing approximately 30% inhibition of AChE, rat plasma albumin binding in vitro by azamethiphos (oxon), chlorfenvinphos (oxon), chlorpyrifos-oxon, diazinon-oxon and malaoxon was reduced from controls by 9+/-1%, 67+/-2%, 56+/-2%, 54+/-2% and 8+/-1%, respectively. After 1 h of incubation with 19 microM (3)H-DFP alone, the level of binding to rat or human plasma albumins reached 0.011 or 0.039 moles of DFP per mole of albumin, respectively. This level of binding could be further increased by raising the concentration of (3)H-DFP, increasing the (3)H-DFP incubation time, or by substitution of commercial albumins for native albumin. Pesticide binding to albumin was presumed covalent since it survived 24 h dialysis. After dosing rats with pirimiphos-methyl (dimethoxy) or chlorfenvinphos (oxon) (diethoxy) pesticides, the resultant albumin binding were still significant 7 days after dosing. As in vitro, dosing of rats with malathion did not result in significant albumin binding in vivo. Our results suggest albumin may be a useful additional biomonitor for moderately low-level exposures to several widely used pesticides, and that this binding differs markedly between pesticides.

  11. Early management after self-poisoning with an organophosphorus or carbamate pesticide – a treatment protocol for junior doctors

    PubMed Central

    Eddleston, Michael; Dawson, Andrew; Karalliedde, Lakshman; Dissanayake, Wasantha; Hittarage, Ariyasena; Azher, Shifa; Buckley, Nick A

    2004-01-01

    Severe organophosphorus or carbamate pesticide poisoning is an important clinical problem in many countries of the world. Unfortunately, little clinical research has been performed and little evidence exists with which to determine best therapy. A cohort study of acute pesticide poisoned patients was established in Sri Lanka during 2002; so far, more than 2000 pesticide poisoned patients have been treated. A protocol for the early management of severely ill, unconscious organophosphorus/carbamate-poisoned patients was developed for use by newly qualified doctors. It concentrates on the early stabilisation of patients and the individualised administration of atropine. We present it here as a guide for junior doctors in rural parts of the developing world who see the majority of such patients and as a working model around which to base research to improve patient outcome. Improved management of pesticide poisoning will result in a reduced number of suicides globally. PMID:15566582

  12. Cannabinoid CB1 receptor as a target for chlorpyrifos oxon and other organophosphorus pesticides.

    PubMed

    Quistad, Gary B; Nomura, Daniel K; Sparks, Susan E; Segall, Yoffi; Casida, John E

    2002-09-05

    Binding of the endocannabinoid anandamide or of Delta(9)-tetrahydrocannabinol to the agonist site of the cannabinoid receptor (CB1) is commonly assayed with [3H]CP 55,940. Potent long-chain alkylfluorophosphonate inhibitors of agonist binding suggest an additional, important and closely-coupled nucleophilic site, possibly undergoing phosphorylation. We find that the CB1 receptor is also sensitive to inhibition in vitro and in vivo by several organophosphorus pesticides and analogs. Binding of [3H]CP 55,940 to mouse brain CB1 receptor in vitro is inhibited 50% by chlorpyrifos oxon at 14 nM, chlorpyrifos methyl oxon at 64 nM and paraoxon, diazoxon and dichlorvos at 1200-4200 nM. Some 15 other organophosphorus pesticides and analogs are less active in vitro. The plant defoliant tribufos inhibits CB1 in vivo, without cholinergic poisoning signs, by 50% at 50 mg/kg intraperitoneally with a recovery half-time of 3-4 days, indicating covalent derivatization. [3H-ethyl]Chlorpyrifos oxon may be suitable for radiolabeling and characterization of this proposed nucleophilic site.

  13. A gold-based nanobeacon probe for fluorescence sensing of organophosphorus pesticides.

    PubMed

    Dou, Xiaowen; Chu, Xianfeng; Kong, Weijun; Luo, Jiaoyang; Yang, Meihua

    2015-09-03

    A nanomaterials-based novel molecular beacon has attracted growing attentions in fluorescent assays as many nanomaterials possess excellent quenching efficiency. In this work, a gold-based nanobeacon probe was established to detect organophosphorus pesticides for the first time. The constructed gold-based nanobeacon acted as a signal indicator and could display the decreasing of the intensity in the presence of targets, which competitively bound to single strand DNA. To achieve a high sensitive probe, some parameters including solution pH, temperature and reaction time were investigated and optimized. The gold-based nanobeacon probe assay was proved to be rapid and sensitive to achieve a detection limit of 0.035 μM for isocarbophos, 0.134 μM for profenofos, 0.384 μM for phorate and 2.35 μM for omethoate, respectively. The prepared nanobeacon effectively reduced the background and improved the detection sensitivity and selectivity. The probe is stable, easy to operate and does not need sophisticated instruments. These features makes the probe feasible for screening trace organophosphorus pesticides in real samples.

  14. a Enzyme-Based Electrochemical Sensor for Sensitive Detection of Organophosphorus Pesticides

    NASA Astrophysics Data System (ADS)

    Zhou, Nong; Li, Chengyong; Mo, Rijian; Zhang, Peng; He, Lei; Nie, Fanghong; Su, Weiming; Liu, Shucheng; Gao, Jing; Shao, Haiyan; Qian, Zhong-Ji; Ji, Hongwu

    2016-12-01

    A sensitive and fast sensor for quantitative detection of organophosphorus pesticides (OPs) is obtained using acetylcholinesterase (AChE) biosensor based on graphene oxide (GO)-chitosan (CS) composite film. This new biosensor is prepared via depositing GO-CS composite film on glassy carbon electrode (GCE) and then assembling AChE on the composite film. The GO-CS composite film shows an excellent biocompatibility with AChE and enhances immobilization efficiency of AChE. GO homogeneously disperses in the GO-CS composite films and exhibits excellent electrocatalytic activity to thiocholine oxidation, which is from acetylthiocholine catalyzed by AChE. The results show that the inhibition of carbaryl/trichlorfon on AChE activity is proportional to the concentration of carbaryl/trichlorfon. The detection of linear range for carbaryl is from 10nM to 100nM and the correlation coefficients of 0.993. The detection limit for carbaryl is calculated to be about 2.5nM. In addition, the detection of linear range for trichlorfon is from 10nM to 60nM and the correlation coefficients of 0.994. The detection limit for trichlorfon is calculated to be about 1.2nM. This biosensor provides a new promising tool for trace organophosphorus pesticide detection.

  15. Development of Phage Immuno-Loop-Mediated Isothermal Amplification Assays for Organophosphorus Pesticides in Agro-products

    PubMed Central

    2015-01-01

    Two immuno-loop-mediated isothermal amplification assays (iLAMP) were developed by using a phage-borne peptide that was isolated from a cyclic eight-peptide phage library. One assay was used to screen eight organophosphorus (OP) pesticides with limits of detection (LOD) between 2 and 128 ng mL–1. The iLAMP consisted of the competitive immuno-reaction coupled to the LAMP reaction for detection. This method provides positive results in the visual color of violet, while a negative response results in a sky blue color; therefore, the iLAMP allows one to rapidly detect analytes in yes or no fashion. We validated the iLAMP by detecting parathion-methyl, parathion, and fenitrothion in Chinese cabbage, apple, and greengrocery, and the detection results were consistent with the enzyme-linked immunosorbent assay (ELISA). In conclusion, the iLAMP is a simple, rapid, sensitive, and economical method for detecting OP pesticide residues in agro-products with no instrumental requirement. PMID:25135320

  16. Development of phage immuno-loop-mediated isothermal amplification assays for organophosphorus pesticides in agro-products.

    PubMed

    Hua, Xiude; Yin, Wei; Shi, Haiyan; Li, Ming; Wang, Yanru; Wang, Hong; Ye, Yonghao; Kim, Hee Joo; Gee, Shirley J; Wang, Minghua; Liu, Fengquan; Hammock, Bruce D

    2014-08-19

    Two immuno-loop-mediated isothermal amplification assays (iLAMP) were developed by using a phage-borne peptide that was isolated from a cyclic eight-peptide phage library. One assay was used to screen eight organophosphorus (OP) pesticides with limits of detection (LOD) between 2 and 128 ng mL(-1). The iLAMP consisted of the competitive immuno-reaction coupled to the LAMP reaction for detection. This method provides positive results in the visual color of violet, while a negative response results in a sky blue color; therefore, the iLAMP allows one to rapidly detect analytes in yes or no fashion. We validated the iLAMP by detecting parathion-methyl, parathion, and fenitrothion in Chinese cabbage, apple, and greengrocery, and the detection results were consistent with the enzyme-linked immunosorbent assay (ELISA). In conclusion, the iLAMP is a simple, rapid, sensitive, and economical method for detecting OP pesticide residues in agro-products with no instrumental requirement.

  17. Determination of Pesticide Residues in Cannabis Smoke

    PubMed Central

    Sullivan, Nicholas; Elzinga, Sytze; Raber, Jeffrey C.

    2013-01-01

    The present study was conducted in order to quantify to what extent cannabis consumers may be exposed to pesticide and other chemical residues through inhaled mainstream cannabis smoke. Three different smoking devices were evaluated in order to provide a generalized data set representative of pesticide exposures possible for medical cannabis users. Three different pesticides, bifenthrin, diazinon, and permethrin, along with the plant growth regulator paclobutrazol, which are readily available to cultivators in commercial products, were investigated in the experiment. Smoke generated from the smoking devices was condensed in tandem chilled gas traps and analyzed with gas chromatography-mass spectrometry (GC-MS). Recoveries of residues were as high as 69.5% depending on the device used and the component investigated, suggesting that the potential of pesticide and chemical residue exposures to cannabis users is substantial and may pose a significant toxicological threat in the absence of adequate regulatory frameworks. PMID:23737769

  18. Transformation of Organophosphorus Pesticides in the Presence of Aqueous Chlorine: Kinetics, Pathways, and Structure-Activity Relationships

    EPA Science Inventory

    The fate of organophosphorus (OP) pesticides in the presence of aqueous chlorine was investigated under simulated drinking water treatment conditions. Intrinsic rate coefficients were found for the reaction of hypochlorous acid (kHOCl,OP) and hypochlorite ion (kOCl,OP) for eight...

  19. DEVELOPMENT OF A RISK ASSESSMENT MODEL FOR THE EFFECTS OF ORGANOPHOSPHORUS PESTICIDES ON INFECTIOUS DISEASE SUSCEPTIBILITY AND THE IMMUNE SYSTEM

    EPA Science Inventory

    There is increased concern about the sublethal effects of organophosphorus (OP) pesticides on human and animal health. This class of chemicals has been shown to affect the immune function of macrophages and lymphocytes. Malathion, an OP compound, is one of the most widely used ...

  20. DEVELOPMENT OF A RISK ASSESSMENT MODEL FOR THE EFFECTS OF ORGANOPHOSPHORUS PESTICIDES ON INFECTIOUS DISEASE SUSCEPTIBILITY AND THE IMMUNE SYSTEM

    EPA Science Inventory

    There is increased concern about the sublethal effects of organophosphorus (OP) pesticides on human and animal health. This class of chemicals has been shown to affect the immune function of macrophages and lymphocytes. Malathion, an OP compound, is one of the most widely used ...

  1. DEVELOPMENT OF AN IN VITRO ASSAY THAT MAY IDENTIFY WHICH ORGANOPHOSPHORUS PESTICIDES ARE MORE TOXIC TO THE YOUNG.

    EPA Science Inventory

    Some, but not all, organophosphorus pesticides are more acutely toxic to the young as compared to adults. We have developed an in vitro assay which measures the detoxification potential (via carboxylesterase and A-esterases) of tissues. Previous results using this in vitro assay ...

  2. [Determination of 21 organophosphorus pesticides in tea by gas chromatography-mass spectrometry coupled with hydroxylated multi-walled carbon nanotubes based on dispersive solid-phase extraction].

    PubMed

    Rong, Jiefeng; Wei, Hang; Li, Yijun; Huang, Huoshui; Xu, Meizhu

    2016-02-01

    A rapid determination method of 21 organophosphorus pesticides in tea was developed by QuEChERS method using modified multi-walled carbon nanotubes (MWCNTs-OH), primary-secondary amine (PSA) and MgSO4 coupled with gas chromatography-mass spectrometry. The pesticide residues in tea were extracted with a hexane-acetone (2:1, v/v) mixture, and cleaned up by dispersive solid-phase extraction using MWCNTs-OH and primary-secondary amine (PSA) as the sorbents. After centrifugation and filtration, the target compounds were analyzed by gas chromatography-mass spectrometry and quantified by the external standard method. Under the optimized conditions, good linearities were obtained in the range of 0. 01- 0. 50 mg/kg. The average recoveries were in the range of 81. 5% -109. 4% at three spiked levels, with relative standard deviations (RSDs, n = 5 ) of 2. 3% - 10. 6%. The limits of quantification were 0. 001-0. 040 mg/kg. This method is simple, fast, sensitive, cheap, and can meet the requirements of the rapid detection of organophosphorus pesticides in tea.

  3. Nanomaterials - Acetylcholinesterase Enzyme Matrices for Organophosphorus Pesticides Electrochemical Sensors: A Review

    PubMed Central

    Periasamy, Arun Prakash; Umasankar, Yogeswaran; Chen, Shen-Ming

    2009-01-01

    Acetylcholinesterase (AChE) is an important cholinesterase enzyme present in the synaptic clefts of living organisms. It maintains the levels of the neurotransmitter acetylcholine by catalyzing the hydrolysis reaction of acetylcholine to thiocholine. This catalytic activity of AChE is drastically inhibited by trace amounts of organophosphorus (OP) pesticides present in the environment. As a result, effective monitoring of OP pesticides in the environment is very desirable and has been done successfully in recent years with the use of nanomaterial-based AChE sensors. In such sensors, the enzyme AChE has been immobilized onto nanomaterials like multiwalled carbon nanotubes, gold nanoparticles, zirconia nanoparticles, cadmium sulphide nano particles or quantum dots. These nanomaterial matrices promote significant enhancements of OP pesticide determinations, with the thiocholine oxidation occurring at much lower oxidation potentials. Moreover, nanomaterial-based AChE sensors with rapid response, increased operational and long storage stability are extremely well suited for OP pesticide determination over a wide concentration range. In this review, the unique advantages of using nanomaterials as AChE immobilization matrices are discussed. Further, detection limits, sensitivities and correlation coefficients obtained using various electroanalytical techniques have also been compared with chromatographic techniques. PMID:22408512

  4. Adsorption of organophosphorus pesticides in tropical soils: The case of karst landscape of northwestern Yucatan.

    PubMed

    Alfonso, Lorenzo-Flores; Germán, Giácoman Vallejos; María Del Carmen, Ponce Caballero; Hossein, Ghoveisi

    2017-01-01

    This article discusses the adsorption of four organophosphorus pesticides-diazinon, dimethoate, methyl parathion, and sulfotep-in soil samples from four sites-Komchén, Xcanatún, Chablekal and Mocochá- in the northwest of Yucatan, Mexico. These pesticides have been detected in groundwater at concentrations greater than 5 (μg/L) during recent monitoring campaigns in the study area. In this region, groundwater contamination is exacerbated by its karst aquifer, which is susceptible to contamination and is considered very vulnerable. The experimental work was carried out using the batch equilibrium technique. Pesticide analyses by solid-phase extraction and gas chromatography were performed. The equilibrium adsorption data were analyzed by Henry, Langmuir and Freundlich models. The results indicate that the Freundlich model provides the best correlation of the experimental data. Freundlich adsorption coefficients Kf were in the range of 1.62-2.35 for sulfotep, 2.43 to 3.25 for dimethoate, from 5.54 to 9.27 for methyl parathion, and 3.22 to 5.17 for diazinon. Freundlich adsorption coefficients were normalized to the content of organic carbon in the soil to estimate the sorption coefficient of organic carbon (KOC). KOC values were in the range of 9.45-71.80, indicated that four pesticides have low adsorption on the four studied soils, which represents a high risk of contamination to the aquifer. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Development of a solid-phase extraction coupling chemiluminescent enzyme immunoassay for determination of organophosphorus pesticides in environmental water samples.

    PubMed

    Xu, Zhen-Lin; Sun, Wen-Jia; Yang, Jin-Yi; Jiang, Yue-Ming; Campbell, Katrina; Shen, Yu-Dong; Lei, Hong-Tao; Zeng, Dao-Ping; Wang, Hong; Sun, Yuan-Ming

    2012-03-07

    Solid-phase extraction (SPE) and direct competitive chemiluminescence enzyme immunoassay (dcCL-EIA) were combined for the detection of organophosphorus pesticides (OPs) in environmental water samples. dcCL-EIA based on horseradish peroxidase labeled with a broad-specificity monoclonal antibody against OPs was developed, and the effects of several physicochemical parameters on dcCL-EIA performance were studied. SPE was used for the pretreatment of water samples to remove interfering substances and to concentrate the OP analytes. The coupling of SPE and dcCL-EIA can detect seven OPs (parathion, coumaphos, phoxim, quinalphos, triazophos, dichlofenthion, and azinphos-ethyl) with the limit of quantitation below 0.1 ng/mL. The recoveries of OPs from spiked water samples ranged from 62.5% to 131.7% by SPE-dcCL-EIA and 69.5% to 112.3% by SPE-HPLC-MS/MS. The screening of OP residues in real-world environmental water samples by the developed SPE-dcCL-EIA and their confirmatory analysis using SPE-HPLC-MS/MS demonstrated that the assay is ideally suited as a monitoring method for OP residues prior to chromatographic analysis.

  6. Effects of a provincial ban of two toxic organophosphorus insecticides on pesticide poisoning hospital admissions

    PubMed Central

    2012-01-01

    Background. Pesticide self-poisoning causes one third of global suicides. Sri Lanka halved its suicide rate by banning WHO Class I organophosphorus (OP) insecticides and then endosulfan. However, poisoning with Class II toxicity OPs, particularly dimethoate and fenthion, remains a problem. We aimed to determine the effect and feasibility of a ban of the two insecticides in one Sri Lankan district. Methods. Sale was banned in June 2003 in most of Polonnaruwa District, but not Anuradhapura District. Admissions with pesticide poisoning to the district general hospitals was prospectively recorded from 2002. Results. Hospital admissions for dimethoate and fenthion poisoning fell by 43% after the ban in Polonnaruwa, while increasing by 23% in Anuradhapura. The pesticide case fatality fell from 14.4% to 9.0% in Polonnaruwa (odds ratio [OR] 0.59, 95% confidence interval [CI] 0.41–0.84) and 11.3% to 10.6% in Anuradhapura (OR 0.93, 95%CI 0.70–1.25; p = 0.051). This reduction was not sustained, with case fatality in Polonnaruwa rising to 12.1% in 2006–2007. Further data analysis indicated that the fall in case fatality had actually been due to a coincidental reduction in case fatality for pesticide poisoning overall, in particular for paraquat poisoning. Conclusions. We found that the insecticides could be effectively banned from agricultural practice, as shown by the fall in hospital admissions, with few negative consequences. However, the ban had only a minor effect on pesticide poisoning deaths because it was too narrow. A study assessing the agricultural and health effects of a more comprehensive ban of highly toxic pesticides is necessary to determine the balance between increased costs of agriculture and reduced health care costs and fewer deaths. PMID:22372788

  7. Dietary intake and its contribution to longitudinal organophosphorus pesticide exposure in urban/suburban children.

    PubMed

    Lu, Chensheng; Barr, Dana B; Pearson, Melanie A; Waller, Lance A

    2008-04-01

    The widespread use of organophosphorus (OP) pesticides has led to frequent exposure in adults and children. Because such exposure may cause adverse health effects, particularly in children, the sources and patterns of exposure need to be studied further. We assessed young urban/suburban children's longitudinal exposure to OP pesticides in the Children's Pesticide Exposure Study (CPES) conducted in the greater Seattle, Washington, area, and used a novel study design that allowed us to determine the contribution of dietary intake to the overall OP pesticide exposure. Twenty-three children 3-11 years of age who consumed only conventional diets were recruited for this 1-year study conducted in 2003-2004. Children switched to organic diets for 5 consecutive days in the summer and fall sampling seasons. We measured specific urinary metabolites for malathion, chlorpyrifos, and other OP pesticides in urine samples collected twice daily for a period of 7, 12, or 15 consecutive days during each of the four seasons. By substituting organic fresh fruits and vegetables for corresponding conventional food items, the median urinary metabolite concentrations were reduced to nondetected or close to non-detected levels for malathion and chlorpyrifos at the end of the 5-day organic diet intervention period in both summer and fall seasons. We also observed a seasonal effect on the OP urinary metabolite concentrations, and this seasonality corresponds to the consumption of fresh produce throughout the year. The findings from this study demonstrate that dietary intake of OP pesticides represents the major source of exposure in young children.

  8. Occurrence of pesticide residues in Spanish beeswax.

    PubMed

    Calatayud-Vernich, Pau; Calatayud, Fernando; Simó, Enrique; Picó, Yolanda

    2017-12-15

    Beeswax from Spain was collected during 2016 to determine pesticide residues incidence. The 35 samples were divided in foundation, old combs, cappings or virgin beeswax to compare pesticide content between groups. Wax was screened for 58 pesticides or their degradation products by QuEChERS extraction and liquid chromatography mass spectrometry (LC-MS/MS). Beeswax was uniformly contaminated with acaricides and, to a much lesser extent, with insecticide and fungicide residues. Virgin followed by cappings were less contaminated than foundation and old combs beeswax. The miticides applied in-hive had a contribution to average pesticide load higher than 95%. Compounds widely used as acaricides, as coumaphos (100%), fluvalinate (86%) and amitraz (83%), were the pesticides most frequently detected with maximum concentrations of 26,858, 3593 and 6884ng·g(-1), respectively. Chlorfenvinphos, acrinathrin and flumethrin, also acaricides, were detected in 77, 71 and 54%, respectively. Frequencies of pesticides used in crops were 40% for chlorpyrifos, 29% for dichlofenthion, 9% for malathion, 6% for fenthion-sulfoxide and 3% for azinphos-methyl, carbendazim, ethion, hexythiazox, imazalil and pyriproxyfen. Pesticide assessment in beeswax could be an excellent monitoring tool to establish veterinary treatments applied by beekeepers and environmental contaminants exposure of honey bees. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. [Simultaneous determination of organophosphorus pesticides in cruciferous vegetables by dual-column GC with pulsed FPD and FTD].

    PubMed

    Ueno, Eiji; Oshima, Harumi; Saito, Isao; Matsumoto, Hiroshi; Nakazawa, Hiroyuki

    2004-02-01

    We evaluated simultaneous analytical methods for organophosphorus pesticides in cruciferous vegetables by gas chromatography (GC). Firstly, 36 pesticides were selected on the basis of monitoring data (April 1996-March 2003) in Aichi Prefecture. A sample was extracted with acetonitrile and the acetonitrile layer was separated by salting-out. The extract was cleaned up with gel permeation chromatography (GPC), and then with a tandem silica-gel/PSA mini-column. The test solution was subjected to dual-column GC equipped with a pulsed FPD (P mode, Rtx-OPPesticides column) and a FTD (Rtx-OPPesticides 2 column). Organophosphorus pesticides in such sulfur-rich matrices as cabbage and radish were determined without any serious interfering peaks on the pulsed FPD chromatograms after diluting the extracts 10- to 20-fold (0.25-0.5 mg/L of sample). The method was applied to cruciferous vegetables to demonstrate its usefulness in routine analysis.

  10. Multiwalled carbon nanotubes as solid-phase extraction materials for the gas chromatographic determination of organophosphorus pesticides in waters.

    PubMed

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Angel Rodríguez-Delgado, Miguel

    2008-10-01

    In the present work, a GC method with nitrogen-phosphorus detection (NPD) was developed for the simultaneous determination of eight organophosphorus pesticide (OPP) residues (i.e., ethoprofos, diazinon, chlorpyrifos-methyl, fenitrothion, malathion, chlorpyrifos, fenamiphos, and buprofezin) in water samples. Preconcentration of the water samples was carried out using an SPE procedure with multiwalled carbon nanotubes (MWCNTs) of 10-15 nm od, 2-6 nm id, and 0.1-10 microm length as stationary phase. Extraction parameters, such as the amount of MWCNTs, sample volume, pH, and type and amount of the eluent were optimized. The most favorable conditions were as follows: 40 mg MWCNTs, 800 mL water, pH 6.0, and 20 mL dichloromethane, respectively. The MWCNTs-SPE-GC-NPD method was applied to the determination of these pesticides in real water samples: mineral and ground water as well as run-off water from an agricultural area collected shortly before opening out onto the sea. A recovery study was developed with five consecutive extractions of the three types of water spiked at three concentration levels (n = 15). Mean recovery values were in the range of 75-116% for mineral water (RSD < 6.3%), 67-119% for ground water (RSD < 5.8%), and 57-81% for run-off waters (RSDs < 6.9%), except for fenamiphos (mean recovery values between 40 and 84% for the three types of waters, RSDs < 8.9%). LODs were in the low ng/L level (i.e., levels below the maximum residue limits (MRLs) established by the European Union (EU) legislation for these compounds in waters). The proposed method was also applied to the analysis of six water samples (two of each type: mineral, ground, and run-off waters) in which no residues of the selected pesticides were found. Results show that the MWCNTs used in this work have a high adsorbability of the pesticides under study. The main advantage of the use of these MWCNTs is their low cost when compared with those MWCNTs previously used in the literature and with

  11. Determinants of organophosphorus pesticide urinary metabolite levels in young children living in an agricultural community.

    PubMed

    Bradman, Asa; Castorina, Rosemary; Barr, Dana Boyd; Chevrier, Jonathan; Harnly, Martha E; Eisen, Ellen A; McKone, Thomas E; Harley, Kim; Holland, Nina; Eskenazi, Brenda

    2011-04-01

    Organophosphorus (OP) pesticides are used in agriculture and several are registered for home use. As young children age they may experience different pesticide exposures due to varying diet, behavior, and other factors. We measured six OP dialkylphosphate (DAP) metabolites (three dimethyl alkylphosphates (DMAP) and three diethyl alkylphosphates (DEAP)) in urine samples collected from ~400 children living in an agricultural community when they were 6, 12, and 24 months old. We examined bivariate associations between DAP metabolite levels and determinants such as age, diet, season, and parent occupation. To evaluate independent impacts, we then used generalized linear mixed multivariable models including interaction terms with age. The final models indicated that DMAP metabolite levels increased with age. DMAP levels were also positively associated with daily servings of produce at 6- and 24-months. Among the 6-month olds, DMAP metabolite levels were higher when samples were collected during the summer/spring versus the winter/fall months. Among the 12-month olds, DMAP and DEAP metabolites were higher when children lived ≤ 60 meters from an agricultural field. Among the 24-month-olds, DEAP metabolite levels were higher during the summer/spring months. Our findings suggest that there are multiple determinants of OP pesticide exposures, notably dietary intake and temporal and spatial proximity to agricultural use. The impact of these determinants varied by age and class of DAP metabolite.

  12. Determinants of Organophosphorus Pesticide Urinary Metabolite Levels in Young Children Living in an Agricultural Community

    PubMed Central

    Bradman, Asa; Castorina, Rosemary; Barr, Dana Boyd; Chevrier, Jonathan; Harnly, Martha E.; Eisen, Ellen A.; McKone, Thomas E.; Harley, Kim; Holland, Nina; Eskenazi, Brenda

    2011-01-01

    Organophosphorus (OP) pesticides are used in agriculture and several are registered for home use. As young children age they may experience different pesticide exposures due to varying diet, behavior, and other factors. We measured six OP dialkylphosphate (DAP) metabolites (three dimethyl alkylphosphates (DMAP) and three diethyl alkylphosphates (DEAP)) in urine samples collected from ∼400 children living in an agricultural community when they were 6, 12, and 24 months old. We examined bivariate associations between DAP metabolite levels and determinants such as age, diet, season, and parent occupation. To evaluate independent impacts, we then used generalized linear mixed multivariable models including interaction terms with age. The final models indicated that DMAP metabolite levels increased with age. DMAP levels were also positively associated with daily servings of produce at 6- and 24-months. Among the 6-month olds, DMAP metabolite levels were higher when samples were collected during the summer/spring versus the winter/fall months. Among the 12-month olds, DMAP and DEAP metabolites were higher when children lived ≤60 meters from an agricultural field. Among the 24-month-olds, DEAP metabolite levels were higher during the summer/spring months. Our findings suggest that there are multiple determinants of OP pesticide exposures, notably dietary intake and temporal and spatial proximity to agricultural use. The impact of these determinants varied by age and class of DAP metabolite. PMID:21695029

  13. Biological monitoring of organophosphorus pesticide exposure among children of agricultural workers in central Washington State.

    PubMed Central

    Loewenherz, C; Fenske, R A; Simcox, N J; Bellamy, G; Kalman, D

    1997-01-01

    Children up to 6 years of age who lived with pesticide applicators were monitored for increased risk of pesticide exposure: 48 pesticide applicator and 14 reference families were recruited from an agricultural region of Washington State in June 1995. A total of 160 spot urine samples were collected from 88 children, including repeated measures 3-7 days apart. Samples were assayed by gas chromatography flame photometric detector for dimethylphosphate metabolites. Dimethylthiophosphate (DMTP) was the dominant metabolite. DMTP levels were significantly higher in applicator children than in reference children (p = 0.015), with median concentrations of 0.021 and 0.005 microg/ml, respectively; maximum concentrations were 0.44 and 0.10 microg/ml, respectively. Percentages of detectable samples were 47% for applicator children and 27% for reference children. A marginally significant trend of increasing concentration was observed with decreasing age among applicator children (p = 0.060), and younger children within these families had significantly higher concentrations when compared to their older siblings (p = 0.040). Applicator children living less than 200 feet from an orchard were associated with higher frequency of detectable DMTP levels than nonproximal applicator children (p =0.036). These results indicate that applicator children experienced higher organophosphorus pesticide exposures than did reference children in the same community and that proximity to spraying is an important contributor to such exposures. Trends related to age suggest that child activity is an important variable for exposure. It is unlikely that any of the observed exposures posed a hazard of acute intoxication. This study points to the need for a more detailed understanding of pesticide exposure pathways for children of agricultural workers. Images Figure 1. Figure 2. Figure 3. PMID:9405329

  14. A review on the molecular mechanisms involved in insulin resistance induced by organophosphorus pesticides.

    PubMed

    Lasram, Mohamed Montassar; Dhouib, Ines Bini; Annabi, Alya; El Fazaa, Saloua; Gharbi, Najoua

    2014-08-01

    There is increasing evidence reporting that organophosphorus pesticides (OPs) impair glucose homeostasis and cause insulin resistance and type 2 diabetes. Insulin resistance is a complex metabolic disorder that defies explanation by a single etiological pathway. Formation of advanced glycation end products, accumulation of lipid metabolites, activation of inflammatory pathways and oxidative stress have all been implicated in the pathogenesis of insulin resistance. Ultimately, these molecular processes activate a series of stress pathways involving a family of serine kinases, which in turn have a negative effect on insulin signaling. Experimental and clinical data suggest an association between these molecular mechanisms and OPs compounds. It was first reported that OPs induce hyperglycemia. Then a concomitant increase of blood glucose and insulin was pointed out. For some years only, we have begun to understand that OPs promote insulin resistance and increase the risk of type 2 diabetes. Overall, this review outlines various mechanisms that lead to the development of insulin resistance by OPs exposure.

  15. A systematic review on human exposure to organophosphorus pesticides in Iran.

    PubMed

    Shadboorestan, Amir; Vardanjani, Hossein Molavi; Abdollahi, Mohammad; Goharbari, Mohammad Hadi; Khanjani, Narges

    2016-07-02

    Human exposure to organophosphorus (OP) pesticides is a serious health challenge. We conducted a systematic review by searching international and national databases for published literature on any human exposure to OPs in Iran from 1990 to March 2015. Qualified papers were in two categories including studies in which biomarkers of exposure were assessed (n = 13; total no. of subjects = 759) and studies that had reported prevalence of OPs-induced poisoning (OPP) and mortality (n = 26; total no. of subjects = 5428). The mean level of activity of acetyl-cholinesterase and butyryl-cholinesterase were 68.65% and 74.2%, respectively. Overall proportion (%) of OPP was estimated (16; 95% CI, 14 to 19).

  16. Concentrations of dialkyl phosphate metabolites of organophosphorus pesticides in the U.S. population.

    PubMed Central

    Barr, Dana B; Bravo, Roberto; Weerasekera, Gayanga; Caltabiano, Lisa M; Whitehead, Ralph D; Olsson, Anders O; Caudill, Samuel P; Schober, Susan E; Pirkle, James L; Sampson, Eric J; Jackson, Richard J; Needham, Larry L

    2004-01-01

    We report population-based concentrations, stratified by age, sex, and racial/ethnic groups, of dialkyl phosphate (DAP) metabolites of multiple organophosphorus pesticides. We measured dimethylphosphate (DMP), dimethylthiophosphate (DMTP), dimethyldithiophosphate (DMDTP), diethylphosphate (DEP), diethylthiophosphate (DETP), and diethyldithiophosphate (DEDTP) concentrations in 1,949 urine samples collected in U.S. residents 6-59 years of age during 1999 and 2000 as a part of the ongoing National Health and Nutrition Examination Survey (NHANES). We detected each DAP metabolite in more than 50% of the samples, with DEP being detected most frequently (71%) at a limit of detection of 0.2 microg/L. The geometric means for the metabolites detected in more than 60% of the samples were 1.85 microg/L for DMTP and 1.04 microg/L for DEP. The 95th percentiles for each metabolite were DMP, 13 microg/L; DMTP, 46 microg/L; DMDTP, 19 micro g/L; DEP, 13 microg/L; DETP, 2.2 microg/L; and DEDTP, 0.87 microg/L. We determined the molar sums of the dimethyl-containing and diethyl-containing metabolites; their geometric mean concentrations were 49.4 and 10.5 nmol/L, respectively, and their 95th percentiles were 583 and 108 nmol/L, respectively. These data are also presented as creatinine-adjusted concentrations. Multivariate analyses showed concentrations of DAPs in children 6-11 years of age that were consistently significantly higher than in adults and often higher than in adolescents. Although the concentrations between sexes and among racial/ethnic groups varied, no significant differences were observed. These data will be important in evaluating the impact of organophosphorus pesticide exposure in the U.S. population and the effectiveness of regulatory actions. PMID:14754573

  17. Impact of prechlorination on organophosphorus pesticides during drinking water treatment: Removal and transformation to toxic oxon byproducts.

    PubMed

    Li, Wei; Wu, Ruiqing; Duan, Jinming; Saint, Christopher P; van Leeuwen, John

    2016-11-15

    Prechlorination is commonly used to minimize operational problems associated with biological growth as well as taste and odor control during drinking water treatment. However, prechlorination can also oxidise micropollutants into intermediate byproducts. This could impose profound effects on the safety of the finished water if the transformed byproducts are more toxic and less removable. This study investigated the effect of prechlorination on decomposition and subsequent removal of the four organophosphorus pesticides (OPPs): chlorpyrifos, diazinon, malathion and tolclofos-methyl using a simulated conventional water treatment process of powdered activated carbon assisted coagulation-sedimentation-filtration (PAC-CSF) and postchlorination. It was found that, following prechlorination, not only did the percentage of OPPs oxidation vary significantly, but also the concentration of transformed oxons, which are more toxic than their parent compounds, increased as the major identified oxidation byproducts in water. Removal of these oxons proved to be more difficult by the PAC-CSF than their parent OPPs, because they are more water soluble and more hydrophilic. Both the OPP oxidation and oxon formation increased with chlorine dose during prechlorination. Meanwhile, the continuing chlorination of OPPs by residual free chlorine during PAC-CSF further complicated the pesticide removal processes, generally resulting in a gradually increased formation of oxons. Moreover, in the final treatment stage of postchlorination, the more chlorine-reactive pesticides, malathion and diazinon, were completely oxidised and the formation of corresponding oxons was increased with the prechlorine dose. In contrast, a certain amount of the less chlorine-reactive pesticide tolclofos-methyl still remained in solution after postchlorination, accompanied by an increased formation of tolclofos-methyl oxon with prechlorine dose. Since the oxons are resistant to further oxidation and less adsorbable

  18. Ecological risk of pesticide residues in the British Columbia environment: 1973-2012.

    PubMed

    Wan, Michael T

    2013-01-01

    An updated ecological risk assessment was conducted to re-evaluate and review the overall risk of pesticide residues to certain aquatic life. The focus was the impact on offsite non-target, freshwater organisms of pesticide operational sprays in British Columbia from 1973 until 2012. The values of risk quotients for pesticides of selected indicator organisms were determined to measure the effect. When compared with organophosphorus, carbamate, and other miscellaneous pesticides, this risk assessment analysis suggests that the historical use of persistent and highly toxic organochlorine pesticides posed, and continue to pose, a deleterious ecological risk. The risk is both short-term acute and long-term sub-acute, chronic toxicity to offsite, non-target aquatic invertebrates and juvenile salmonid fish. Data indicated that these organisms were, and remain, subjected to harmful effects of pesticide residues to varying degrees. Most vulnerable were, and also are, benthic organisms inhabiting bottom sediments. This substrate is the natural sink for persistent pesticide residues, predominantly organochlorine pesticides from historical use, as well as dioxins, furans, and polycyclic aromatic hydrocarbons from wood preservatives, and other sources. Environment Canada's main aquatic protection strategy was a 10 metre no-treatment buffer zone, augmented with an additional appropriate setback along shorelines of fishery and wildlife resource-sensitive water bodies. This study discusses why this guideline was necessary, useful and effective, but was only partially successful. The physical-chemical properties of pesticide residues, from either an individual compound or different compounds in combination, also influence the nature of biological impacts on non-target, aquatic organisms. Few studies have been conducted in British Columbia aquatic environments to investigate the significance of this aspect.

  19. Optimisation of octadecyl (C18) sorbent amount in QuEChERS analytical method for the accurate organophosphorus pesticide residues determination in low-fatty baby foods with response surface methodology.

    PubMed

    Georgakopoulos, Panagiotis; Zachari, Rodanthi; Mataragas, Marios; Athanasopoulos, Panagiotis; Drosinos, Eleftherios H; Skandamis, Panagiotis N

    2011-09-15

    Three low-fatty baby food matrices were fortified with 0.01-0.2mg/kg of phorate, diazinon, chlorpyrifos and methidathion. A "quick, easy, cheap, effective, rugged and safe" - like method (QuEChERS) was used. Quantities of octadecyl (C18) sorbent differed with fortification level and matrix fat, based on central composite experimental design. Quantification was performed by Nitrogen-Phosphorus Detector gas chromatography, using matrix-matched standards. The highest (p<0.05) recoveries were observed for methidathion, the lowest fortification levels for a specific C18 amount and the lowest C18 amounts. In meals containing vegetables (1.9% fat) and lamb (3.0% fat), 180-210mg C18 gave recoveries from 67.0% to 105.0% and absence of co-extracts. Yogurt dessert (4.5% fat) required 200-230mg C18 for similar results. Recoveries could also be predicted with <20% error by a polynomial model. The results suggest that modified QuEChERS could be effectively used in the low-fatty baby meals residue analysis.

  20. Monitoring of pesticide residues in vegetarian diet.

    PubMed

    Kumari, Beena; Kathpal, T S

    2009-04-01

    Samples (28) of complete vegetarian diet consumed from morning till night i.e. tea, milk, breakfast, lunch, snacks, dinner, sweet dish etc. were collected from homes, hostels and hotels periodically from Hisar and analysed for detecting the residues of organochlorine, synthetic pyrethriod, organophosphate and carbamate insecticides. The estimation was carried out by using multi-residue analytical technique employing gas chromatograph (GC)-electron capture detector and GC-nitrogen phosphorous detector systems equipped with capillary columns. The whole diet sample was macerated in a mixer grinder and a representative sample in duplicate was analyzed for residues keeping the average daily diet of an adult to be 1,300 g. On comparing the data, it was found that actual daily intake (microgram/person/day) of lindane in two and endosulfan in four samples exceeded the acceptable daily intake. Residues of other pesticides in all the diet samples were lower than the acceptable daily intake (ADI) of the respective pesticides. The study concluded that although all the diet samples were found contaminated with one or the other pesticide, the actual daily intake of only a few pesticides was higher than their respective ADI. More extensive study covering other localities of Haryana has been suggested to know the overall scenario of contamination of vegetarian diet.

  1. Detection of pesticides residues in water samples from organic and conventional paddy fields of Ledang, Johor, Malaysia

    NASA Astrophysics Data System (ADS)

    Abdullah, Md Pauzi; Othman, Mohamed Rozali; Ishak, Anizan; Nabhan, Khitam Jaber

    2016-11-01

    Pesticides have been used extensively by the farmers in Malaysia during the last few decades. Sixteen water samples, collected from paddy fields both organic and conventional, from Ledang, Johor, were analyzed to determine the occurrence and distribution of organochlorine (OCPs) and organophosphorus (OPPs) pesticide residues. GC-ECD instrument was used to identify and determine the concentrations of these pesticide residues. Pesticide residues were detected in conventional fields in the range about 0.036-0.508 µg/L higher than detected in organic fields about 0.015-0.428 µg/L. However the level of concentration of pesticide residues in water sample from both paddy fields are in the exceed limit for human consumption, according to European Economic Commission (EEC) (Directive 98/83/EC) at 0.1 µg/L for any pesticide or 0.5 µg/L for total pesticides. The results that the organic plot is still contaminated with pesticides although pesticides were not use at all in plot possibly from historical used as well as from airborne contamination.

  2. Determination of organophosphorus pesticides in ginseng by carbon nanotube envelope-based solvent extraction combined with ultrahigh-performance liquid chromatography mass spectrometry.

    PubMed

    Su, Rui; Li, Dan; Wang, Xinghua; Yang, Hongmei; Shi, Xiaoyu; Liu, Shuying

    2016-06-01

    A miniature extraction envelope containing multiwall carbon nanotubes, diatomite, neutral alumina, and anhydrous magnesium sulfate was developed for the solvent extraction of organophosphorus pesticides in dried ginseng. After the powder of dried ginseng sample was introduced into the envelope, the envelope was heat sealed and sonicated in acetonitrile for the extraction and clean-up of analytes. The resulting extracts were analyzed by an ultrahigh-performance liquid chromatograph with an electrospray ion source and a quadrupole orbitrap mass spectrometer (UHPLC-ESI/Q-Orbitrap MS) under target-MS(2) mode, and the analytes were quantified by matrix-match calibration. Finally, the simultaneous identification and quantification of 19 pesticide residues were carried out by the present method. It is noteworthy that in this method the processes of extraction and clean-up for the analytes could be carried out and accomplished in one step. The recoveries and relative standard deviations (RSDs) of analytes were in the range of 82.6-110.8% and 1.0-10.6%, respectively. The limits of detection (LODs) and quantification (LOQs) for analytes were determined to be 0.08-0.29μgkg(-1) and 0.26-0.98μgkg(-1), respectively. Several pesticide residues investigated in this study were found in 4 real samples, with the concentrations lower than the maximum residue limit (0.050mgkg(-1)) established by European Union.

  3. 7 CFR 29.427 - Pesticide residue standards.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 2 2013-01-01 2013-01-01 false Pesticide residue standards. 29.427 Section 29.427... REGULATIONS TOBACCO INSPECTION Regulations Miscellaneous § 29.427 Pesticide residue standards. The maximum concentration of residues of the following pesticides allowed in flue-cured or burley tobacco, expressed as...

  4. 7 CFR 29.427 - Pesticide residue standards.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 2 2014-01-01 2014-01-01 false Pesticide residue standards. 29.427 Section 29.427... REGULATIONS TOBACCO INSPECTION Regulations Miscellaneous § 29.427 Pesticide residue standards. The maximum concentration of residues of the following pesticides allowed in flue-cured or burley tobacco, expressed as...

  5. 7 CFR 29.427 - Pesticide residue standards.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 2 2011-01-01 2011-01-01 false Pesticide residue standards. 29.427 Section 29.427... REGULATIONS TOBACCO INSPECTION Regulations Miscellaneous § 29.427 Pesticide residue standards. The maximum concentration of residues of the following pesticides allowed in flue-cured or burley tobacco, expressed as...

  6. 7 CFR 29.427 - Pesticide residue standards.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 2 2012-01-01 2012-01-01 false Pesticide residue standards. 29.427 Section 29.427... REGULATIONS TOBACCO INSPECTION Regulations Miscellaneous § 29.427 Pesticide residue standards. The maximum concentration of residues of the following pesticides allowed in flue-cured or burley tobacco, expressed as...

  7. 7 CFR 29.427 - Pesticide residue standards.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 2 2010-01-01 2010-01-01 false Pesticide residue standards. 29.427 Section 29.427... REGULATIONS TOBACCO INSPECTION Regulations Miscellaneous § 29.427 Pesticide residue standards. The maximum concentration of residues of the following pesticides allowed in flue-cured or burley tobacco, expressed as...

  8. Structure-activity predictions of properties of organophosphorus pesticides and chemical agents important for optical detection. Master`s thesis

    SciTech Connect

    Porte, R.E.

    1995-12-01

    This thesis presents the results of an investigation for estimating various physicochemical properties of chemical warfare agents and organophosphorus pesticides. The determination of aqueous solubility, - octanol/water partition coefficients, and alkaline hydrolysis rate constants will be used in the development of a chemical sensor using fiber optic spectroscopy. These three parameters will effect the limit of detection for each compound by limiting the concentration in the detector. The parameters were estimated by linear free energy relationships and quantitative structure activity relationships using experimental data for compounds of similar chemical structure. The results of this thesis showed that the hydrophobic medium represented by 1-octanol did concentrate the OP pesticides but did not significantly concentrate CWA, CWA simulants, or CWA hydrolysis products. Correlations were evaluated for six classes of organophosphorus compounds. The limitation of this approach to predicting physicochemical parameters is not in the molecular descriptors used in the regression equations but in the availability of existing experimental data.

  9. Pesticide residues survey in citrus fruits.

    PubMed

    Ortelli, Didier; Edder, Patrick; Corvi, Claude

    2005-05-01

    The use of pesticides is widespread in citrus fruits production for pre- and post-harvest protection and many chemical substances may be applied in order to control undesirable moulds or insects. A survey was carried out to evaluate levels of pesticide residues in citrus fruits. Two multiresidue analytical methods were used to screen samples for more than 200 different fungicides, insecticides and acaricides. A total of 240 samples of citrus fruits including lemon, orange, mandarin, grapefruit, lime, pomelo and kumquat were taken in various markets in the Geneva area during the year 2003. Ninety-five percent of the 164 samples issued from classical agriculture contained pesticides and 38 different compounds have been identified. This high percentage of positive samples was mainly due to the presence of two post-harvest fungicides, imazalil and thiabendazole, detected in 70% and 36% of samples respectively. Only three samples exceeded the Swiss maximum residue limits (MRLs). Fifty-three samples sold with the written indication "without post-harvest treatment" were also controlled. Among theses samples, three exceeded the Swiss MRLs for penconazole or chlorpyrifos and 18 (34%) did not respect the written indication since we found large amounts of post-harvest fungicides. Finally, 23 samples coming from certified organic production were analysed. Among theses samples, three contained small amounts of pesticides and the others were pesticides free.

  10. Synthesis and application of molecularly imprinted polymers for the selective extraction of organophosphorus pesticides from vegetable oils.

    PubMed

    Boulanouar, Sara; Combès, Audrey; Mezzache, Sakina; Pichon, Valérie

    2017-09-01

    The increasing use of pesticides in agriculture causes environmental issues and possible serious health risks to humans and animals. Their determination at trace concentrations in vegetable oils constitutes a significant analytical challenge. Therefore, their analysis often requires both an extraction and a purification step prior to separation with liquid chromatography (LC) and mass spectrometry (MS) detection. This work aimed at developing sorbents that are able to selectively extract from vegetable oil samples several organophosphorus (OPs) pesticides presenting a wide range of physico-chemical properties. Therefore, different conditions were screened to prepare molecularly imprinted polymers (MIPs) by a non-covalent approach. The selectivity of the resulting polymers was evaluated by studying the OPs retention in pure media on both MIPs and non-imprinted polymers (NIP) used as control. The most promising MIP sorbent was obtained using monocrotophos (MCP) as the template, methacrylic acid (MAA) as the monomer and ethylene glycol dimethacrylate (EGDMA) as the cross-linker with a molar ratio of 1/4/20 respectively. The repeatability of the extraction procedure and of the synthesis procedure was demonstrated in pure media. The capacity of this MIP was 1mg/g for malathion. This MIP was also able to selectively extract three OPs from almond oil by applying the optimized SPE procedure. Recoveries were between 73 and 99% with SD values between 4 and 6% in this oil sample. The calculated LOQs (between 0.3 and 2μg/kg) in almond seeds with a SD between 0.1 and 0.4μg/kg were lower than the Maximum Residue Levels (MRLs) established for the corresponding compounds in almond seed. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Emerging pesticide residue issues and analytical approaches.

    PubMed

    Fintschenko, Yolanda; Krynitsky, Alexander J; Wong, Jon W

    2010-05-26

    The 46th Annual Florida Pesticide Residue Workshop of 2009 (FPRW 2009) held in St. Pete Beach, FL, is the latest in an annual tradition drawing scientists from U.S. federal and state government laboratories, industry, and other laboratories worldwide. In 2009, selected FPRW presenters were invited to contribute to this special issue of the Journal of Agricultural and Food Chemistry with a section devoted to emerging pesticide residue issues and analytical approaches. What follows is the written record of what should become a scientific conversation launched at FPRW 2009. There are two distinct approaches to organic residue analysis: instrumental methods and assays. In much of the world, scientists primarily rely on laboratories equipped with instrumentation for analysis, usually gas chromatography and liquid chromatography with some type of selective detector. In the discussion of instrumental approaches, the focus is on chromatography with mass spectrometry as a detection method. Approaches such as biomonitoring and assays fall outside the traditional instrumental method approach to residue analysis. Assays that do not require laboratory equipment are of greater interest for screening and are well-suited to field use. Regardless of the analytical method, the success of multiresidue analysis relies on the appropriate choice of sample preparation and cleanup methodologies. Many new sample preparation and cleanup approaches used for pesticide and other small molecule contaminant residue analyses in a variety of complex sample matrices are discussed in this special issue. The goal of these approaches is to reduce overall analysis time and solvent consumption without compromising the analytical results.

  12. An integrated molecular docking and rescoring method for predicting the sensitivity spectrum of various serine hydrolases to organophosphorus pesticides.

    PubMed

    Yang, Ling-Ling; Yang, Xiao; Li, Guo-Bo; Fan, Kai-Ge; Yin, Peng-Fei; Chen, Xiang-Gui

    2016-04-01

    The enzymatic chemistry method is currently the most widely used method for the rapid detection of organophosphorus (OP) pesticides, but the enzymes used, such as cholinesterases, lack sufficient sensitivity to detect low concentrations of OP pesticides present in given samples. Serine hydrolase is considered an ideal enzyme source in seeking high-sensitivity enzymes used for OP pesticide detection. However, it is difficult to systematically evaluate sensitivities of various serine hydrolases to OP pesticides by in vitro experiments. This study aimed to establish an in silico method to predict the sensitivity spectrum of various serine hydrolases to OP pesticides. A serine hydrolase database containing 219 representative serine hydrolases was constructed. Based on this database, an integrated molecular docking and rescoring method was established, in which the AutoDock Vina program was used to produce the binding poses of OP pesticides to various serine hydrolases and the ID-Score method developed recently by us was adopted as a rescoring method to predict their binding affinities. In retrospective case studies, this method showed good performance in predicting the sensitivities of known serine hydrolases to two OP pesticides: paraoxon and diisopropyl fluorophosphate. The sensitivity spectrum of the 219 collected serine hydrolases to 37 commonly used OP pesticides was finally obtained using this method. Overall, this study presented a promising in silico tool to predict the sensitivity spectrum of various serine hydrolases to OP pesticides, which will help in finding high-sensitivity serine hydrolases for OP pesticide detection. © 2015 Society of Chemical Industry.

  13. Quantum dot-DNA aptamer conjugates coupled with capillary electrophoresis: A universal strategy for ratiometric detection of organophosphorus pesticides.

    PubMed

    Tang, Tingting; Deng, Jingjing; Zhang, Min; Shi, Guoyue; Zhou, Tianshu

    2016-01-01

    Based on the highly sensitivity and stable-fluorescence of water-soluble CdTe/CdS core-shell quantum dots (QDs) with broad-specificity DNA aptamers, a novel ratiometric detection strategy was proposed for the sensitive detection of organophosphorus pesticides by capillary electrophoresis with laser-induced fluorescence (CE-LIF). The as-prepared QDs were first conjugated with the amino-modified oligonucleotide (AMO) by amidation reaction, which is partial complementary to the DNA aptamer of organophosphorus pesticides. Then QD-labeled AMO (QD-AMO) was incubated with the DNA aptamer to form QD-AMO-aptamer duplex. When the target organophosphorus pesticides were added, they could specifically bind the DNA aptamer, leading to the cleavage of QD-AMO-aptamer duplex, accompany with the release of QD-AMO. As a result, the ratio of peak height between QD-AMO and QD-AMO-aptamer duplex changed in the detection process of CE-LIF. This strategy was subsequently applied for the detection of phorate, profenofos, isocarbophos, and omethoate with the detection limits of 0.20, 0.10, 0.17, and 0.23μM, respectively. This is the first report about using QDs as the signal indicators for organophosphorus pesticides detection based on broad-specificity DNA aptamers by CE-LIF, thus contributing to extend the scope of application of QDs in different fields. The proposed method has great potential to be a universal strategy for rapid detection of aptamer-specific small molecule targets by simply changing the types of aptamer sequences. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Development of dispersive liquid-liquid microextraction method for the analysis of organophosphorus pesticides in tea.

    PubMed

    Moinfar, Soleyman; Hosseini, Mohammad-Reza Milani

    2009-09-30

    In this article, a new method for the determination of organophosphorus pesticides (OPPs) in tea was developed by using dispersive liquid-liquid microextraction (DLLME) and gas chromatography-flame photometric detection (GC-FPD). A mixture of acetonitrile and n-hexane was used as an extraction solvent for the extraction of OPPs from tea samples. When the extraction process was finished, the mixture of solvents was rapidly dispersed in water; target analyte was extracted to a small volume of n-hexane, using DLLME. Recovery tests were performed for concentration 5.0 microg/kg. The recovery for each target analyte was in the range between 83.3 and 117.4%. The repeatability of the proposed method, expressed as relative standard deviation, varied between 3 and 7.8% (n=3). The detection limit of the method for tea was found ranging from 0.030 to 1 microg/kg for all the target pesticides. Compared with the conventional sample preparation method, the proposed method has the advantage of being quick and easy to operate, and has high-enrichment factors and low consumption of organic solvent.

  15. Organophosphorus pesticides effect on early stages of the axolotl Ambystoma mexicanum (Amphibia: Caudata).

    PubMed

    Robles-Mendoza, C; García-Basilio, C; Cram-Heydrich, S; Hernández-Quiroz, M; Vanegas-Pérez, C

    2009-02-01

    Ambystoma mexicanum is an endemic salamander of Xochimilco, a wetland of the basin of Mexico valley. Nowadays, axolotl populations are decreasing due environmental stressors. Particularly, studies about organophosphorus pesticides (OPPs; i.e. chlorpyrifos and malathion) toxicity are of great importance due to their intensive use in agricultural activities in Xochimilco. Thus, the aim of this study was to evaluate under controlled conditions the toxicity of chlorpyrifos (CPF) and malathion (MLT) on embryos and larvae (stage 44 and 54) of A. mexicanum. Embryos and larvae were exposure 96h from 0.5 to 3mg CPFL(-1) and from 10 to 30mg MLTL(-1) in independent tests. Embryos at the end of this period were maintained 9d without pesticide in order to identify possible recuperation. Differences obtained in mortality, hatching success, development, morphological abnormalities, behaviour and activity, suggest that toxicity of CPF and MLT differs in embryos and larval stages. Embryos were less sensitive to OPPs acute exposure than axolotl larvae; additionally, toxicity of CPF in larval stages was greater than MLT. On the other hand, data obtained in axolotl embryos during the period of recuperation to CPF in particular as delay and inhibition of development, malformations and success of hatching, indicated that these responses turned out more sensitive than mortality. This study allowed to identify the toxicological potential of OPPs on early developmental stages of A. mexicanum and it is a valuable contribution for the future management of the axolotl wild population.

  16. Biosensor based on Prussian blue nanocubes/reduced graphene oxide nanocomposite for detection of organophosphorus pesticides

    SciTech Connect

    Zhang, Lin; Zhang, Aidong; Du, Dan; Lin, Yuehe

    2012-07-13

    We demonstrate a facile procedure to efficiently prepare Prussian blue nanocubes/reduced graphene oxide (PBNCs/rGO) nanocomposite by directly mixing Fe3+ and [Fe(CN)6]3 in the presence of GO in polyethyleneimine aqueous solution, resulting in a novel acetylcholinesterase (AChE) biosensor for detection of organophosphorus pesticides (OPs). The obtained nanocomposite was characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy dispersive X-ray (EDX) microanalysis. It was clearly observed that the nanosheet has been decorated with cubic PB nanoparticles and nearly all the nanoparticles are distributed uniformly only on the surface of the reduced GO. No isolated PB nanoparticles were observed, indicating the strong interaction between PB nanocubes and the reduced GO and the formation of PBNCs/rGO nanocomposite. The obtained PBNCs/rGO based AChE biosensor make the peak potential shift negatively to 220 mV. The AChE biosensor shows rapid response and high sensitivity for detection of monocrotophos. These results suggest that the PBNCs/rGO hybrids nanocomposite exhibited high electrocatalytic activity towards the oxidation of thiocholine, which lead to the sensitive detection of OP pesticides.

  17. Parameters affecting microwave-assisted extraction of organophosphorus pesticides from agricultural soil.

    PubMed

    Fuentes, Edwar; Báez, María E; Labra, Ronnie

    2007-10-26

    This work describes an optimised method for the determination of six representative organophosphorus pesticides (OPPs) (diazinon, parathion, methyl pirimiphos, methyl parathion, ethoprophos, and fenitrothion) in agricultural soils. The method is based on microwave-assisted extraction using a water-methanol modified mixture for desorption and simultaneous partitioning on n-hexane (MAEP), together with gas chromatography-flame photometric detection (GC-FPD). To improve GC-FPD signals (peak intensity and shape) olive oil was used effectively as a "matrix mimic". The optimisation of the extraction method was achieved in two steps: an initial approach through experimental design and principal component analysis where recovery of compounds using a water-methanol mixture ranged from 54 to 77%, and the second one by studying the addition of KH2PO4 to the extracting solution where recoveries were significantly increased, molecular replacing of OPPs from adsorption sites by phosphate being the probable extraction mechanism. Under optimised conditions, recoveries of pesticides from different soils were higher than 73%, except for methyl parathion in some soils, with SD equal or lower than 11% and detection limits ranging from 0.004 to 0.012 microg g(-1). The proposed method was used to determine OPPs in soil samples from different agricultural zones of Chile.

  18. Biosensors and their applications in detection of organophosphorus pesticides in the environment.

    PubMed

    Hassani, Shokoufeh; Momtaz, Saeideh; Vakhshiteh, Faezeh; Maghsoudi, Armin Salek; Ganjali, Mohammad Reza; Norouzi, Parviz; Abdollahi, Mohammad

    2017-01-01

    This review discusses the past and recent advancements of biosensors focusing on detection of organophosphorus pesticides (OPs) due to their exceptional use during the last decades. Apart from agricultural benefits, OPs also impose adverse toxicological effects on animal and human population. Conventional approaches such as chromatographic techniques used for pesticide detection are associated with several limitations. A biosensor technology is unique due to the detection sensitivity, selectivity, remarkable performance capabilities, simplicity and on-site operation, fabrication and incorporation with nanomaterials. This study also provided specifications of the most OPs biosensors reported until today based on their transducer system. In addition, we highlighted the application of advanced complementary materials and analysis techniques in OPs detection systems. The availability of these new materials associated with new sensing techniques has led to introduction of easy-to-use analytical tools of high sensitivity and specificity in the design and construction of OPs biosensors. In this review, we elaborated the achievements in sensing systems concerning innovative nanomaterials and analytical techniques with emphasis on OPs.

  19. Determination of organophosphorus pesticides by gas chromatography with mass spectrometry using a large-volume injection technique after magnetic extraction.

    PubMed

    Nedaei, Maryam; Salehpour, Ali-Reza; Mozaffari, Shahla; Yousefi, Seyedeh Mahboobeh; Yousefi, Seyed Reza

    2014-09-01

    A fast and efficient method was developed for the extraction and determination of organophosphorus pesticides in water samples. Organophosphorus pesticides were extracted by solid-phase extraction using magnetic multi-walled carbon nanotubes and determined by gas chromatography with ion-trap mass spectrometry. Parameters affecting the extraction were investigated. Under optimum conditions of the method, 10 mg magnetic multi-walled carbon nanotubes were added into 10 mL sample. After 2 min, adsorbent particles settled at the bottom of test tube with a magnet. After removing aqueous supernatant, the analytes were desorbed with acetonitrile. Then, 70 μL of acetonitrile phase was injected into the gas chromatography and mass spectrometry system that had an ion-trap analyzer. To achieve high sensitivity, the large-volume-injection technique was used with a programmed temperature vaporization inlet, and the ion-trap mass spectrometer was operated in single ion storage mode. Under the best conditions, the enrichment factors and extraction recoveries were in the range of 113-124 and 74-103%, respectively. The limits of detection were between 3 and 15 ng/L, and the relative standard deviations were < 10%. This method was successfully used for the determination of organophosphorus pesticides in dam water, lagoon water, and river water samples with good reproducibility and recovery.

  20. Earthworm-induced carboxylesterase activity in soil: Assessing the potential for detoxification and monitoring organophosphorus pesticides.

    PubMed

    Sanchez-Hernandez, Juan C; Notario del Pino, J; Domínguez, Jorge

    2015-12-01

    Soil enzyme activities are attracting widespread interest due to its potential use in contaminant breakdown, and as indicators of soil deterioration. However, given the multiple environmental and methodological factors affecting their activity levels, assessment of soil pollution using these biochemical endpoints is still complex. Taking advantage of the well-known stimulatory effect of earthworms on soil microbes, and their associated enzyme activities, we explored some toxicological features of carboxylesterases (CbEs) in soils inoculated with Lumbricus terrestris. A microplate-scale spectrophotometric assay using soil-water suspensions was first optimized, in which kinetic assay parameters (Km, Vmax, dilution of soil homogenate, and duration of soil homogenization) were established for further CbE determinations. Optimal conditions included a soil-to-water ratio of 1:50 (w/v), 30-min of shaking, and 2.5mM of substrate concentration. As expected, CbE activity increased significantly in soils treated with L. terrestris. This bioturbed soil was used for exploring the role of CbE activity as a bioscavenger for organophosphorus (OP) pesticides. Soil treated with two formulations of chlorpyrifos revealed that CbE activity was a significant molecular sink for this pesticide, reducing its impact on soil microbial activity as shown by the unchanged dehydrogenase activity. Dose-dependent curves were adjusted to an exponential kinetic model, and the median ecological dose (ED50) for both pesticide formulations was calculated. ED50 values decreased as the time of pesticide exposure increased (14 d-ED50s=20.4-26.7 mg kg(-1), and 28 d-ED50s=1.8-2.3 mg kg(-1)), which suggested that chlorpyrifos was progressively transformed into its highly toxic metabolite chlorpyrifos-oxon, but simultaneously was inactivated by CbEs. These results were confirmed by in vitro assays that showed chlorpyrifos-oxon was a more potent CbE inhibitor (IC50=35.5-4.67 nM) than chlorpyrifos (0.41-0.84

  1. Gas chromatographic evaluation of pesticide residue contents in nectarines after non-toxic washing treatments.

    PubMed

    Pugliese, P; Moltó, J C; Damiani, P; Marín, R; Cossignani, L; Mañes, J

    2004-10-01

    Washing with aqueous solutions of citric acid, ethanol, glycerol, hydrogen peroxide, potassium permanganate, sodium metabisulfite, sodium laurylsulfate (SLS), sodium hypochlorite, and urea is evaluated for pesticide residue reduction in nectarines and compared with simple tap water washing. Residues of pesticides commonly utilized in nectarines (chlorpyrifos, fenarimol, iprodione, malathion, methidathion, myclobutanil, parathion and pirimicarb) are extracted with ethyl acetate and anhydrous sodium sulfate, extract is concentred and analyzed by GC with nitrogen-phosphorus detection. The formation of possible toxic by-products (chlorpyrifos oxon, malaoxon, methidaoxon and paraoxon methyl) is studied by GC-MS. No toxic by-products are identified in the extracts of the washed samples for the washing-time and concentrations studied, but high levels of sodium hypochlorite, hydrogen peroxide and potassium permanganate form oxons from the organophosphorus pesticides. Ethanol, glycerol and SLS solutions removed near the 50% of the pesticide residues. The other solutions were not more effective than tap water washing. The amount of pesticide removed by washings is related to its water solubility and octanol-water partition coefficient.

  2. Chronic cumulative risk assessment of the exposure to organophosphorus, carbamate and pyrethroid and pyrethrin pesticides through fruit and vegetables consumption in the region of Valencia (Spain).

    PubMed

    Quijano, Leyre; Yusà, Vicent; Font, Guillermina; Pardo, Olga

    2016-03-01

    In the present study, the chronic cumulative exposure to organophosphorus (OPs), carbamates (CBs) and pyrethroid and pyrethrin (PPs) pesticides in the region of Valencia through fruit and vegetables consumption is presented. A total of 752 samples and 84 pesticides were studied of which, 52 were OPs, 23 CBs and 9 PPs. Residue data were derived from the Valencia Region monitoring program 2007-2011 and food consumption levels from a questionnaire-based dietary survey conducted in 2010 in the same area. The relative potency factor (RPFs) approach was used to estimate chronic cumulative dietary exposure to OPs, CBs and PPs using acephate, oxamyl and deltamethrin as index compounds, respectively. The exposure was estimated using a deterministic approach and two scenarios were assumed for left-censored results: the lower-bound (LB) scenario, in which unquantified results (below the limit of quantification (LOQ)) were set to zero and the upper-bound (UB) scenario, in which unquantified results were set to the LOQ. Results demonstrate that the chronic exposure of the young (<16 years) and adult (≥ 16 years) population to pesticides through fruits and vegetables is under control (even at high or frequent consumption of fruits and vegetables), for the three groups of pesticides. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Sensitive Detection of Organophosphorus Pesticides in Medicinal Plants Using Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction Combined with Sweeping Micellar Electrokinetic Chromatography.

    PubMed

    Wei, Jin-Chao; Hu, Ji; Cao, Ji-Liang; Wan, Jian-Bo; He, Cheng-Wei; Hu, Yuan-Jia; Hu, Hao; Li, Peng

    2016-02-03

    A simple, rapid, and sensitive method using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) combined with sweeping micellar electrokinetic chromatography (sweeping-MEKC) has been developed for the determination of nine organophosphorus pesticides (chlorfenvinphos, parathion, quinalphos, fenitrothion, azinphos-ethyl, parathion-methyl, fensulfothion, methidathion, and paraoxon). The important parameters that affect the UA-DLLME and sweeping efficiency were investigated. Under the optimized conditions, the proposed method provided 779.0-6203.5-fold enrichment of the nine pesticides compared to the normal MEKC method. The limits of detection ranged from 0.002 to 0.008 mg kg(-1). The relative standard deviations of the peak area ranged from 1.2 to 6.5%, indicating the good repeatability of the method. Finally, the developed UA-DLLME-sweeping-MEKC method has been successfully applied to the analysis of the investigated pesticides in several medicinal plants, including Lycium chinense, Dioscorea opposite, Codonopsis pilosula, and Panax ginseng, indicating that this method is suitable for the determination of trace pesticide residues in real samples with complex matrices.

  4. Binary combinations of organophosphorus pesticides exhibit differential toxicity under oxidised and un-oxidised conditions.

    PubMed

    Arora, Sumitra; Kumar, Anu

    2015-05-01

    Acetylcholinesterase (AChE) inhibition has been demonstrated to be useful as a biomarker for exposure to organophosphorus (OP) insecticides in many environments. The objective of this study was to investigate the response of housefly (Musca domestica) head AChE (HF-AChE) exposed to five OPs as individual compounds and their binary mixtures under in vitro conditions. To examine the effects of oxidation on OP potency in the HF-AChE system, bromine water was used as an oxidisng agent. With oxidation, the sensitivity of HF-AChE to chlorpyrifos (CPF), malathion (MLT) and triazophos (TRZ) increased significantly. Monocrotophos (MCP) and profenofos (PRF) did not exhibit any significant differences in toxicity under oxidised and un-oxidised conditions. The toxicological interaction of five organophosphorus pesticides was evaluated using the concentration addition model, the combination index-isobologram equation and the toxic unit approach. All three models provided similar predictions for the 10 binary combinations of OPs under oxidised and un-oxidised conditions. In the present study, the antagonistic effects of the binary combination of OPs (CPF+PRF, CPF+MLT, MCP+MLT, PRF+MLT, MLT+TRZ and PRF+TRZ) were observed under oxidised conditions. This may be due to dispositional and/or receptor antagonism. Most of the binary combinations assayed under un-oxidised conditions exhibited synergistic responses. Triazophos showed very strong synergism in binary combinations with CPF, MCP and PRF un-oxidised conditions. In contrast, under oxidised conditions, only CPF+TRZ exhibited synergism. The results obtained indicate differential toxicity of binary combinations of OPs under oxidised and un-oxidised conditions. This information could be a valuable tool in understanding the mechanisms of OPs interactions and the interpretation of future in vivo studies with mixtures of OP insecticides. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Prenatal Organophosphorus Pesticide Exposure and Child Neurodevelopment at 24 Months: An Analysis of Four Birth Cohorts

    PubMed Central

    Engel, Stephanie M.; Bradman, Asa; Wolff, Mary S.; Rauh, Virginia A.; Harley, Kim G.; Yang, Jenny H.; Hoepner, Lori A.; Barr, Dana Boyd; Yolton, Kimberly; Vedar, Michelle G.; Xu, Yingying; Hornung, Richard W.; Wetmur, James G.; Chen, Jia; Holland, Nina T.; Perera, Frederica P.; Whyatt, Robin M.; Lanphear, Bruce P.; Eskenazi, Brenda

    2015-01-01

    Background: Organophosphorus pesticides (OPs) are used in agriculture worldwide. Residential use was common in the United States before 2001. Objectives: We conducted a pooled analysis of four birth cohorts (children’s centers; n = 936) to evaluate associations of prenatal exposure to OPs with child development at 24 months. Methods: Using general linear models, we computed site-specific and pooled estimates of the association of total dialkyl (ΣDAP), diethyl (ΣDEP), and dimethylphosphate (ΣDMP) metabolite concentrations in maternal prenatal urine with mental and psychomotor development indices (MDI/PDI) and evaluated heterogeneity by children’s center, race/ethnicity, and PON1 genotype. Results: There was significant heterogeneity in the center-specific estimates of association for ΣDAP and ΣDMP and the MDI (p = 0.09, and p = 0.05, respectively), as well as heterogeneity in the race/ethnicity-specific estimates for ΣDAP (p = 0.06) and ΣDMP (p = 0.02) and the MDI. Strong MDI associations in the CHAMACOS population per 10-fold increase in ΣDAP (β = –4.17; 95% CI: –7.00, –1.33) and ΣDMP (β = –3.64; 95% CI: –5.97, –1.32) were influential, as were associations among Hispanics (β per 10-fold increase in ΣDAP = –2.91; 95% CI: –4.71, –1.12). We generally found stronger negative associations of ΣDAP and ΣDEP with the 24-month MDI for carriers of the 192Q PON1 allele, particularly among blacks and Hispanics. Conclusions: Data pooling was complicated by center-related differences in subject characteristics, eligibility, and changes in regulations governing residential use of OPs during the study periods. Pooled summary estimates of prenatal exposure to OPs and neurodevelopment should be interpreted with caution because of significant heterogeneity in associations by center, race/ethnicity, and PON1 genotype. Subgroups with unique exposure profiles or susceptibilities may be at higher risk for adverse neurodevelopment following prenatal

  6. Prenatal Organophosphorus Pesticide Exposure and Child Neurodevelopment at 24 Months: An Analysis of Four Birth Cohorts.

    PubMed

    Engel, Stephanie M; Bradman, Asa; Wolff, Mary S; Rauh, Virginia A; Harley, Kim G; Yang, Jenny H; Hoepner, Lori A; Barr, Dana Boyd; Yolton, Kimberly; Vedar, Michelle G; Xu, Yingying; Hornung, Richard W; Wetmur, James G; Chen, Jia; Holland, Nina T; Perera, Frederica P; Whyatt, Robin M; Lanphear, Bruce P; Eskenazi, Brenda

    2016-06-01

    Organophosphorus pesticides (OPs) are used in agriculture worldwide. Residential use was common in the United States before 2001. We conducted a pooled analysis of four birth cohorts (children's centers; n = 936) to evaluate associations of prenatal exposure to OPs with child development at 24 months. Using general linear models, we computed site-specific and pooled estimates of the association of total dialkyl (ΣDAP), diethyl (ΣDEP), and dimethylphosphate (ΣDMP) metabolite concentrations in maternal prenatal urine with mental and psychomotor development indices (MDI/PDI) and evaluated heterogeneity by children's center, race/ethnicity, and PON1 genotype. There was significant heterogeneity in the center-specific estimates of association for ΣDAP and ΣDMP and the MDI (p = 0.09, and p = 0.05, respectively), as well as heterogeneity in the race/ethnicity-specific estimates for ΣDAP (p = 0.06) and ΣDMP (p = 0.02) and the MDI. Strong MDI associations in the CHAMACOS population per 10-fold increase in ΣDAP (β = -4.17; 95% CI: -7.00, -1.33) and ΣDMP (β = -3.64; 95% CI: -5.97, -1.32) were influential, as were associations among Hispanics (β per 10-fold increase in ΣDAP = -2.91; 95% CI: -4.71, -1.12). We generally found stronger negative associations of ΣDAP and ΣDEP with the 24-month MDI for carriers of the 192Q PON1 allele, particularly among blacks and Hispanics. Data pooling was complicated by center-related differences in subject characteristics, eligibility, and changes in regulations governing residential use of OPs during the study periods. Pooled summary estimates of prenatal exposure to OPs and neurodevelopment should be interpreted with caution because of significant heterogeneity in associations by center, race/ethnicity, and PON1 genotype. Subgroups with unique exposure profiles or susceptibilities may be at higher risk for adverse neurodevelopment following prenatal exposure. Engel SM, Bradman A, Wolff MS, Rauh VA, Harley KG, Yang JH, Hoepner

  7. Computational Enzymology and Organophosphorus Degrading Enzymes: Promising Approaches Toward Remediation Technologies of Warfare Agents and Pesticides

    SciTech Connect

    Ramalho, Teodorico C.; DeCastro, Alexandre A.; Silva, Daniela R.; Silva, Maria Cristina; Franca, Tanos C.C.; Bennion, Brian J.; Kuca, Kamil

    2015-08-26

    The re-emergence of chemical weapons as a global threat in hands of terrorist groups, together with an increasing number of pesticides intoxications and environmental contaminations worldwide, has called the attention of the scientific community for the need of improvement in the technologies for detoxification of organophosphorus (OP) compounds. A compelling strategy is the use of bioremediation by enzymes that are able to hydrolyze these molecules to harmless chemical species. Several enzymes have been studied and engineered for this purpose. However, their mechanisms of action are not well understood. Theoretical investigations may help elucidate important aspects of these mechanisms and help in the development of more efficient bio-remediators. In this review, we point out the major contributions of computational methodologies applied to enzyme based detoxification of OPs. Furthermore, we highlight the use of PTE, PON, DFP, and BuChE as enzymes used in OP detoxification process and how computational tools such as molecular docking, molecular dynamics simulations and combined quantum mechanical/molecular mechanics have and will continue to contribute to this very important area of research.The re-emergence of chemical weapons as a global threat in hands of terrorist groups, together with an increasing number of pesticides intoxications and environmental contaminations worldwide, has called the attention of the scientific community for the need of improvement in the technologies for detoxification of organophosphorus (OP) compounds. A compelling strategy is the use of bioremediation by enzymes that are able to hydrolyze these molecules to harmless chemical species. Several enzymes have been studied and engineered for this purpose. However, their mechanisms of action are not well understood. Theoretical investigations may help elucidate important aspects of these mechanisms and help in the development of more efficient bio-remediators. In this review, we point out

  8. Computational Enzymology and Organophosphorus Degrading Enzymes: Promising Approaches Toward Remediation Technologies of Warfare Agents and Pesticides

    DOE PAGES

    Ramalho, Teodorico C.; DeCastro, Alexandre A.; Silva, Daniela R.; ...

    2015-08-26

    The re-emergence of chemical weapons as a global threat in hands of terrorist groups, together with an increasing number of pesticides intoxications and environmental contaminations worldwide, has called the attention of the scientific community for the need of improvement in the technologies for detoxification of organophosphorus (OP) compounds. A compelling strategy is the use of bioremediation by enzymes that are able to hydrolyze these molecules to harmless chemical species. Several enzymes have been studied and engineered for this purpose. However, their mechanisms of action are not well understood. Theoretical investigations may help elucidate important aspects of these mechanisms and helpmore » in the development of more efficient bio-remediators. In this review, we point out the major contributions of computational methodologies applied to enzyme based detoxification of OPs. Furthermore, we highlight the use of PTE, PON, DFP, and BuChE as enzymes used in OP detoxification process and how computational tools such as molecular docking, molecular dynamics simulations and combined quantum mechanical/molecular mechanics have and will continue to contribute to this very important area of research.The re-emergence of chemical weapons as a global threat in hands of terrorist groups, together with an increasing number of pesticides intoxications and environmental contaminations worldwide, has called the attention of the scientific community for the need of improvement in the technologies for detoxification of organophosphorus (OP) compounds. A compelling strategy is the use of bioremediation by enzymes that are able to hydrolyze these molecules to harmless chemical species. Several enzymes have been studied and engineered for this purpose. However, their mechanisms of action are not well understood. Theoretical investigations may help elucidate important aspects of these mechanisms and help in the development of more efficient bio-remediators. In this review, we

  9. Development of a biotinylated broad-specificity single-chain variable fragment antibody and a sensitive immunoassay for detection of organophosphorus pesticides.

    PubMed

    Zhao, Fengchun; Tian, Yuan; Wang, Huimin; Liu, Jiye; Han, Xiao; Yang, Zhengyou

    2016-09-01

    Organophosphorus pesticides (OPs) are the most widely used pesticides in agriculture, and OP residues have been broadly reported in food and environmental samples. The aim of this study is to develop a recombinant antibody-based broad-specificity immunoassay for OPs. A phage display library was prepared from a mouse pre-immunized with a generic immunogen of OPs, and a single-chain variable fragment (scFv) antibody was selected. The selected scFv antibody was fused with biotin acceptor domain (BAD) and overexpressed as an inclusion body in Escherichia coli BL21 (DE3). Then, the protein was refolded by stepwise urea gradient dialysis and biotinylated in vitro by E. coli biotin ligase (BirA). Subsequently, the scFv-BAD protein was purified from the biotinylated system with high yield (66.7 mg L(-1)) and confirmed by SDS-PAGE and Western blot. Based on the biotinylated scFv-BAD, a sensitive and broad-specificity competitive indirect enzyme-linked immunosorbent assay (ciELISA) for detection of OPs was developed. The cross-reactivity (CR) studies demonstrated that the ciELISA described here exhibited the broadest detection spectrum for OPs up to now, and 30 OPs could be determined with 50 % inhibition value (IC50) values ranging from 19.4 to 515.2 ng mL(-1). Moreover, the developed ciELISA was used for the recovery study of the spiked samples and showed satisfactory recoveries. Graphical Abstract Schematic diagram of the development of biotinylated broad-specificity single-chain variable fragment antibody-based immunoassay for organophosphorus pesticides.

  10. Dissipation kinetics of organophosphorus pesticides in milled toasted maize and wheat flour (gofio) during storage.

    PubMed

    González-Curbelo, Miguel Ángel; Socas-Rodríguez, Bárbara; Herrero, Miguel; Herrera-Herrera, Antonio V; Hernández-Borges, Javier

    2017-08-15

    The dissipation/degradation of the pesticides dimethoate, terbufos, disulfoton, and pirimiphos-methyl were evaluated in milled toasted maize and wheat flour (gofio) during three months of storage. Their dissipation kinetics and residual levels were determined, as well as their possible decomposition into some of their main transformation products (disulfoton sulfoxide, terbufos sulfone and disulfoton sulfone). For this purpose, pesticide-free milled toasted maize and wheat samples were spiked with the pesticides, and they were then stored in the darkness at ambient temperature in a closed container to simulate current storage conditions of such packed food. A multiresidue analysis based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was performed for the simultaneous determination of these pesticides and their metabolites. After three months of storage, the dissipation of residues ranged between 34% (pirimiphos-methyl) and 86% (disulfoton) for maize gofio and between 69% (terbufos) and 92% (disulfoton and pirimiphos-methyl) for wheat gofio. The results demonstrated that the degradation was slower in gofio than in wheat gofio and that none of the selected metabolites were detected in any of the samples. Dissipation curves of all studied pesticides fitted to a first-order decay curve in both types of cereals.

  11. Pesticide residue levels in Argentinian pasteurised milk.

    PubMed

    Maitre, M I; de la Sierra, P; Lenardon, A; Enrique, S; Marino, F

    1994-10-14

    Pasteurised milk--120 samples--was analysed (in Santa Fe City, Argentina) to determine organochlorinated pesticides. Almost all samples showed the presence of such residues; the compounds more frequently detected being: heptachlor and its epoxide (98%) and hexachlorocyclohexane .HCH. alpha and gamma isomers. Residues of aldrin and dieldrin; chlordane (alpha and gamma); endosulfan (I and II); DDT (o,p-DDT, p,p'-DDE, o,p-DDD, p,p'-DDD) as well as hexachlorocyclobenzene (HCB) were also found. Despite their presence high concentrations are sporadic, the mean values being less than FAO/OMS tolerance limits. Relations between maxima concentrations and seasons were not found.

  12. Pesticides residues in the Prochilodus costatus (Valenciennes, 1850) fish caught in the São Francisco River, Brazil.

    PubMed

    Oliveira, Fabiano A; Reis, Lilian P G; Soto-Blanco, Benito; Melo, Marília M

    2015-01-01

    The objective of this study was to determine the levels of pesticides in the fish Prochilodus costatus caught in São Francisco River, one of most important rivers in Brazil. Thirty-six fish were captured in three different areas, and samples of the dorsal muscle and pooled viscera were collected for toxicological analysis. We evaluated the presence of 150 different classes of insecticides, fungicides, herbicides and acaricides by multiresidue analysis technique using liquid chromatography-tandem mass spectrometry (LC-MS/MS), with the limit of detection of 5 ppb. In this study, organophosphorus and carbamate pesticides were detected at the highest levels in the caught fish. Among the 41 organophosphorus pesticides surveyed, nine types were detected (chlorpyrifos, diazinon, dichlorvos, disulfoton, ethion, etrimfos, phosalone, phosmet and pyrazophos) in the muscle, viscera pool, or both in 22 (61.1%) fish. Sampled tissues of 20 (55.6%) fish exhibited at least one of the eight evaluated carbamate pesticides and their metabolites: aldicarb, aldicarb sulfoxide, carbaryl, carbofuran, carbosulfan, furathiocarb, methomyl and propoxur. Fungicides (carbendazim, benalaxyl, kresoxim-methyl, trifloxystrobin, pyraclostrobin and its metabolite BF 500 pyraclostrobin), herbicides (pyridate and fluasifop p-butyl), acaricide (propargite) and pyrethroid (flumethrin) were also detected. In conclusion, P. costatus fish caught in the São Francisco River contained residues of 17 different pesticides, in both muscles and the viscera pool, indicating heavy environmental contamination by pesticides in the study area.

  13. Biosensor based on Prussian blue nanocubes/reduced graphene oxide nanocomposite for detection of organophosphorus pesticides.

    PubMed

    Zhang, Lin; Zhang, Aidong; Du, Dan; Lin, Yuehe

    2012-08-07

    We demonstrate a facile procedure to efficiently prepare Prussian blue nanocubes/reduced graphene oxide (PBNCs/rGO) nanocomposite by directly mixing Fe(3+) and [Fe(CN)(6)]((3)-) in the presence of GO in polyethyleneimine aqueous solution, resulting in a novel acetylcholinesterase (AChE) biosensor for detection of organophosphorus pesticides (OPs). The obtained nanocomposite was characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) microanalysis. It was clearly observed that the nanosheet has been decorated with cubic PB nanoparticles and nearly all the nanoparticles are distributed uniformly only on the surface of the reduced GO. No isolated PB nanoparticles were observed, indicating the strong interaction between PB nanocubes and the reduced GO and the formation of PBNCs/rGO nanocomposite. The obtained PBNCs/rGO based AChE biosensor make the peak potential shift negatively to 220 mV. The over-potential decreases ∼460 mV compared to that on a bare electrode, suggesting that PBNCs/rGO has a high electrocatalytic activity towards the oxidation of thiocholine. The AChE biosensor shows rapid response and high sensitivity for detection of monocrotophos with a linear range from 1.0 to 600 ng mL(-1) and a detection limit of 0.1 ng mL(-1). These results suggest that the PBNCs/rGO hybrids nanocomposite exhibited high electrocatalytic activity towards the oxidation of thiocholine, which lead to the sensitive detection of OP pesticides.

  14. In vitro kinetic interactions of DEET, pyridostigmine and organophosphorus pesticides with human cholinesterases.

    PubMed

    Wille, Timo; Thiermann, Horst; Worek, Franz

    2011-04-25

    The simultaneous use of the repellent DEET, pyridostigmine, and organophosphorus pesticides has been assumed as a potential cause for the Gulf War Illness and combinations have been tested in different animal models. However, human in vitro data on interactions of DEET with other compounds are scarce and provoked the present in vitro study scrutinizing the interactions of DEET, pyridostigmine and pesticides with human acetylcholinesterase (hAChE) and butyrylcholinesterase (hBChE). DEET showed to be a weak and reversible inhibitor of hAChE and hBChE. The IC(50) of DEET was calculated to be 21.7mM DEET for hAChE and 3.2mM DEET for hBChE. The determination of the inhibition kinetics of pyridostigmine, malaoxon and chlorpyrifos oxon with hAChE in the presence of 5mM DEET resulted in a moderate reduction of the inhibition rate constant k(i). The decarbamoylation velocity of pyridostigmine-inhibited hAChE was not affected by DEET. In conclusion, the in vitro investigation of interactions between human cholinesterases, DEET, pyridostigmine, malaoxon and chlorpyrifos oxon showed a weak inhibition of hAChE and hBChE by DEET. The inhibitory potency of the tested cholinesterase inhibitors was not enhanced by DEET and it did not affect the regeneration velocity of pyridostigmine-inhibited AChE. Hence, this in vitro study does not give any evidence of a synergistic effect of the tested compounds on human cholinesterases. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  15. Functionalized polyacrylamide as an acetylcholinesterase-inspired biomimetic device for electrochemical sensing of organophosphorus pesticides.

    PubMed

    Sgobbi, Livia F; Machado, Sergio A S

    2017-09-14

    A plethora of publications has continuously reported electrochemical biosensors for detection of pesticides. However, those devices rarely accomplish commercial application due to technical issues associated with the lack of stability and high cost of the biological recognition element (enzyme). Alternatively, the biomimetic catalysts have arisen as a candidate for application in electrochemical biosensors to overcome the enzymatic drawbacks, combining low cost scalable materials with superior stability. Herein, for the first time, we propose a biomimetic biosensor for organophosphorus pesticide detection employing a functionalized polyacrylamide, polyhydroxamicalkanoate (PHA), which mimics the performance of the acetylcholinesterase (AChE) enzyme. The PHA bears functional groups inserted along its backbone chain working as active sites. Thereby, PHA was immobilized on screen printed electrodes (SPE) through a blend formation with poly(ethylene glycol) methyl ether (mPEG) to prevent its leaching out from the surface. Under optimum conditions, the biomimetic sensor was employed for the amperometric detection of paraoxon-ethyl, fenitrothion and chlorpyrifos ranging from 1.0 and 10.0μmolL(-1) with a limit of detection of 0.36μmolL(-1), 0.61μmol L(-1), and 0.83μmolL(-1), respectively. Typical AChE-based interfering species did not affect the PHA performance, which endorsed its superior behavior. The proposed biomimetic biosensor, denoted as SPE/PHA/mPEG, represents a significant advance in the field, offering a new path for low cost devices by means of an artificial enzyme, simple configuration and superior stability. Moreover, the biosensor performance can be further improved by modifying the electrode surface to enhance electronic transfer rate. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Enzyme-linked immunosorbent assay for the determination of five organophosphorus pesticides in camellia oil.

    PubMed

    Liu, Yihua; Guo, Yirong; Zhu, Guonian; Tang, Fubin

    2014-07-01

    A matrix solid-phase dispersion and direct competitive enzyme-linked immunosorbent assay (MSPD-ELISA) was developed for five organophosphorus pesticides (OPs) in camellia oil. Seven haptens with different substituents in the aromatic ring were used to prepare different competitors; the ELISA showed highest sensitivity and specificity to OPs when the competitor had moderate heterology to the immunizing hapten. Several assay conditions were optimized to increase the ELISA sensitivity. The optimized ELISA for five OPs had 50% inhibitory concentrations of 6.3 ng/ml (parathion), 18.9 ng/ml (methyl parathion), 120.7 ng/ml (fenitrothion), 110.4 ng/ml (fenthion), and 20.7 ng/ml (phoxim). The average recoveries of five OPs in camellia oil ranged from 75.7 to 105.3%, with the interassay coefficient of variations ranging from 6.0 to 13.4%. Compared with the results previously reported, the ELISA that was developed in the present study showed a much higher sensitivity. Additionally, MSPD was used in the sample preparation to minimize the matrix effect. Recoveries from the method developed here were in agreement with those obtained by gas chromatography, which indicated that the detection performance of the MSPD-ELISA could meet the regulatory requirements of different governments and international organizations.

  17. Extraction of organophosphorus pesticides in water and juice using ultrasound-assisted emulsification-microextraction.

    PubMed

    Jia, Chunhong; Zhu, Xiaodan; Chen, Li; He, Min; Yu, Pingzhong; Zhao, Ercheng

    2010-02-01

    In this study, a microextraction method termed as ultrasound-assisted emulsification-microextraction (USAEME) has been developed for the extraction of organophosphorus pesticides (OPPs) in water and orange juice samples. In the USAEME method, aliquots of 50 microL chlorobenzene used as extraction solvent was added to 10 mL water sample in a conical glass centrifugal tube. Factors influencing the USAEME extraction efficiency such as sonication time, extraction solvent, extraction volume and salt addition were evaluated. Under the optimum conditions, enrichment factors ranged from 241 to 311, LOD varied from 5.3 to 10.0 ng/L and linearity with a coefficient of estimation (r(2)) varied from 0.9991 to 0.9998 in the concentration level range of 0.05-2.5 microg/L for the extraction of OPPs in water samples. Finally, the proposed USAEME method was used for the extraction of OPPs from water and orange juice. The recoveries were in the range of 80.0-110.0%, and the repeatability of the method expressed as RSD (n=3) varied between 1.6 and 13%. The USAEME method has the advantage of being easy to operate, low consumption of organic solvent and high extraction efficiency.

  18. Computational Enzymology and Organophosphorus Degrading Enzymes: Promising Approaches Toward Remediation Technologies of Warfare Agents and Pesticides.

    PubMed

    Ramalho, Teodorico C; de Castro, Alexandre A; Silva, Daniela R; Silva, Maria Cristina; Franca, Tanos C C; Bennion, Brian J; Kuca, Kamil

    2016-01-01

    The re-emergence of chemical weapons as a global threat in hands of terrorist groups, together with an increasing number of pesticides intoxications and environmental contaminations worldwide, has called the attention of the scientific community for the need of improvement in the technologies for detoxification of organophosphorus (OP) compounds. A compelling strategy is the use of bioremediation by enzymes that are able to hydrolyze these molecules to harmless chemical species. Several enzymes have been studied and engineered for this purpose. However, their mechanisms of action are not well understood. Theoretical investigations may help elucidate important aspects of these mechanisms and help in the development of more efficient bio-remediators. In this review, we point out the major contributions of computational methodologies applied to enzyme based detoxification of OPs. Furthermore, we highlight the use of PTE, PON, DFP, and BuChE as enzymes used in OP detoxification process and how computational tools such as molecular docking, molecular dynamics simulations and combined quantum mechanical/molecular mechanics have and will continue to contribute to this very important area of research.

  19. Antiandrogenic activity and metabolism of the organophosphorus pesticide fenthion and related compounds.

    PubMed Central

    Kitamura, Shigeyuki; Suzuki, Tomoharu; Ohta, Shigeru; Fujimoto, Nariaki

    2003-01-01

    We investigated the endocrine-disrupting actions of the organophosphorus pesticide fenthion and related compounds and the influence of metabolic transformation on the activities of these compounds. Fenthion acted as an antagonist of the androgenic activity of dihydrotestosterone (10(-7)M) in the concentration range of 10(-6)-10(-4)M in an androgen-responsive element-luciferase reporter-responsive assay using NIH3T3 cells. The antiandrogenic activity of fenthion was similar in magnitude to that of flutamide. Fenthion also tested positive in the Hershberger assay using castrated male rats. Marked estrogenic and antiestrogenic activities of fenthion and related compounds were not observed in MCF-7 cells. When fenthion was incubated with rat liver microsomes in the presence of NADPH, the antiandrogenic activity markedly decreased, and fenthion sulfoxide was detected as a major metabolite. The oxidase activity toward fenthion was exhibited by cytochrome P450 and flavin-containing monooxygenase. Fenthion sulfoxide was negative in the screening test for antiandrogens, as was fenthion sulfone. However, when fenthion sulfoxide was incubated with liver cytosol in the presence of 2-hydroxypyrimidine, an electron donor of aldehyde oxidase, the extract of the incubation mixture exhibited antiandrogenic activity. In this case, fenthion was detected as a major metabolite of the sulfoxide. Metabolic interconversion between fenthion and fenthion sulfoxide in the body seems to maintain the antiandrogenic activity. PMID:12676606

  20. Fe3O4 magnetic nanoparticle peroxidase mimetic-based colorimetric assay for the rapid detection of organophosphorus pesticide and nerve agent.

    PubMed

    Liang, Minmin; Fan, Kelong; Pan, Yong; Jiang, Hui; Wang, Fei; Yang, Dongling; Lu, Di; Feng, Jing; Zhao, Jianjun; Yang, Liu; Yan, Xiyun

    2013-01-02

    Rapid and sensitive detection methods are in urgent demand for the screening of extensively used organophosphorus pesticides and highly toxic nerve agents for their neurotoxicity. In this study, we developed a novel Fe(3)O(4) magnetic nanoparticle (MNP) peroxidase mimetic-based colorimetric method for the rapid detection of organophosphorus pesticides and nerve agents. The detection assay is composed of MNPs, acetylcholinesterase (AChE), and choline oxidase (CHO). The enzymes AChE and CHO catalyze the formation of H(2)O(2) in the presence of acetylcholine, which then activates MNPs to catalyze the oxidation of colorimetric substrates to produce a color reaction. After incubation with the organophosphorus neurotoxins, the enzymatic activity of AChE was inhibited and produced less H(2)O(2), resulting in a decreased catalytic oxidation of colorimetric substrates over MNP peroxidase mimetics, accompanied by a drop in color intensity. Three organophosphorus compounds were tested on the assay: acephate and methyl-paraoxon as representative organophosphorus pesticides and the nerve agent Sarin. The novel assay displayed substantial color change after incubation in organophosphorus neurotoxins in a concentration-dependent manner. As low as 1 nM Sarin, 10 nM methyl-paraoxon, and 5 μM acephate are easily detected by the novel assay. In conclusion, by employing the peroxidase-mimicking activity of MNPs, the developed colorimetric assay has the potential of becoming a screening tool for the rapid and sensitive assessment of the neurotoxicity of an overwhelming number of organophosphate compounds.

  1. Activity-Based Protein Profiling of Organophosphorus and Thiocarbamate Pesticides Reveals Multiple Serine Hydrolase Targets in Mouse Brain

    PubMed Central

    NOMURA, DANIEL K.; CASIDA, JOHN E.

    2010-01-01

    Organophosphorus (OP) and thiocarbamate (TC) agrochemicals are used worldwide as insecticides, herbicides, and fungicides, but their safety assessment in terms of potential off-targets remains incomplete. In this study, we used a chemoproteomic platform, termed activity-based protein profiling, to broadly define serine hydrolase targets in mouse brain of a panel of 29 OP and TC pesticides. Among the secondary targets identified, enzymes involved in degradation of endocannabinoid signaling lipids, monoacylglycerol lipase and fatty acid amide hydrolase, were inhibited by several OP and TC pesticides. Blockade of these two enzymes led to elevations in brain endocannabinoid levels and dysregulated brain arachidonate metabolism. Other secondary targets include enzymes thought to also play important roles in the nervous system and unannotated proteins. This study reveals a multitude of secondary targets for OP and TC pesticides and underscores the utility of chemoproteomic platforms in gaining insights into biochemical pathways that are perturbed by these toxicants. PMID:21341672

  2. Pesticide residues in birds and mammals

    USGS Publications Warehouse

    Stickel, L.F.; Edwards, C.A.

    1973-01-01

    SUMMARY: Residues of organochlorine pesticides and their breakdown products are present in the tissues of essentially all wild birds throughout the world. These chemicals accumulate in fat from a relatively small environmental exposure. DDE and dieldrin are most prevalent. Others, such as heptachlor epoxide, chlordane, endrin, and benzene hexachloride also occur, the quantities and kinds generally reflecting local or regional use. Accumulation may be sufficient to kill animals following applications for pest control. This has occurred in several large-scale programmes in the United States. Mortality has also resulted from unintentional leakage of chemical from commercial establishments. Residues may persist in the environment for many years, exposing successive generations of animals. In general, birds that eat other birds, or fish, have higher residues than those that eat seeds and vegetation. The kinetic processes of absorption, metabolism, storage, and output differ according to both kind of chemical and species of animal. When exposure is low and continuous, a balance between intake and excretion may be achieved. Residues reach a balance at an approximate animal body equilibrium or plateau; the storage is generally proportional to dose. Experiments with chickens show that dieldrin and heptachlor epoxide have the greatest propensity for storage, endrin next, then DDT, then lindane. The storage of DDT was complicated by its metabolism to DDE and DDD, but other studies show that DDE has a much greater propensity for storage than either DDD or DDT. Methoxychlor has little cumulative capacity in birds. Residues in eggs reflect and parallel those in the parent bird during accumulation, equilibrium, and decline when dosage is discontinued. Residues with the greatest propensity for storage are also lost most slowly. Rate of loss of residues can be modified by dietary components and is speeded by weight loss of the animal. Under sublethal conditions of continuous

  3. Microwave accelerated selective Soxhlet extraction for the determination of organophosphorus and carbamate pesticides in ginseng with gas chromatography/mass spectrometry.

    PubMed

    Zhou, Ting; Xiao, Xiaohua; Li, Gongke

    2012-07-03

    Microwave accelerated selective Soxhlet extraction (MA-SSE), a novel selective extraction technique, was investigated in this study. A Soxhlet extraction system containing a glass filter was designed as an extractor. During the procedure of MA-SSE, both the target analytes and the interfering components were extracted from the sample into the extraction solvent enhanced by microwave irradiation. After the solvent flowed though the sorbent, the interfering components were adsorbed by the sorbent, and the target analytes remaining in the solvent were collected in the extraction bottle. No cleanup or filtration was required after extraction. The efficiency of the MA-SSE approach was demonstrated in the determination of organophosphorus and carbamate pesticide residues in ginseng by gas chromatography/mass spectrometry (GC/MS). Under the optimized conditions, low limits of detection (0.050-0.50 μg/kg) were obtained. The recoveries were in the range of 72.0-110.1% with relative standard deviations less than 7.1%. Because of the effect of microwave irradiation, MA-SSE showed significant advantage compared with other extraction techniques. The sorbent used in this study showed good cleanup ability. The mechanism of MA-SSE was demonstrated to be based on the rupture of the cell walls according to the structural changes of ginseng samples. On the basis of the results, MA-SSE as a simple and effective sample preparation technique for the analysis of pesticide residues in complex matrixes shows great promise.

  4. Pesticide residues in apples grown under a conventional and integrated pest management system.

    PubMed

    Mladenova, R; Shtereva, D

    2009-06-01

    This paper describes method validation for determination of more than 40 pesticides in apples using a GC technique. Target compounds belonged to the organochlorine, organophosphorus, carbamates, pyrethroids, triazoles, dicarboximides and strobilurins groups, among others. Sample preparation consisted of acetone extraction and subsequent cleanup/concentration by SPE with a polymer-based sorbent. Single quadrupole GC-MS operating in SIM mode and electron impact ionization was used for identification and quantification of the pesticides. Average recoveries for analytes ranged between 70 and 110% at three fortification levels - 0.01, 0.1 and 0.2 mg kg(-1). Relative standard deviations were lower than 20% for all tested compounds. Calculated limits of detection and limits of quantification were below 0.01 mg kg(-1), which were sufficiently low compared to the maximum residue levels (MRLs) established by European legislation. The proposed method was applied for determination of pesticide residue in four selected apple varieties after harvesting. Whole and processed fruits (peel and peeled fruits) were analyzed from different treatment systems: two conventional, one based on integrated pest management (IPM) and two variants based on organic production (controls). Higher levels of pesticide residues were found in apple fruits under conventional conditions. Fenitrothion and chlorpyrifos residues were detected frequently in apple peel at concentrations up to 0.45 and 0.77 mg kg(-1), respectively. The levels found in the whole fruits of the same samples were much lower than in peel and below the respective MRLs (0.5 mg kg(-1) for both pesticides). Measurable residues of triadimenol only, up to 0.05 mg kg(-1), concentrated in the peel, were found in the apples from IPM.

  5. Extraction and preconcentration of organophosphorus pesticides in water by using a polymethacrylate-based sorbent modified with magnetic nanoparticles.

    PubMed

    Meseguer-Lloret, Susana; Torres-Cartas, Sagrario; Catalá-Icardo, Mónica; Simó-Alfonso, Ernesto F; Herrero-Martínez, José M

    2017-03-14

    A polymethacrylate-based sorbent modified with magnetic nanoparticles (MNPs) has been synthesized and used as sorbent for solid-phase extraction (SPE) and magnetic solid-phase extraction (MSPE) of three organophosphorus pesticides (phosmet, pirimiphos-methyl, and chlorpyrifos) in water samples followed by high-performance liquid chromatography-diode array detection. The sorbent was prepared from a glycidyl methacrylate-based polymer, modified with a silanizing agent, followed by immobilization of MNPs on the surface of the material. The sorbent was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. Comparative studies of this support were done both in conventional SPE cartridge and MSPE approach. Several extraction parameters (loading pH, elution solvent, eluting volume, and loading flow rate) were investigated in detail. Under optimal conditions, the proposed sorbent gave an excellent enrichment efficiency of analytes and detection limits between 0.01 and 0.25 μg L(-1). The recoveries of organophosphorus pesticides in spiked water samples were in the range of 71-98%, and the developed sorbent showed a high reusability (up to 50 uses without losses in recovery). The proposed method was satisfactorily applied to the analysis of these pesticides in water samples from different sources.

  6. Distribution, fate and effects of pesticide residues in tropical coastal lagoons of northwestern Mexico.

    PubMed

    Carvalho, F P; Gonzalez-Farias, F; Villeneuve, J P; Cattini, C; Hernandez-Garza, M; Mee, L D; Fowler, S W

    2002-11-01

    Analyses of pesticide residues in sediments, water and biota of the Altata-Ensenada del Pabellon coastal lagoon system in Sinaloa, Mexico, showed the presence of organochlorine and organophosphorus compounds. For all the compounds analysed, concentrations in sediments were higher near the points of water discharge from ponds and drainage from the agricultural area. Among the organochlorines, total DDTs displayed the largest sedimentary reservoir, followed by total endosulfans and chlorpyrifos. In sediments, as well as in biota, pp'-DDT concentrations were lower than those of DDT metabolites, which confirms the reduction in the previous massive use of this compound in agriculture. Endosulfan is currently used in the region and endosulfan residues in lagoon sediments attained levels considered to be toxic to meiofauna, therefore constituting an ecological risk to lagoon ecosystems. There was a large sedimentary reservoir of chlorpyrifos but its ecotoxicological risk is difficult to assess due to lack of adequate comparative data. Nevertheless, concentrations of chlorpyrifos which approach acute toxic levels for shrimp were recorded in lagoon water. This suggests that drainage from agricultural fields during high runoff may, on occasion, cause mass mortality of shrimp and fish Organophosphorus pesticides are widely regarded to degrade very rapidly in aquatic systems. Experimental research performed with 14C-labelled chlorpyrifos and parathion has shown that they may be stabilised for relatively long periods of time through sediment-water partitioning. This extension of their environmental half-lives increases their potential for impacting on coastal ecosystems. Since organophosphorus pesticides are highly toxic for aquatic organisms at concentrations generally lower than organochlorines, their presence in the lagoon water and sediment is a matter for much concern. The increased use of tropical coastal lagoons for shrimp and fish farming requires the implementation of

  7. Evaluation of pesticide residues in fruits and vegetables from Algeria.

    PubMed

    Mebdoua, Samira; Lazali, Mohamed; Ounane, Sidi Mohamed; Tellah, Sihem; Nabi, Fahima; Ounane, Ghania

    2017-06-01

    A total of 160 samples of 13 types of fresh fruits and vegetables from domestic production and import were analysed to detect the presence of pesticide residues. Analysis was performed by multi-residual extraction followed by gas chromatography-mass spectrometry. In 42.5% of the tested samples, no residues were found and 12.5% of samples contained pesticide residues above maximum residue limits. Risk assessment for long-term exposure was done for all pesticides detected in this study. Except chlorpyrifos and lambda-cyhalothrin, exposure to pesticides from vegetables and fruits was below 1% of the acceptable daily intake. Short-term exposure assessment revealed that in seven pesticide/commodity combinations, including three pesticides (chlorpyrifos, deltamethrin and lambda-cyhalothrin), the acute reference dose had been exceeded.

  8. Effects of the organophosphorus pesticide Folisuper 600 (methyl parathion) on the heart function of bullfrog tadpoles, Lithobates catesbeianus (Shaw, 1802).

    PubMed

    Costa, M J; Ribeiro, L R; Salla, R F; Gamero, F U; Alves, L M L M; Silva-Zacarin, E C M

    2015-11-01

    The aim of this work was to evaluate whether the heart function of bullfrog tadpoles (25 Gosner stage) is affected by their acute exposure (48 h) to a sub-lethal concentration (10 µg.L-1) of the active principle of the organophosphorus pesticide Folisuper 600R (methyl parathion - MP). Our results demonstrated that MP causes not only a reduction in tadpoles' cardiac ventricular mass, resulting in a marked reduction in their cardiac twitch force, but also impairs their swimming performance, irrespective of increasing their heart rate. Together, these findings indicate that low and realistic concentration of MP have a negative impact on tadpoles' performance, jeopardizing their survival.

  9. A natural matrix (pureed tomato) candidate reference material containing residue concentrations of pesticide chemicals.

    PubMed

    Armishaw, P; Millar, R

    2001-06-01

    NARL (the Australian National Analytical Reference Laboratory) is preparing a pureed tomato reference material spiked with residue concentrations of a range of pesticide chemicals relevant to the Australian horticultural industry. Traceable certified pesticide concentration values will be established using both isotope dilution mass spectrometry primary methods (developed within NARL) and measurements carried out by a number of experienced laboratories. As far as we are aware, there is no other similar CRM available anywhere in the world. The need for such a material is evident from the results of interlaboratory proficiency studies conducted by NARL among Australian and Asia-Pacific residue testing laboratories. Many participants are experiencing difficulties with the analysis of pesticide residues in fruit and vegetables at concentrations of regulatory significance. Chemicals such as methamidophos (an organophosphorus pesticide widely used on tomato crops) are causing particular problems. In a pilot study, a number of units of control (unspiked tomato) and the candidate reference material were prepared and packaged into lacquered steel cans which were sealed and sterilised by immersion in boiling water. Accelerated stability testing of the packaged material was conducted using isochronous measurement. All of the pesticides showed some degree of degradation after 4 weeks of storage at 50 degrees C, and after 168 days of storage at room temperature. However, all appeared to be stable after 168 days of freezer storage. Homogeneity testing involved duplicate test portions taken from every 50th unit of reference material. An experimental protocol was devised with the aim of minimising the analytical variability and assuring the quality of the data generated. There is some degree of inhomogeneity in the prepared material and a small fill trend is also indicated. Potential improvements to the spiking and preparation procedure have been identified and it is planned to

  10. Determination of organophosphorus pesticides in soil by dispersive liquid-liquid microextraction and gas chromatography.

    PubMed

    Yang, Zhonghua; Liu, Yu; Liu, Donghui; Zhou, Zhiqiang

    2012-01-01

    In this article, a rapid and sensitive sample pretreatment technique for the determination of organophosphorus pesticides (OPPs) in soil samples is developed by using dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography-flame photometric detection. Experimental conditions, including the kind of extraction and disperser solvent and their volumes, the extraction time, and the salt addition, are investigated, and the following experiment factors are used: 20 µL chlorobenzene as the extraction solvent; 1.0 mL acetonitrile as the disperser solvent; no addition of salt; and an extraction time of 1 min. Under the optimum conditions, the linearities for the three target OPPs (ethoprophos, chlorpyriphos, and profenofos) are obtained by five points in the concentration range of 2.5-1500 µg/kg, and three replicates are used for each point. Correlation coefficients vary from 0.9987 to 0.9997. The repeatability is tested by spiking soil samples at a concentration level of 5.0 µg/kg. The relative standard deviation (n = 3) varied between 2.0% and 6.6%. The limits of detection, based on a signal-to-noise ratio (S/N) of 3, range from 200 to 500 pg/g. This method is applied to the analysis of the spiked samples S1, S2, and S3, which are collected from the China Agriculture University's orchard, lawn, and garden, respectively. The recoveries for each target analyte are in the range between 87.9% and 108.0%, 87.4% and 108.0%, and 86.7% and 107.2%, respectively.

  11. Is oxygen required before atropine administration in organophosphorus or carbamate pesticide poisoning? – A cohort study

    PubMed Central

    Konickx, L. A.; Bingham, K.

    2014-01-01

    Background Early and adequate atropine administration in organophosphorus (OP) or carbamate insecticide poisoning improves outcome. However, some authors advise that oxygen must be given before atropine due to the risk of inducing ventricular dysrhythmias in hypoxic patients. Because oxygen is frequently unavailable in district hospitals of rural Asia, where the majority of patients with insecticide poisoning present, this guidance has significant implications for patient care. The published evidence for this advice is weak. We therefore performed a patient cohort analysis to look for early cardiac deaths in patients poisoned by anticholinesterase pesticides. Methods We analysed a prospective Sri Lankan cohort of OP or carbamate-poisoned patients treated with early atropine without the benefit of oxygen for evidence of early deaths. The incidence of fatal primary cardiac arrests within 3 h of admission was used as a sensitive (but non-specific) marker of possible ventricular dysrhythmias. Results The cohort consisted of 1957 patients. The incidence of a primary cardiac death within 3 h of atropine administration was 4 (0.2%) of 1957 patients. The majority of deaths occurred at a later time point from respiratory complications of poisoning. Conclusion We found no evidence of a high number of early deaths in an observational study of 1957 patients routinely given atropine before oxygen that might support guidance that oxygen must be given before atropine. The published literature indicates that early and rapid administration of atropine during resuscitation is life-saving. Therefore, whether oxygen is available or not, early atropinisation of OP- and carbamate-poisoned patients should be performed. PMID:24810796

  12. A role for solvents in the toxicity of agricultural organophosphorus pesticides

    PubMed Central

    Eddleston, Michael; Street, Jonathan M.; Self, Ian; Thompson, Adrian; King, Tim; Williams, Nicola; Naredo, Gregorio; Dissanayake, Kosala; Yu, Ly-Mee; Worek, Franz; John, Harald; Smith, Sionagh; Thiermann, Horst; Harris, John B.; Eddie Clutton, R.

    2012-01-01

    Organophosphorus (OP) insecticide self-poisoning is responsible for about one-quarter of global suicides. Treatment focuses on the fact that OP compounds inhibit acetylcholinesterase (AChE); however, AChE-reactivating drugs do not benefit poisoned humans. We therefore studied the role of solvent coformulants in OP toxicity in a novel minipig model of agricultural OP poisoning. Gottingen minipigs were orally poisoned with clinically relevant doses of agricultural emulsifiable concentrate (EC) dimethoate, dimethoate active ingredient (AI) alone, or solvents. Cardiorespiratory physiology and neuromuscular (NMJ) function, blood AChE activity, and arterial lactate concentration were monitored for 12 h to assess poisoning severity. Poisoning with agricultural dimethoate EC40, but not saline, caused respiratory arrest within 30 min, severe distributive shock and NMJ dysfunction, that was similar to human poisoning. Mean arterial lactate rose to 15.6 [SD 2.8] mM in poisoned pigs compared to 1.4 [0.4] in controls. Moderate toxicity resulted from poisoning with dimethoate AI alone, or the major solvent cyclohexanone. Combining dimethoate with cyclohexanone reproduced severe poisoning characteristic of agricultural dimethoate EC poisoning. A formulation without cyclohexanone showed less mammalian toxicity. These results indicate that solvents play a crucial role in dimethoate toxicity. Regulatory assessment of pesticide toxicity should include solvents as well as the AIs which currently dominate the assessment. Reformulation of OP insecticides to ensure that the agricultural product has lower mammalian toxicity could result in fewer deaths after suicidal ingestion and rapidly reduce global suicide rates. PMID:22365945

  13. Is oxygen required before atropine administration in organophosphorus or carbamate pesticide poisoning? - A cohort study.

    PubMed

    Konickx, L A; Bingham, K; Eddleston, M

    2014-06-01

    Early and adequate atropine administration in organophosphorus (OP) or carbamate insecticide poisoning improves outcome. However, some authors advise that oxygen must be given before atropine due to the risk of inducing ventricular dysrhythmias in hypoxic patients. Because oxygen is frequently unavailable in district hospitals of rural Asia, where the majority of patients with insecticide poisoning present, this guidance has significant implications for patient care. The published evidence for this advice is weak. We therefore performed a patient cohort analysis to look for early cardiac deaths in patients poisoned by anticholinesterase pesticides. We analysed a prospective Sri Lankan cohort of OP or carbamate-poisoned patients treated with early atropine without the benefit of oxygen for evidence of early deaths. The incidence of fatal primary cardiac arrests within 3 h of admission was used as a sensitive (but non-specific) marker of possible ventricular dysrhythmias. The cohort consisted of 1957 patients. The incidence of a primary cardiac death within 3 h of atropine administration was 4 (0.2%) of 1957 patients. The majority of deaths occurred at a later time point from respiratory complications of poisoning. We found no evidence of a high number of early deaths in an observational study of 1957 patients routinely given atropine before oxygen that might support guidance that oxygen must be given before atropine. The published literature indicates that early and rapid administration of atropine during resuscitation is life-saving. Therefore, whether oxygen is available or not, early atropinisation of OP- and carbamate-poisoned patients should be performed.

  14. Organophosphorus Pesticides Decrease M2 Muscarinic Receptor Function in Guinea Pig Airway Nerves via Indirect Mechanisms

    PubMed Central

    Proskocil, Becky J.; Bruun, Donald A.; Thompson, Charles M.; Fryer, Allison D.; Lein, Pamela J.

    2010-01-01

    Background Epidemiological studies link organophosphorus pesticide (OP) exposures to asthma, and we have shown that the OPs chlorpyrifos, diazinon and parathion cause airway hyperreactivity in guinea pigs 24 hr after a single subcutaneous injection. OP-induced airway hyperreactivity involves M2 muscarinic receptor dysfunction on airway nerves independent of acetylcholinesterase (AChE) inhibition, but how OPs inhibit neuronal M2 receptors in airways is not known. In the central nervous system, OPs interact directly with neurons to alter muscarinic receptor function or expression; therefore, in this study we tested whether the OP parathion or its oxon metabolite, paraoxon, might decrease M2 receptor function on peripheral neurons via similar direct mechanisms. Methodology/Principal Findings Intravenous administration of paraoxon, but not parathion, caused acute frequency-dependent potentiation of vagally-induced bronchoconstriction and increased electrical field stimulation (EFS)-induced contractions in isolated trachea independent of AChE inhibition. However, paraoxon had no effect on vagally-induced bradycardia in intact guinea pigs or EFS-induced contractions in isolated ileum, suggesting mechanisms other than pharmacologic antagonism of M2 receptors. Paraoxon did not alter M2 receptor expression in cultured cells at the mRNA or protein level as determined by quantitative RT-PCR and radio-ligand binding assays, respectively. Additionally, a biotin-labeled fluorophosphonate, which was used as a probe to identify molecular targets phosphorylated by OPs, did not phosphorylate proteins in guinea pig cardiac membranes that were recognized by M2 receptor antibodies. Conclusions/Significance These data indicate that neither direct pharmacologic antagonism nor downregulated expression of M2 receptors contributes to OP inhibition of M2 function in airway nerves, adding to the growing evidence of non-cholinergic mechanisms of OP neurotoxicity. PMID:20479945

  15. Biologic monitoring of exposure to organophosphorus pesticides in 195 Italian children.

    PubMed

    Aprea, C; Strambi, M; Novelli, M T; Lunghini, L; Bozzi, N

    2000-06-01

    One hundred ninety-five 6- to 7-year-old children who lived in the municipality of Siena (Tuscany, Italy), underwent biologic monitoring to evaluate urinary excretion of several alkylphosphates that are metabolites of organophosphorus pesticides. We evaluated dimethylphosphate (DMP), dimethylthiophosphate (DMTP), dimethyldithiophosphate (DMDTP), diethylphosphate (DEP), diethylthiophosphate (DETP), and diethyldithiophosphate (DEDTP). We obtained urine samples taken in the children's schools, and each sample was accompanied by a questionnaire about lifestyle and dietary habits. We found DMP and DMTP in detectable concentrations in the greatest number of samples (96 and 94%, respectively). The DMP values were geometric mean (GM) 116.7, [geometric standard deviation (GSD) 2.5], and a range of 7.4-1,471.5 nmol/g creatinine. The corresponding DMTP values were GM 104.3 (GSD 2.8) and a range of 4.0-1,526.0 nmol/g creatinine. DMDTP, DEP, DETP, and DEDTP concentrations were GM 14.1, (GSD 3.0), and a range of 3.3-754.6 nmol/g creatinine in 34% of the children; GM 33.2, (GSD 2.4), and a range of 5.1-360.1 nmol/g creatinine in 75% of the children; GM 16.0, (GSD 2.9), and a range of 3.1-284.7 in 48% of the children; and GM 7.7, (GSD 2.1), and a range of 2.3-140.1 in 12% of the children, respectively. The significant variable for urinary excretion of these metabolites in children was pest control operations performed inside or outside the house in the preceding month; however, the presence of a vegetable garden near the house rarely emerged. The urinary excretion of alkylphosphates in children was significantly higher than in a group of the adult population resident in the same province.

  16. Determination of Organophosphorus Pesticides in Soil by Dispersive Liquid–Liquid Microextraction and Gas Chromatography

    PubMed Central

    Yang, Zhonghua; Liu, Yu; Liu, Donghui; Zhou, Zhiqiang

    2012-01-01

    In this article, a rapid and sensitive sample pretreatment technique for the determination of organophosphorus pesticides (OPPs) in soil samples is developed by using dispersive liquid–liquid microextraction (DLLME) combined with gas chromatography–flame photometric detection. Experimental conditions, including the kind of extraction and disperser solvent and their volumes, the extraction time, and the salt addition, are investigated, and the following experiment factors are used: 20 µL chlorobenzene as the extraction solvent; 1.0 mL acetonitrile as the disperser solvent; no addition of salt; and an extraction time of 1 min. Under the optimum conditions, the linearities for the three target OPPs (ethoprophos, chlorpyriphos, and profenofos) are obtained by five points in the concentration range of 2.5–1500 µg/kg, and three replicates are used for each point. Correlation coefficients vary from 0.9987 to 0.9997. The repeatability is tested by spiking soil samples at a concentration level of 5.0 µg/kg. The relative standard deviation (n = 3) varied between 2.0% and 6.6%. The limits of detection, based on a signal-to-noise ratio (S/N) of 3, range from 200 to 500 pg/g. This method is applied to the analysis of the spiked samples S1, S2, and S3, which are collected from the China Agriculture University's orchard, lawn, and garden, respectively. The recoveries for each target analyte are in the range between 87.9% and 108.0%, 87.4% and 108.0%, and 86.7% and 107.2%, respectively. PMID:22291051

  17. Dietary exposure of Hong Kong adults to pesticide residues: results of the first Hong Kong Total Diet Study.

    PubMed

    Wong, Waiky W K; Yau, Arthur T C; Chung, Stephen W C; Lam, Chi-ho; Ma, Stephanie; Ho, Y Y; Xiao, Ying

    2014-01-01

    The use of pesticides and other chemicals has become a common practice in modern agriculture to enhance and stabilise crop yield, protect the nutritional integrity of food, facilitate food storage to assure year-round supplies, and provide attractive and appealing food products. With the adoption of strict good agricultural practice (GAP), only minimal amounts of pesticide residues should remain on the crops or in connected foods of animal origin up the food chain. To assess their associated health risk to local people, the dietary exposure of Hong Kong adults to residues of four groups of pesticides or their metabolites - organophosphorus pesticides (OPPs), carbamates, pyrethrins and pyrethroids, and dithiocarbamate (DTC) metabolites - is estimated in the first Hong Kong Total Diet Study (TDS). A total of 150 commonly consumed food items were collected and prepared "as consumed". A total of 600 composite food samples were analysed for 85 pesticides or their metabolites by liquid chromatography-tandem mass spectrometry (LC-MS/MS). These pesticides were primarily found at low levels (highest mean = 350 μg kg⁻¹) in food samples of plant origin such as vegetables and fruits. Dietary exposures to pesticide residues were estimated based on the analytical results and the food consumption data of the local residents. The estimated dietary exposures of Hong Kong adults to all individual pesticides were well below their respective acceptable daily intakes (ADIs). The percentage contributions of the estimated mean and 95th percentile dietary exposures to the ADIs of individual pesticides were <6% and <24% for the OPPs, <1% for the carbamates and pyrethrins and pyrethroids, and <1% and <4% for the DTC metabolites, respectively. The findings indicate that dietary exposures to all the pesticide residues analysed in this study were unlikely to pose unacceptable health risks to the Hong Kong population.

  18. Pesticide and plasticizer residues in bergamot essential oils from Calabria (Italy).

    PubMed

    Di Bella, Giuseppa; Saitta, Marcello; La Pera, Lara; Alfa, Maria; Dugo, Giacomo

    2004-08-01

    Organophosphorus and organochlorine pesticides, phosphorated plasticizers, chloroparaffins and phthalate esters contamination in bergamot essential oils produced in Calabria in the crop years 1999-2000 was studied by HRGC in connection with detectors FPD, ECD, MS. Residues of dicofol and tetradifon were found in oils from both crop years. The mean dicofol concentration was 0.26 mg/l in samples from 1999 and 0.20 mg/l in those from 2000; the mean tetradifon content was 0.06 mg/l for both the crop years. Among plasticizers, residues of diisobutyl phthalate, di-n-butyl phthalate, and bis(2-ethylhexyl) phthalate were found in samples from crop years 1999 and 2000, the mean content were 1.22 and 1.23 mg/l, 1.51 and 1.65 mg/l, 1.38 and 1.42 mg/l respectively.

  19. Novel sol-gel hybrid methyltrimethoxysilane-tetraethoxysilane as solid phase extraction sorbent for organophosphorus pesticides.

    PubMed

    Wan Ibrahim, Wan Aini; Veloo, Krishna Veni; Sanagi, Mohd Marsin

    2012-03-16

    A novel sol-gel hybrid methyltrimethoxysilane-tetraethoxysilane (MTMOS-TEOS) was produced and applied as sorbent for solid phase extraction (SPE). Five selected organophosphorus pesticides (OPPs) were employed as model compounds to evaluate the extraction performance of the synthesized sol-gel organic-inorganic hybrid MTMOS-TEOS. Analysis was performed using gas chromatography-mass spectrometry. Several important SPE parameters were optimized. Under the optimum extraction conditions, the method using the sol-gel organic-inorganic hybrid MTMOS-TEOS as SPE sorbent showed good linearity in the range of 0.001-1 μg L(-1), good repeatability (RSD 2.1-3.1%, n=5), low limits of detection at S/N=3 (0.5-0.9 pg mL(-1)) and limit of quantification (1-3 pg mL(-1), S/N=10). The performance of the MTMOS-TEOS SPE was compared to commercial C18 Supelclean SPE since C18 SPE is widely used for OPPs. The MTMOS-TEOS SPE method LOD was 500-600 × lower than the LOD of commercial C18 SPE. The LOD achieved with the sol-gel organic-inorganic hybrid MTMOS-TEOS SPE sorbent allowed the detection of these OPPs in drinking water well below the level set by European Union (EU) at 0.1 μg L(-1) of each pesticides. The developed MTMOS-TEOS SPE method was successfully applied to real sample analysis of the selected OPPs from several water samples and its application extended to the analysis of several fruits samples. Excellent recoveries and RSDs of the OPPs were obtained from the various water samples (recoveries: 97-111%, RSDs 0.4-2.8%, n=3) and fruit samples (recoveries: 96-111%), RSDs 1-4%, n=5) using the sol-gel organic-inorganic hybrid MTMOS-TEOS SPE sorbent. Recoveries and RSDs of OPPs from river water samples and fruit samples using C18 Supelclean SPE sorbent were 91-97%, RSD 0.9-2.6, n=3 and 86-96%, RSD 3-8%, n=5, respectively). The novel sol-gel hybrid MTMOS-TEOS SPE sorbent demonstrate the potential as an alternative inexpensive extraction sorbent for OPPs with higher sensitivity for

  20. [Rapid Detection of Trace Dimethoate Pesticide Residues Based on Colorimetric Spectroscopy].

    PubMed

    Li, Wen; Sun, Ming; Li, Min-zan; Sun, Hong

    2015-07-01

    In order to detect dimethoate pesticide residues rapidly and safely, a feasible method based on colorimetric spectroscopy was developed. Because dimethoate is one of organophosphorus pesticides containing sulfur, its sulfenyl can react with Pd2+ to produce a yellow complex named palladium sulfide. PdCl2 was used as the color agent, which was dissolved in acetic acid instead of the common concentrated hydrochloric acid. The dimethoate solution was prepared by dissolving the commercial pesticides into distilled water at different concentrations. The pesticide samples were reacted with the same amount of PdC2 solution respectively. The absorbance spectra of the samples after coloring reaction were measured in the region of 300-900 nm by a spectrophotometer. The result showed that the effect of using acetic acid instead of concentrated hydrochloric acid was not only safe but also preferable, and 0.5 mg x kg(-1) was the minimum concentration of the pesticide that could be distinguished in the spectra. The result met the pesticide residue detecting requirements of part fruits and vegetables in the national standard GB2763-2012 regulations. Further studies on random 40 dimethoate samples from 0.5 to 88 mg x kg(-1) were carried out. Thirty samples were randomly selected to establish the training model and remaining 10 samples were used to test the model. The preprocessing methods were carried on the spectrum data such as normalization and smoothing to get a better effect through comparison their prediction results with the correlation coefficient (r) and the root mean square error of cross-validation (RMSEP). The principal component analysis (PCA) method and partial least squares (PLS) method were used to establish prediction models respectively in the different wave ranges. By calculating the correlation coefficient of dimethoate samples in 350-900 nm the maximum of 0.9572 was obtained at wavelength 458 nm, so 453-463 and 400-600 nm were selected as feather regions

  1. [Organochlorine pesticide residues in human adipose tissue in Costa Rica].

    PubMed

    Barquero, M; Constenla, M A

    1986-06-01

    Organochlorine pesticide residues were found in 82 samples of human adipose material from 82 surgical cases in 16 Costa Rica hospitals. Identification was made by gas-liquid chromatography. The highest pesticide concentration was that of DDT and its metabolites (33.16 micrograms/g). Residues of almost all commercial pesticides were also found. Concentrations of alpha-chlordane. Aldrin and Polychlorinated biphenyls were not significant.

  2. The 49th annual Florida Pesticide Residue Workshop.

    PubMed

    Turnipseed, Sherri B; Romano, Joe

    2013-03-13

    The papers in this special issue of Journal of Agricultural and Food Chemistry were originally presented at the 49th annual Florida Pesticide Residue Workshop (FPRW). The FPRW is an annual meeting for scientists specializing in trace level analysis of pesticides, veterinary drug residues, and other chemical contaminants in food, animal feed, and environmental samples.

  3. Urinary Concentrations of Dialkylphosphate Metabolites of Organophosphorus Pesticides: National Health and Nutrition Examination Survey 1999–2004

    PubMed Central

    Barr, Dana Boyd; Wong, Lee-Yang; Bravo, Roberto; Weerasekera, Gayanga; Odetokun, Martins; Restrepo, Paula; Kim, Do-Gyun; Fernandez, Carolina; Whitehead, Ralph D.; Perez, Jose; Gallegos, Maribel; Williams, Bryan L.; Needham, Larry L.

    2011-01-01

    Organophosphorus (OP) insecticides were among the first pesticides that EPA reevaluated as part of the Food Quality Protection Act of 1996. Our goal was to assess exposure to OP insecticides in the U.S. general population over a six-year period. We analyzed 7,456 urine samples collected as part of three two-year cycles of the National Health and Nutrition Examination Survey (NHANES) from 1999–2004. We measured six dialkylphosphate metabolites of OP pesticides to assess OP pesticide exposure. In NHANES 2003–2004, dimethylthiophosphate was detected most frequently with median and 95th percentile concentrations of 2.03 and 35.3 μg/L, respectively. Adolescents were two to three times more likely to have diethylphosphate concentrations above the 95th percentile estimate of 15.5 μg/L than adults and senior adults. Conversely, for dimethyldithiophosphate, senior adults were 3.8 times and 1.8 times more likely to be above the 95th percentile than adults and adolescents, respectively, while adults were 2.1 times more likely to be above the 95th percentile than the adolescents. Our data indicate that the most vulnerable segments of our population—children and older adults—have higher exposures to OP pesticides than other population segments. However, according to DAP urinary metabolite data, exposures to OP pesticides have declined during the last six years at both the median and 95th percentile levels. PMID:21909292

  4. Multi-walled carbon nanotubes as efficient solid-phase extraction materials of organophosphorus pesticides from apple, grape, orange and pineapple fruit juices.

    PubMed

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Angel

    2008-11-21

    Multi-walled carbon nanotubes (MWCNTs) have been used for the first time as solid-phase extraction (SPE) sorbents for the extraction of eight organophosphorus pesticides (i.e. ethoprophos, diazinon, chlorpyriphos-methyl, fenitrothion, malathion, chlorpyriphos, fenamiphos and buprofezin) from different commercial fruit juices (i.e. apple, grape, orange and pineapple). The developed method, which involves SPE and direct gas chromatography with nitrogen phosphorus detection analysis, is very fast, simple and cheap: only 1:1 dilution with Milli-Q water and pH adjustment to 6.0 of 10 mL of juice is necessary prior to a quick MWCNTs-SPE procedure that used only 40 mg of stationary phase (MWCNTs of 10-15 nm o.d., 2-6 nm i.d. and 0.1-10 microm length). Mean recovery values were above 73% for all the pesticides and fruit juices (between 77 and 101% for apple juice, 75 and 103% for grape juice, 73 and 103% for orange juice and 73 and 93% for pineapple juice) with a relative standard deviation (RSD) lower than 8.5% in all cases. Matrix matched calibration was carried out for each sample matrix since statistical differences between the calibration curves constructed is pure solvent and in the reconstructed juice extracts were found. Limits of detection ranged between 1.85 and 7.32 microg/L (which also represents LODs between 1.85 and 7.34 microg/kg) well below the European Union maximum residue limits for the raw fruits. The proposed method, which is demonstrated to be quick, cheap, accurate and highly selective, was also applied to the analysis of this group of pesticides in several commercial juices in which none of the selected pesticides were found.

  5. DETOXIFICATION OF ORGANOPHOSPHATE PESTICIDES BY IMMOBILIZED ESCHERICHIA COLI EXPRESSING ORGANOPHOSPHORUS HYDROLASE ON CELL SURFACE. (R823663)

    EPA Science Inventory

    An improved whole-cell technology for detoxifying organophosphate nerve agents was recently developed based on genetically engineered Escherichia coli with organophosphorus hydrolase anchored on the surface. This article reports the immobilization of these novel biocatalys...

  6. DETOXIFICATION OF ORGANOPHOSPHATE PESTICIDES BY IMMOBILIZED ESCHERICHIA COLI EXPRESSING ORGANOPHOSPHORUS HYDROLASE ON CELL SURFACE. (R823663)

    EPA Science Inventory

    An improved whole-cell technology for detoxifying organophosphate nerve agents was recently developed based on genetically engineered Escherichia coli with organophosphorus hydrolase anchored on the surface. This article reports the immobilization of these novel biocatalys...

  7. Detectable organophosphorus pesticide exposure in the blood of Nebraska and Iowa residents measured by mass spectrometry of butyrylcholinesterase adducts.

    PubMed

    Jiang, Wei; Lockridge, Oksana

    2013-03-25

    The Centers for Disease Control and Prevention detected organophosphorus pesticide (OP) metabolites in the urine of 96% of Americans, for urine collected before the ban on nonagricultural use of OP in December 2001. It was not known whether exposure was to OP degradation products or to live OP. Our goal was to determine whether exposure was to live OP in the years 2001, 2003, and 2005. Our test for exposure was the presence of OP adducts on plasma butyrylcholinesterase (BChE) detected by mass spectrometry. We purified three lots of BChE from the pooled plasma of 600-800 individuals each, in the years 2001, 2003, and 2005. Blood donors were healthy adults living in Nebraska and Iowa, two agricultural states that grow corn and soybeans. The purified BChE was tested for the presence of OP adducts on serine 198 using MALDI-TOF/TOF mass spectrometry. Low levels of methoxyphosphate-labeled BChE were found. The amount of adducted BChE was highest (1%) in blood collected in the year 2001 and lowest (0.2%) in blood collected in the year 2005. A negative control sample of BChE purified from cord blood collected in the year 2012 had no detectable adducts. It was concluded that Nebraska and Iowa residents were exposed to very low levels of live, intact organophosphorus pesticides, and that exposure levels in the pooled samples declined after the year 2001.

  8. Novel restricted access materials combined to molecularly imprinted polymers for selective solid-phase extraction of organophosphorus pesticides from honey.

    PubMed

    He, Juan; Song, Lixin; Chen, Si; Li, Yuanyuan; Wei, Hongliang; Zhao, Dongxin; Gu, Keren; Zhang, Shusheng

    2015-11-15

    A novel restricted access materials (RAM) combined to molecularly imprinted polymers (MIPs), using malathion as template molecule and glycidilmethacrylate (GMA) as pro-hydrophilic co-monomer, were prepared for the first time. RAM-MIPs with hydrophilic external layer were characterized by scanning electron microscopy and recognition and selectivity properties were compared with the restricted access materials-non-molecularly imprinted polymers (RAM-NIPs) and unmodified MIPs. RAM-MIPs were used as the adsorbent enclosed in solid phase extraction column and several important extraction parameters were comprehensively optimized to evaluate the extraction performance. Under the optimum extraction conditions, RAM-MIPs exhibited comparable or even higher selectivity with greater extraction capacity toward six kinds of organophosphorus pesticides (including malathion, ethoprophos, phorate, terbufos, dimethoate, and fenamiphos) compared with the MIPs and commercial solid phase extraction columns. The RAM-MIPs solid phase extraction coupled with gas chromatography was successfully applied to simultaneously determine six kinds of organophosphorus pesticides from honey sample. The new established method showed good linearity in the range of 0.01-1.0 μg mL(-1), low limits of detection (0.0005-0.0019 μg mL(-1)), acceptable reproducibility (RSD, 2.26-4.81%, n = 6), and satisfactory relative recoveries (90.9-97.6%). It was demonstrated that RAM-MIPs solid phase extraction with excellent selectivity and restricted access function was a simple, rapid, selective, and effective sample pretreatment method.

  9. Pharmacokinetics and effects on serum cholinesterase activities of organophosphorus pesticides acephate and chlorpyrifos in chimeric mice transplanted with human hepatocytes.

    PubMed

    Suemizu, Hiroshi; Sota, Shigeto; Kuronuma, Miyuki; Shimizu, Makiko; Yamazaki, Hiroshi

    2014-11-01

    Organophosphorus pesticides acephate and chlorpyrifos in foods have potential to impact human health. The aim of the current study was to investigate the pharmacokinetics of acephate and chlorpyrifos orally administered at lowest-observed-adverse-effect-level doses in chimeric mice transplanted with human hepatocytes. Absorbed acephate and its metabolite methamidophos were detected in serum from wild type mice and chimeric mice orally administered 150mg/kg. Approximately 70% inhibition of cholinesterase was evident in plasma of chimeric mice with humanized liver (which have higher serum cholinesterase activities than wild type mice) 1day after oral administrations of acephate. Adjusted animal biomonitoring equivalents from chimeric mice studies were scaled to human biomonitoring equivalents using known species allometric scaling factors and in vitro metabolic clearance data with a simple physiologically based pharmacokinetic (PBPK) model. Estimated plasma concentrations of acephate and chlorpyrifos in humans were consistent with reported concentrations. Acephate cleared similarly in humans and chimeric mice but accidental/incidental overdose levels of chlorpyrifos cleared (dependent on liver metabolism) more slowly from plasma in humans than it did in mice. The data presented here illustrate how chimeric mice transplanted with human hepatocytes in combination with a simple PBPK model can assist evaluations of toxicological potential of organophosphorus pesticides. Copyright © 2014 Elsevier Inc. All rights reserved.

  10. Development and comparative study of chemosynthesized antigen and mimotope-based immunoassays for class-specific analysis of O,O-dimethyl organophosphorus pesticides

    PubMed Central

    Zhao, Fengchun; Wang, Huimin; Han, Xiao; Yang, Zhengyou

    2016-01-01

    The multi-residue determination of organophosphorus pesticides (OPs) is an important task due to the wide application and high toxicity of OPs. However, there is no promising immunoassay to monitor the multi-residue of O,O-dimethyl OPs. In this study, a monoclonal antibody (mAb) against a generic hapten of O,O-dimethyl OPs (O,O-dimethyl O-(3-carboxyphenyl)phosphorothioate) was prepared. To develop an effective class-specific immunoassay, two strategies were performed to select the appropriate coating antigen or competing antigen. On the one hand, a total of 20 haptens were chemosynthesized, attached to ovalbumin for use as coating antigen candidates, and selected by direct competitive ELISA (dcELISA). As a second strategy, mimotopes of the mAb were selected from a random phage-display peptide library by panning, and the optimum mimotope was expressed as a fusion protein and biotinylated in vitro. Based on the selected chemosynthesized coating antigen and the biotinylated mimotope fusion protein, two sensitive broad-specificity dcELISAs were developed. The sensitivity, selectivity and practicability of the two immunoassays were compared. The results demonstrated that both methods showed similar selectivity and sensitivity and were reliable for O,O-dimethyl OP residues screening. However, the screening operation of mimotopes was much simpler and safer compared to the preparation of chemosynthesized coating antigens. PMID:27874102

  11. Combination of dispersive solid-phase extraction and salting-out homogeneous liquid-liquid extraction for the determination of organophosphorus pesticides in cereal grains.

    PubMed

    Jia, Chunhong; Zhu, Xiaodan; Wang, Jihua; Zhao, Ercheng; He, Min; Chen, Li; Yu, Pingzhong

    2014-07-01

    A new analytical method for the determination of organophosphorus pesticides in cereal samples was developed by combining dispersive SPE (d-SPE) and salting-out homogeneous liquid-liquid extraction (SHLLE). The pesticides were first extracted from cereal grains with acetonitrile, followed by d-SPE cleanup. A 2 mL aliquot of the extract was then added to a centrifuge tube containing 9.2 mL water and 3.3 g NaCl for SHLLE. Analysis of the extract was carried out by gas chromatography coupled with flame photometric detection. The d-SPE procedure effectively provides the necessary cleanup of the extract while SHLLE is used as an efficient concentration technique. Experimental parameters influencing the extraction efficiency including amounts of added water and salt were investigated. Recovery studies were carried out at three fortification levels, yielding recoveries in the range of 57.7-98.1% with the RSD from 3.7 to 10.9%. The reported limits of determination obtained from this study were 1 μg/kg, which is better than the conventional methods. In the analysis of 40 wheat and corn samples taken from Beijing suburbs, only two wheat samples have chlorpyrifos residue over the limits of determination.

  12. Extraction and determination of organophosphorus pesticides in water samples by a new liquid phase microextraction-gas chromatography-flame photometric detection.

    PubMed

    Khalili-Zanjani, Mohammad Reza; Yamini, Yadollah; Yazdanfar, Najmeh; Shariati, Shahab

    2008-01-14

    A rapid, sensitive and efficient liquid phase microextraction (LPME) method was developed to determine trace concentrations of some organophosphorus pesticides in water samples. This method combines liquid phase microextraction with gas chromatographic (GC) analysis in a simple and inexpensive apparatus involving very little organic solvent consumption. It involves exposing a floated drop of an organic solvent on the surface of aqueous solution in a sealed vial. Experimental parameters which control the performance of LPME such as type of organic solvent, organic solvent and sample volumes, sample stirring rate, sample solution temperature, salt addition and exposure time were investigated and optimized. Finally, the enrichment factor, dynamic linear range (DLR), limit of detection (LOD) and precision of the method were evaluated by the water samples spiked with organophosphorus pesticides. Using optimum extraction conditions, very low detection limits (0.01-0.04mugL(-1)) and good linearities (0.9983organophosphorus pesticides in different types of natural water samples and acceptable recoveries (96-104%) and precisions (3.5organophosphorus pesticides in water samples.

  13. Broad-specificity immunoassay for O,O-diethyl organophosphorus pesticides: Application of molecular modeling to improve assay sensitivity and study antibody recognition

    USDA-ARS?s Scientific Manuscript database

    A monoclonal antibody (MAb) against 4-(diethoxyphosphorothioyloxy)benzoic acid (hapten 1) was raised and used to develop a broad-specificity competitive indirect enzyme-linked immunosorbent assay (ciELISA) for 14 O,O-diethyl organophosphorus pesticides (OPs). Computer-assisted molecular modeling was...

  14. Production and characterization of a broad-specificity polyclonal antibody for O,O-diethyl organophosphorus pesticides and a quantitative structure-activity relationship study of antibody recognition

    USDA-ARS?s Scientific Manuscript database

    Polyclonal antibody (PAb) with broad-specificity for O,O-diethyl organophosphorus pesticides (OPs) against a generic hapten, 4-(diethoxyphosphoro thioyloxy) benzoic acid, was produced. The obtained PAb showed high sensitivity to seven commonly used O,O-diethyl OPs in a competitive indirect enzyme-l...

  15. A simple, rapid, and high-throughput fluorescence polarization immunoassay for simultaneous detection of organophosphorus pesticides in vegetable and environmental water samples

    USDA-ARS?s Scientific Manuscript database

    A simple, rapid, and high-throughput fluorescent polarization immunoassay (FPIA) for simultaneous determination of organophosphorus pesticides (OPs) was developed. Three haptens were labeled with a fluorescein probe and used as tracers to develop a homogenous FPIA using a broad-specificity monoclon...

  16. Are pesticide residues in honey related to oilseed rape treatments?

    PubMed

    Karise, Reet; Raimets, Risto; Bartkevics, Vadims; Pugajeva, Iveta; Pihlik, Priit; Keres, Indrek; Williams, Ingrid H; Viinalass, Haldja; Mänd, Marika

    2017-12-01

    Pesticide treatments before and during the flowering of honey bee forage crops may lead to residues in honey. In northern regions oilseed rape belongs to the main forage crops that is mostly cultivated by means of intensive agriculture, including several pesticide treatments. However, in addition to the focal forage crops, pesticides from non-forage crops can spread to wild flowers around fields, and thus the residues in honey would reflect the whole range of pesticides used in the agricultural landscape. The aim of our study was to clarify which currently used pesticides are present in honey gathered from heterogeneous agricultural landscapes after the end of flowering of oilseed crops. Honey samples (N = 33) were collected from beehives of Estonia during 2013 and 2014, and analysed for residues of 47 currently used agricultural pesticides using the multiresidue method with HPLC-MS/MS and GC-MS and a single residue method for glyphosate, aminopyralid and clopyralid. Residues of eight different active ingredients with representatives from all three basic pesticide classes were determined. Although no correlation was detected between the cumulative amount of pesticide residues and percent of oilseed crops in the foraging territory, most of the residues are those allowed for oilseed rape treatments. Among all pesticides, herbicide residues prevailed in 2013 but not in 2014. Despite the relatively small agricultural impact of Estonia, the detected levels of pesticide residues sometimes exceeded maximum residue level; however, these concentrations do not pose a health risk to consumers, also acute toxicity to honey bees would be very unlikely. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Assessment of the residual toxicity to Anopheles gambiae of the organophosphorus insecticides malathion and Baytex

    PubMed Central

    Smith, A.; Hocking, K. S.

    1962-01-01

    As part of a WHO programme to evaluate possible substitutes for the chlorinated hydrocarbons to which anopheline mosquitos in many countries have become resistant, two organophosphorus insecticides, malathion and Baytex, were tested as residual sprays on various types of surface against Anopheles gambiae adults in experimental huts at Magugu in Tanganyika. The long-lasting toxicity of both insecticides on relatively impervious surfaces was confirmed, but—as is the case with the chlorinated hydrocarbons—shorter persistence was obtained on sorptive surfaces. As most of the mosquitos rested on the roof, its surface was of much greater importance than the wall surface in determining kill; trials with naturally entering mosquitos indicated that where the roof was of grass malathion was to be preferred to Baytex. Observations confirmed that control huts attracted far more mosquitos than the treated huts and that the insecticide vapour apparently masked the human odour. PMID:13993107

  18. A smartphone-readable barcode assay for the detection and quantitation of pesticide residues.

    PubMed

    Guo, Juan; Wong, Jessica X H; Cui, Caie; Li, Xiaochun; Yu, Hua-Zhong

    2015-08-21

    In this paper, we present a smartphone-readable barcode assay for the qualitative detection of methyl parathion residues, a toxic organophosphorus pesticide that is popularly used in agriculture worldwide. The detection principle is based on the irreversible inhibition of the enzymatic activity of acetylcholinesterase (AchE) by methyl parathion; AchE catalytically hydrolyzes acetylthiocholine iodine to thiocholine that in turn dissociates dithiobis-nitrobenzoate to produce a yellow product (deprotonated thio-nitrobenzoate). The yellow intensity of the product was confirmed to be inversely dependent on the concentration of the pesticide. We have designed a barcode-formatted assay chip by using a PDMS (polydimethylsiloxane) channel plate (as the reaction reservoir), situated under a printed partial barcode, to complete the whole barcode such that it can be directly read by a barcode scanning app installed on a smartphone. The app is able to qualitatively present the result of the pesticide test; the absence or a low concentration of methyl parathion results in the barcode reading as "-", identifying the test as negative for pesticides. Upon obtaining a positive result (the app reads a "+" character), the captured image can be further analyzed to quantitate the methyl parathion concentration in the sample. Besides the portability and simplicity, this mobile-app based colorimetric barcode assay compares favorably with the standard spectrophotometric method.

  19. [Feasibility investigation of hydrogen instead of helium as carrier gas in the determination of five organophosphorus pesticides by gas chromatography-mass spectrometry].

    PubMed

    Liu, Zhenxue; Zhou, Shixue

    2015-01-01

    Helium is almost the only choosable carrier gas used in gas chromatography-mass spectrometry (GC-MS). A mixed standard solution of five organophosphorus pesticides was analyzed by using GC-MS, and hydrogen or helium as carrier gas, so as to study the feasibility of hydrogen instead of helium as carrier gas for the determination of organophosphorus pesticides. Combining a mass spectrum database built by ourselves, the results were deconvolved and identified by Automated Mass Spectral Deconvolution & Identification System (AMDIS32), a software belonging to the workstation of the instrument. Then, the statistical software, IBM SPSS Statistics 19.0 was used for the clustering analysis of the data. The results indicated that when hydrogen was used as carrier gas, the peaks of the pesticides detected were slightly earlier than those when helium used as carrier gas, but the resolutions of the chromatographic peaks were lower, and the fraction good indices (Frac. Good) were lower, too. When hydrogen was used as carrier gas, the signals of the pesticides were unstable, the measuring accuracies of the pesticides were reduced too, and even more, some compounds were undetectable. Therefore, considering the measuring accuracy, the signal stability, and the safety, etc., hydrogen should be cautiously used as carrier gas in the determination of organophosphorus pesticides by GC-MS.

  20. Biological monitoring survey of organophosphorus pesticide exposure among pre-school children in the Seattle metropolitan area.

    PubMed

    Lu, C; Knutson, D E; Fisker-Andersen, J; Fenske, R A

    2001-03-01

    In this study we assessed organophosphorus (OP) pesticide exposure among children living in two Seattle metropolitan area communities by measuring urinary metabolites, and identified possible exposure risk factors through a parental interview. We recruited children in clinic and outpatient waiting rooms. We obtained spot urine samples in the spring and fall of 1998 from 110 children ages 2-5 years, from 96 households. We analyzed urine samples for six dialkylphosphate (DAP) compounds, the common metabolites of the OP pesticides. Through parental interviews we gathered demographic and residential pesticide use data. At least one of the DAP metabolites was measured in 99% of the children, and the two predominant metabolites (DMTP and DETP) were measured in 70-75% of the children. We found no significant differences in DAP concentrations related to season, community, sex, age, family income, or housing type. Median concentrations of dimethyl and diethyl DAPs were 0.11 and 0.04 micromol/L, respectively (all children). Concentrations were significantly higher in children whose parents reported pesticide use in the garden (0.19 vs. 0.09 micromol/L for dimethyl metabolites, p = 0.05; 0.04 vs. 0.03 micromol/L for diethyl metabolites, p = 0.02), but were not different based on reported pet treatment or indoor residential use. Nearly all children in this study had measurable levels of OP pesticide metabolites. Some of this exposure was likely due to diet. Garden pesticide use was associated with elevated metabolite levels. It is unlikely that these exposure levels would cause acute intoxication, but the long-term health effects of such exposures are unknown. We recommend that OP pesticide use be avoided in areas where children are likely to play.

  1. Simultaneous determination of nine trace organophosphorous pesticide residues in fruit samples using molecularly imprinted matrix solid-phase dispersion followed by gas chromatography.

    PubMed

    Wang, Xilong; Qiao, Xuguang; Ma, Yue; Zhao, Tao; Xu, Zhixiang

    2013-04-24

    How to determine trace multipesticide residues in fruits is an important problem. This paper reports a molecularly imprinted polymer (MIP) that was prepared using 4-(dimethoxyphosphorothioylamino)butanoic acid as the template, acrylamide as the functional monomer, and ethylene glycol dimethacrylate (EGDMA) as the cross-linker. The novel imprinted polymer was characterized by static and kinetic adsorption experiments, and it exhibited good recognition ability and fast adsorption-desorption dynamicd toward trichlorfon, malathion, acephate, methamidophos, omethoate, dimethoate, phosphamidon, monocrotophos, and methyl parathion. Using this imprinted polymer as sorbent, matrix solid-phase dispersion coupled to gas chromatography for simultaneous determination of nine trace organophosphorus pesticide residues was first presented. Under the optimized conditions, the LOD (S/N = 3) of this method for the nine organophosphorus was 0.3-1.6 μg kg(-1); the RSD for three replicate extractions ranged from 1.2 to 4.8%. The apple and pear samples spiked with nine organophosphate pesticides at levels of 20 and 100 μg kg(-1) were determined according to this method with good recoveries ranging from 81 to 105%. Moreover, this developed method was successfully applied to the quantitative detection of the nine organophosphorus pesticide residues in orange samples.

  2. Human hepatic cytochrome P450-specific metabolism of the organophosphorus pesticides methyl parathion and diazinon.

    PubMed

    Ellison, Corie A; Tian, Yuan; Knaak, James B; Kostyniak, Paul J; Olson, James R

    2012-01-01

    Organophosphorus pesticides (OPs) are a public health concern due to their worldwide use and documented human exposures. Phosphorothioate OPs are metabolized by cytochrome P450s (P450s) through either a dearylation reaction to form an inactive metabolite, or through a desulfuration reaction to form an active oxon metabolite, which is a potent cholinesterase inhibitor. This study investigated the rate of desulfuration (activation) and dearylation (detoxification) of methyl parathion and diazinon in human liver microsomes. In addition, recombinant human P450s were used to determine the P450-specific kinetic parameters (K(m) and V(max)) for each compound for future use in refining human physiologically based pharmacokinetic/pharmacodynamic (PBPK/PD) models of OP exposure. The primary enzymes involved in bioactivation of methyl parathion were CYP2B6 (K(m) = 1.25 μM; V(max) = 9.78 nmol · min(-1) · nmol P450(-1)), CYP2C19 (K(m) = 1.03 μM; V(max) = 4.67 nmol · min(-1) · nmol P450(-1)), and CYP1A2 (K(m) = 1.96 μM; V(max) = 5.14 nmol · min(-1) · nmol P450(-1)), and the bioactivation of diazinon was mediated primarily by CYP1A1 (K(m) = 3.05 μM; V(max) = 2.35 nmol · min(-1) · nmol P450(-1)), CYP2C19 (K(m) = 7.74 μM; V(max) = 4.14 nmol · min(-1) · nmol P450(-1)), and CYP2B6 (K(m) = 14.83 μM; V(max) = 5.44 nmol · min(-1) · nmol P450(-1)). P450-mediated detoxification of methyl parathion only occurred to a limited extent with CYP1A2 (K(m) = 16.8 μM; V(max) = 1.38 nmol · min(-1) · nmol P450(-1)) and 3A4 (K(m) = 104 μM; V(max) = 5.15 nmol · min(-1) · nmol P450(-1)), whereas the major enzyme involved in diazinon detoxification was CYP2C19 (K(m) = 5.04 μM; V(max) = 5.58 nmol · min(-1) · nmol P450(-1)). The OP- and P450-specific kinetic values will be helpful for future use in refining human PBPK/PD models of OP exposure.

  3. [Effect of rhubarb and Glauber's salt cathartic intervention on acute organophosphorus pesticide poisoning].

    PubMed

    Zhu, Jia-ying; Chen, Cha-hua; Yan, Xiao-lian; Xiao, Ling; Huang, Min

    2012-06-01

    To investigate the effect of nasal tube feeding of rhubarb solution and umbilical compress of Glauber's salt for purgation in the treatment of patients with severe acute organophosphorus pesticide poisoning (AOPP). A retrospective study was conducted. Eighty patients with severe AOPP were divided into two groups according to different treatment, with 40 patients in each group. A thorough gastric lavage was done, followed by cholinesterase complex agent and atropine were given for all the patients. On the base of this treatment, one group of patients were given nasogastric feeding of rhubarb solution (200 ml) and Glauber's salt solution ( 100 g) for umbilical compress (rhubarb plus Glauber group),and another group of patients were fed with 20% mannitol (200 ml)as a control group (mannitol group).The time of first defecation, number of passing stools, the time of normalization of cholinesterase (ChE) activity, time of atropinization, dosage of atropinization, and total amount of atropine given, incidence of adverse reactions, and hospital stay in two groups were observed, a statistical analysis of the data was conducted. In rhubarb plus Glauber group, all the conditions were improved better than those of mannitol group [first defecation time (minutes):134.13 ± 31.31 vs.154.35 ± 34.78,the number of stools (times/d):2.60 ± 0.81 vs.2.14 ± 0.63,time of ChE activity returned to normal (days):9.65 ± 1.42 vs.10.66 ± 1.74,atropinization time ( hours ):3.00 ± 0.73 vs.3.56 ± 1.02,dosage of atropinization (mg):51.43 ± 7.03 vs. 57.65 ± 7.74,the total amount of atropine given (mg):229.78 ± 28.96 vs. 248.41 ± 31.45, the incidence of adverse reactions: abdominal pain 0 vs. 17.5%,abdominal distention 0 vs. 20.0%,hospital stay (days):10.43 ± 1.68 vs.11.59 ± 2.121,and all the differences were statistically significant (all P<0.01). Combination usage with aqueous rhubarb solution and Glauber's salt in AOPP patients could yield quick clearance of toxin, reduced

  4. Distinct patterns of gene and protein expression elicited by organophosphorus pesticides in Caenorhabditis elegans

    PubMed Central

    Lewis, John A; Szilagyi, Maria; Gehman, Elizabeth; Dennis, William E; Jackson, David A

    2009-01-01

    Background The wide use of organophosphorus (OP) pesticides makes them an important public health concern. Persistent effects of exposure and the mechanism of neuronal degeneration are continuing issues in OP toxicology. To elucidate early steps in the mechanisms of OP toxicity, we studied alterations in global gene and protein expression in Caenorhabditis elegans exposed to OPs using microarrays and mass spectrometry. We tested two structurally distinct OPs (dichlorvos and fenamiphos) and employed a mechanistically different third neurotoxicant, mefloquine, as an out-group for analysis. Treatment levels used concentrations of chemical sufficient to prevent the development of 10%, 50% or 90% of mid-vulval L4 larvae into early gravid adults (EGA) at 24 h after exposure in a defined, bacteria-free medium. Results After 8 h of exposure, the expression of 87 genes responded specifically to OP treatment. The abundance of 34 proteins also changed in OP-exposed worms. Many of the genes and proteins affected by the OPs are expressed in neuronal and muscle tissues and are involved in lipid metabolism, cell adhesion, apoptosis/cell death, and detoxification. Twenty-two genes were differentially affected by the two OPs; a large proportion of these genes encode cytochrome P450s, UDP-glucuronosyl/UDP-glucosyltransferases, or P-glycoproteins. The abundance of transcripts and the proteins they encode were well correlated. Conclusion Exposure to OPs elicits a pattern of changes in gene expression in exposed worms distinct from that of the unrelated neurotoxicant, mefloquine. The functional roles and the tissue location of the genes and proteins whose expression is modulated in response to exposure is consistent with the known effects of OPs, including damage to muscle due to persistent hypercontraction, neuronal cell death, and phase I and phase II detoxification. Further, the two different OPs evoked distinguishable changes in gene expression; about half the differences are in

  5. Human Hepatic Cytochrome P450-Specific Metabolism of the Organophosphorus Pesticides Methyl Parathion and Diazinon

    PubMed Central

    Tian, Yuan; Knaak, James B.; Kostyniak, Paul J.; Olson, James R.

    2012-01-01

    Organophosphorus pesticides (OPs) are a public health concern due to their worldwide use and documented human exposures. Phosphorothioate OPs are metabolized by cytochrome P450s (P450s) through either a dearylation reaction to form an inactive metabolite, or through a desulfuration reaction to form an active oxon metabolite, which is a potent cholinesterase inhibitor. This study investigated the rate of desulfuration (activation) and dearylation (detoxification) of methyl parathion and diazinon in human liver microsomes. In addition, recombinant human P450s were used to determine the P450-specific kinetic parameters (Km and Vmax) for each compound for future use in refining human physiologically based pharmacokinetic/pharmacodynamic (PBPK/PD) models of OP exposure. The primary enzymes involved in bioactivation of methyl parathion were CYP2B6 (Km = 1.25 μM; Vmax = 9.78 nmol · min−1 · nmol P450−1), CYP2C19 (Km = 1.03 μM; Vmax = 4.67 nmol · min−1 · nmol P450−1), and CYP1A2 (Km = 1.96 μM; Vmax = 5.14 nmol · min−1 · nmol P450−1), and the bioactivation of diazinon was mediated primarily by CYP1A1 (Km = 3.05 μM; Vmax = 2.35 nmol · min−1 · nmol P450−1), CYP2C19 (Km = 7.74 μM; Vmax = 4.14 nmol · min−1 · nmol P450−1), and CYP2B6 (Km = 14.83 μM; Vmax = 5.44 nmol · min−1 · nmol P450−1). P450-mediated detoxification of methyl parathion only occurred to a limited extent with CYP1A2 (Km = 16.8 μM; Vmax = 1.38 nmol · min−1 · nmol P450−1) and 3A4 (Km = 104 μM; Vmax = 5.15 nmol · min−1 · nmol P450−1), whereas the major enzyme involved in diazinon detoxification was CYP2C19 (Km = 5.04 μM; Vmax = 5.58 nmol · min−1 · nmol P450−1). The OP- and P450-specific kinetic values will be helpful for future use in refining human PBPK/PD models of OP exposure. PMID:21969518

  6. One-step extraction for gas chromatography with flame photometric detection of 18 organophosphorus pesticides in Chinese medicine health wines.

    PubMed

    Liu, Qianzhen; Kong, Weijun; Qiu, Feng; Wei, Jianhe; Yang, Shihai; Zheng, Yuguo; Yang, Meihua

    2012-02-15

    An easy, rapid and selective gas chromatography with flame photometric detection (GC-FPD) method was established for simultaneously determining 18 organophosphorus pesticides (OPPs) in 80 Chinese medicine (CM) health wines. This method was based on a simple one-step extraction procedure using a little solvent without any further cleanup steps. The optimized extraction solvent for the pesticides is acetone:dichloromethane (1:1, V/V) with extraction recovery of 79.0-109.1% and relative standard deviation (RSD) of 0.36-12.68%, respectively. The limits of detection (LODs) of the established GC-FPD method for all investigated pesticides ranged from 1 to 15ngmL(-1) and limits of quantification (LOQs) from 4 to 50ngmL(-1). Out of all 80 CM health wines, 18 OPPs were found in 8 samples at low concentrations of 8.2-37.9ngmL(-1). These pesticides were successfully confirmed by GC-MS. This is the first report of determining OPPs in CM health wines, providing references for monitoring the quality of CM health wine in routine analysis.

  7. Experimental strategy for translational studies of organophosphorus pesticide neurotoxicity based on real-world occupational exposures to chlorpyrifos

    PubMed Central

    Lein, Pamela J.; Bonner, Matthew R.; Farahat, Fayssal M.; Olson, James R.; Rohlman, Diane S.; Fenske, Richard A.; Lattal, K. Matthew; Lasarev, Michael R.; Galvin, Kit; Farahat, Taghreed M.; Anger, W. Kent

    2012-01-01

    Translational research is needed to understand and predict the neurotoxic consequences associated with repeated occupational exposures to organophosphorus pesticides (OPs). In this report, we describe a research strategy for identifying biomarkers of OP neurotoxicity, and we characterize pesticide application workers in Egypt’s Menoufia Governorate who serve as our anchor human population for developing a parallel animal model with similar exposures and behavioral deficits and for examining the influence of human polymorphisms in cytochrome P450 (CYP) and paraoxonase 1 (PON1) enzymes on OP metabolism and toxicity. This population has previously been shown to have high occupational exposures and to exhibit a broad range of neurobehavioral deficits. In addition to observational studies of work practices in the field, questionnaires on demographics, lifestyle and work practices were administered to 146 Egyptian pesticide application workers applying pesticides to the cotton crop. Survey results indicated that the application workforce uses standard operating procedures and standardized equipment provided by Egypt’s Ministry of Agriculture, which provides a workforce with a stable work history. We also found that few workers report using personal protective equipment (PPE), which likely contributes to the relatively high exposures reported in these application workers. In summary, this population provides a unique opportunity for identifying biomarkers of OP-induced neurotoxicity associated with occupational exposure. PMID:22240005

  8. Experimental strategy for translational studies of organophosphorus pesticide neurotoxicity based on real-world occupational exposures to chlorpyrifos.

    PubMed

    Lein, Pamela J; Bonner, Matthew R; Farahat, Fayssal M; Olson, James R; Rohlman, Diane S; Fenske, Richard A; Lattal, K Matthew; Lasarev, Michael R; Galvin, Kit; Farahat, Taghreed M; Anger, W Kent

    2012-08-01

    Translational research is needed to understand and predict the neurotoxic consequences associated with repeated occupational exposures to organophosphorus pesticides (OPs). In this report, we describe a research strategy for identifying biomarkers of OP neurotoxicity, and we characterize pesticide application workers in Egypt's Menoufia Governorate who serve as our anchor human population for developing a parallel animal model with similar exposures and behavioral deficits and for examining the influence of human polymorphisms in cytochrome P450 (CYP) and paraoxonase 1 (PON1) enzymes on OP metabolism and toxicity. This population has previously been shown to have high occupational exposures and to exhibit a broad range of neurobehavioral deficits. In addition to observational studies of work practices in the field, questionnaires on demographics, lifestyle and work practices were administered to 146 Egyptian pesticide application workers applying pesticides to the cotton crop. Survey results indicated that the application workforce uses standard operating procedures and standardized equipment provided by Egypt's Ministry of Agriculture, which provides a workforce with a stable work history. We also found that few workers report using personal protective equipment (PPE), which likely contributes to the relatively high exposures reported in these application workers. In summary, this population provides a unique opportunity for identifying biomarkers of OP-induced neurotoxicity associated with occupational exposure.

  9. Determination of organophosphorus insecticides (malathion and diazinon) residue in the drinking water.

    PubMed

    Shayeghi, Mansoreh; Khoobdel, Mehdi; Vatandoost, Hassan

    2007-09-01

    In this study, the amount and origin of the pollution of Karaj river and Amir-Kabir dam, which is the most important supply of Tehrans (capital of Iran) drinking water with malathion and diazinon, have been assessed by High Performance Thin Layer Chromatography (HPTLC) technique. This is a descriptive and cross-sectional study. After initial assessments, four stations were selected for water sampling. In all stations, sampling was done in one day, one week, two weeks, one month, two months and three months after insecticide spraying. Extraction and separating of organophosphorus insecticides from water samples was done by acetone and methylen chloride solvents, using decanter. Then, the residue of malathion and diazinon insecticides was determined using HPTLC technique. The residue of malathion and diazinon in water decreases with increasing the distance and time of spraying. The residues of malathion and diazinon insecticides at station 1 and 2, which were close to spraying places, 1-2 months after spraying was more than allowed limits. But at the ending stations (3 and 4), malathion and diazinon were detectable just in the 1 day and 1 month after spraying, respectively. It is unlikely that Tehran's drinking water be polluted with these two insecticides and the most adverse effect can be seen in the area of spraying. Therefore not only the environment, but also the people in area of Karaj river are at risk of chronic toxicity with malathion and diazinon through consuming polluted water and agriculture products.

  10. [Determination of organophosphorous pesticide residues in red wine by solid phase microextraction-gas chromatography].

    PubMed

    Hu, Yuan; Liu, Wenmin; Zhou, Yanming; Guan, Yafeng

    2006-05-01

    A method for the determination of 12 organophosphorus pesticide residues (OPs) in red wine by fiber solid phase microextraction (SPME) coupled with gas chromatography (GC) was developed and validated. The SPME phase was prepared by sol-gel technology of physical incorporation. The extraction conditions were optimized with the results of stirring rate of 1,250 r/min, NaCl mass concentration of 150 g/L, and extraction time of 30 min. With the sample volume of 25 mL, the relative standard deviations (RSD) of peak areas for most of OPs were below 5%, and the detection limits of OPs were in the range of 5 ng/L-0.38 microg/L. It can be seen from the results that this method has the potential to analyze OPs in other beverages and soft drinking materials.

  11. Assessing intermittent pesticide exposure from flea control collars containing the organophosphorus insecticide tetrachlorvinphos.

    PubMed

    Davis, M Keith; Boone, J Scott; Moran, John E; Tyler, John W; Chambers, Janice E

    2008-11-01

    Fleas are a persistent problem for pets that require implementation of control measures. Consequently, pesticide use by homeowners for flea control is common and may increase pesticide exposure for adults and children. Fifty-five pet dogs (23 in study 1; 22 in study 2) of different breeds and weights were treated with over-the-counter flea collars containing tetrachlorvinphos (TCVP). During study 1, fur of treated dogs was monitored for transferable TCVP residues using cotton gloves to pet the dogs during 5-min rubbings post-collar application. Plasma cholinesterase (ChE) activity was also measured in treated dogs. Average amounts of TCVP transferred from the fur of the neck (rubbing over the collar) and from the back to gloves at 3 days post-collar application were 23,700+/-2100 and 260+/-50 microg/glove, respectively. No inhibition of plasma ChE was observed. During study 2, transferable TCVP residues to cotton gloves were monitored during 5-min rubbings post-collar application. Transferable residues were also monitored on cotton tee shirts worn by children and in the first morning urine samples obtained from adults and children. Average amounts of TCVP transferred to gloves at 5 days post-collar application from the neck (over the collar) and from the back were 22,400+/-2900 and 80+/-20 microg/glove, respectively. Tee shirts worn by children on days 7-11 contained 1.8+/-0.8 microg TCVP/g shirt. No significant differences were observed between adults and children in urinary 2,4,5-trichloromandelic acid (TCMA) levels; however, all TCMA residues (adults and children) were significantly greater than pretreatment concentrations (alpha=0.05). The lack of ChE inhibition in dogs and the low acute toxicity level of TCVP (rat oral LD(50) of 4-5 g/kg) strongly suggest that TCVP is rapidly detoxified and excreted and therefore poses a very low toxicological risk, despite these high residues.

  12. Levels of pesticides residues in the White Nile water in the Sudan.

    PubMed

    Nesser, Gibreel A A; Abdelbagi, Azhari O; Hammad, Ahmed Mohammed Ali; Tagelseed, Mirghani; Laing, Mark D

    2016-06-01

    Twenty-two commonly used pesticides were monitored during autumn, winter, and summer of 2004-2005 in 27 water samples from three sites along the White Nile in Sudan (former Sudan). Sites were selected to reflect pesticides gathered from drainage canals in central Sudan and from upstream sources. Collected samples were extracted and subjected to gas chromatographic analysis. Pesticides levels were measured in nanograms per liter. Pesticides residues were detected in 96 % of the samples with a total residue burden of 4132.6 ng L(-1), and an overall mean concentration and range of 50.99 and not detected-1570 ng L(-1), respectively. Ororganochlorines were the most frequently detected contaminants, which were found in 70 % of the samples, causing a total burden of 2852.8 ng L(-1), followed by pyrethroids 15 % of the samples, with a total burden of 926.5 ng L(-1). The tested herbicides were detected in ˂4 % of the samples with a total burden of 353.3 ng L(-1), while organophosphorus levels were below the detection limit. The most frequent contaminants were the following: heptachlor and its epoxide (52 % of samples), followed by DDTs (dichlorodiphenyltrichloroethanes) (DDT and DDE, in 19 % of the samples), cypermethrin and fenvalerate (in 11 % of the samples), and pendimethalin (in <4 % of the samples). Residues of hexachlorocyclohexane (HCH) isomers (α, β, γ and δ), endosulfan (α and β), p, p-DDD, λ cyhalothrin, deltamethrin, and oxyfluorfen were not detected in the analyzed samples. Generally, levels were least in autumn, and followed by summer and winter. Sources of contamination might include agricultural lands in central Sudan and upstream sources. Both recent and old contaminations were indicated.

  13. Recovery evaluation of organophosphorus pesticides from bee pollen by matrix solid-phase dispersion extraction using sorbents based on silica and titania

    NASA Astrophysics Data System (ADS)

    Torres-Perea, C.; Muñoz-Rodríguez, D.; Medina-Peralta, S.; Carrera-Figueiras, C.; Moguel-Ordóñez, Y. B.

    2013-06-01

    This work focused on the evaluation of the recovery of organophosphorus pesticides from bee pollen after matrix solid phase-dispersion extraction (MSPD). Materials based on silica, titania and titania modified with polivylnylimidazole or polyestirene were used as adsorbents for the extraction of pesticides. Small amounts of fortified pollen (0.1 g, at 1 micro-g/g of pesticides), adsorbent (0.4 g) and solvent elution (1 mL de acetonitrile - ACN) were used in the extractions. For recovery evaluation, pollen extracts were analyzed by gas chromatography coupled with mass spectrometry.

  14. A rapid, cost-effective method for analyzing organophosphorus pesticide metabolites in human urine for counter-terrorism response.

    PubMed

    Weerasekera, Gayanga; Smith, Kimberly D; Needham, Larry L; Barr, Dana B

    2008-01-01

    Organophosphorus (OP) pesticides are used as insecticides in agriculture and pest control and are often called "junior strength" nerve agents because they share the same mechanism of toxicity. OP pesticides are metabolized to dialkylphosphates and other metabolites, which are excreted in urine. In case of a terrorism incident involving widely available OP pesticides, an occurrence that may be likely given their widespread availability, a rapid, accurate, and cost-effective method for detecting exposure is required. We have evaluated several analytical methods to determine the most reliable and cost-effective methods for incident response. Our comparisons have included different internal standards (isotopically labeled standards versus chemically similar surrogate standards), different isolation techniques (some of which are automatable), and different analysis platforms. We found that isotopically labeled standards were a necessity to provide accurate quantification; the chemically similar surrogate was not suitable as an internal standard. The most sensitive and precise method uses isotopically labeled standards with gas chromatography-tandem mass spectrometry analysis. However, the most cost-effective method employed isotopically labeled standards with gas chromatography-single quadrupole-mass spectrometry using a less expensive mass selective detector. Because this method is lower in cost, it may be a more viable option for equipping multiple laboratories with chemical-terrorism response capabilities.

  15. Application of Box-Behnken design for the removal of two organophosphorus pesticides by used Tea leaves

    NASA Astrophysics Data System (ADS)

    Albanis, Triantafyllos; Valileios, Sakkas; Islam, Azharul M.

    2016-04-01

    Removal of two organophosphorus pesticides bromophos methyl [BM: O, O- dimethyl - O - (2, 5-dichloro -4 bromophenyl) phosphorothioate] and quinalphos [QP: O, O-diethyl O-2-quinoxalinyl phosphorothioate] on used tea leaves were studied by batch equilibration method. Adsorption isotherms were conformed well to Langmuir for quinalphos and Freundlich equation for bromophos methyl. The kinetic data fitted well by the pseudo second order model for both pesticides. Box-Behnken design was successfully employed for experimental design and analysis of results. The interactions of pH, initial concentration and adsorbent dose on two pesticides adsorption by used tea leaves were investigated by this model. The optimum pH, initial concentration and adsorbent dose with their corresponding removal efficiency were found to be 7.88, 11.94 mg L-1, 0.37g and 100% for bromophos methyl respectively, for quinalphos 8.72, 6.44 mg L-1, 0.39g and 93.98% respectively. Keywords: Box-Behnken; quinalphos; bromophos methyl; Kinetics; used tea leaves

  16. Colorimetric and Phosphorimetric Dual-Signaling Strategy Mediated by Inner Filter Effect for Highly Sensitive Assay of Organophosphorus Pesticides.

    PubMed

    Zhang, Rong; Li, Na; Sun, Junyong; Gao, Feng

    2015-10-14

    We describe here a colorimetric and phosphorimetric dual-signaling strategy for sensitive assay of organophosphorus pesticides (OPPs). The principle for assay depends on the phenomenon that the phosphorescence of Mn-ZnS quantum dots (QDs) can be dramatically quenched by Au nanoparticles (AuNPs) through the inner filter effect (IFE) and the activity of acetylcholinesterase (AChE), an enzyme that catalytically hydrolyzes acetylthiocholine to thiocholine that can be inhibited by OPPs. By virtue of the variations of absorbance and phosphorescence of the analytical system, a dual-readout assay for OPPs has been proposed. The limits of detection for different OPPs including paraoxon, parathion, omethoate, and dimethyl dichlorovinyl phosphate (DDVP) are found to be 0.29, 0.59, 0.67, and 0.44 ng/L, respectively. The proposed assay was allowed to detect pesticides in real spiked samples and authentic contaminated apples with satisfactory results, suggesting its potential applications to detect pesticides in complicated samples.

  17. Simultaneous degradation of organophosphate and organochlorine pesticides by Sphingobium japonicum UT26 with surface-displayed organophosphorus hydrolase.

    PubMed

    Cao, Xiangyu; Yang, Chao; Liu, Ruihua; Li, Qiang; Zhang, Wei; Liu, Jianli; Song, Cunjiang; Qiao, Chuanling; Mulchandani, Ashok

    2013-04-01

    A genetically engineered microorganism (GEM) capable of simultaneously degrading organophosphate and organochlorine pesticides was constructed for the first time by display of organophosphorus hydrolase (OPH) on the cell surface of a hexachlorocyclohexane (HCH)-degrading Sphingobium japonicum UT26. The GEM could potentially be used for removing the two classes of pesticides that may be present in mixtures at contaminated sites. A surface anchor system derived from the truncated ice nucleation protein (INPNC) from Pseudomonas syringae was used to target OPH onto the cell surface of UT26, reducing the potential substrate uptake limitation. The surface localization of INPNC-OPH fusion was verified by cell fractionation, western blot, proteinase accessibility, and immunofluorescence microscopy. Furthermore, the functionality of the surface-exposed OPH was demonstrated by OPH activity assays. Surface display of INPNC-OPH fusion (82 kDa) neither inhibited cell growth nor affected cell viability. The engineered UT26 could degrade parathion as well as γ-HCH rapidly in minimal salt medium. The removal of parathion and γ-HCH by engineered UT26 in sterile and non-sterile soil was also studied. In both soil samples, a mixture of parathion (100 mg kg(-1)) and γ-HCH (10 mg kg(-1)) could be degraded completely within 15 days. Soil treatment results indicated that the engineered UT26 is a promising multifunctional bacterium that could be used for the bioremediation of multiple pesticide-contaminated environments.

  18. Application of Box-Behnken design for the removal of two organophosphorus pesticides by used Tea leaves

    NASA Astrophysics Data System (ADS)

    Azharul Islam, M.; Sakkas, Vasilios; Albanis, Triantafyllos A.

    2013-04-01

    Removal of two organophosphorus pesticides bromophos methyl [BM: O, O- dimethyl - O - (2, 5-dichloro -4 bromophenyl) phosphorothioate] and quinalphos [QP: O, O-diethyl O-2-quinoxalinyl phosphorothioate] on used tea leaves were studied by batch equilibration method. Adsorption isotherms were conformed well to Langmuir for quinalphos and Freundlich equation for bromophos methyl. The kinetic data fitted well by the pseudo second order model for both pesticides. Box-Behnken design was successfully employed for experimental design and analysis of results. The interactions of pH, initial concentration and adsorbent dose on two pesticides adsorption by used tea leaves were investigated by this model. The optimum pH, initial concentration and adsorbent dose with their corresponding removal efficiency were found to be 7.88, 11.94 mg L-1, 0.37g and 100% for bromophos methyl respectively, for quinalphos 8.72, 6.44 mg L-1, 0.39g and 93.98% respectively. Keywords: Box-Behnken; quinalphos; bromophos methyl; Kinetics; used tea leaves

  19. A new method for analysis of the toxicity of organophosphorus pesticide, dimethoate on rotifer based on response surface methodology.

    PubMed

    Guo, Ruixin; Ren, Xinkun; Ren, Hongqiang

    2012-10-30

    This study analyzed the toxicity of organophosphorus pesticide, dimethoate on freshwater rotifer Brachionus calyciflorus, using swimming angular and linear speed alteration as the sub-lethal endpoints. Response surface methodology (RSM) was applied in experimental design and data analysis to consider two related factors: toxic concentration, exposure time and their interaction. In general, inhibition effect of the pesticide on rotifer swimming was observed clearly at any given toxicant concentration. The highest inhibition rates in angular and linear speed were obtained in the shortest exposure time (11.36 min) and the highest dimethoate concentration (1.85 mg L(-1)). The RSM used for the analysis of treatment combinations showed that a cubic polynomial regression model was in good agreement with experimental results, with R(2)=0.992 and 0.9997, for swimming angular speed inhibition rate and linear speed inhibition rate (p<0.01, F-test, respectively). 3D reference surface plots and contour plots showed that the toxic effect was influenced not only by dimethoate concentration, but also by the exposure time. A time-step effect was observed clearly. Thus, the pesticide dimethoate had toxic stress on the swimming behavior of rotifers.

  20. The 47th annual Florida pesticide residue workshop

    USDA-ARS?s Scientific Manuscript database

    This is an introductory article to a special section of the Journal of Agricultural and Food Chemistry consisting of publications from the 47th Annual Florida Pesticide Residue Workshop held in St. Pete Beach, FL in July of 2010....

  1. Pesticide residue quantification analysis by hyperspectral imaging sensors

    NASA Astrophysics Data System (ADS)

    Liao, Yuan-Hsun; Lo, Wei-Sheng; Guo, Horng-Yuh; Kao, Ching-Hua; Chou, Tau-Meu; Chen, Junne-Jih; Wen, Chia-Hsien; Lin, Chinsu; Chen, Hsian-Min; Ouyang, Yen-Chieh; Wu, Chao-Cheng; Chen, Shih-Yu; Chang, Chein-I.

    2015-05-01

    Pesticide residue detection in agriculture crops is a challenging issue and is even more difficult to quantify pesticide residue resident in agriculture produces and fruits. This paper conducts a series of base-line experiments which are particularly designed for three specific pesticides commonly used in Taiwan. The materials used for experiments are single leaves of vegetable produces which are being contaminated by various amount of concentration of pesticides. Two sensors are used to collected data. One is Fourier Transform Infrared (FTIR) spectroscopy. The other is a hyperspectral sensor, called Geophysical and Environmental Research (GER) 2600 spectroradiometer which is a batteryoperated field portable spectroradiometer with full real-time data acquisition from 350 nm to 2500 nm. In order to quantify data with different levels of pesticide residue concentration, several measures for spectral discrimination are developed. Mores specifically, new measures for calculating relative power between two sensors are particularly designed to be able to evaluate effectiveness of each of sensors in quantifying the used pesticide residues. The experimental results show that the GER is a better sensor than FTIR in the sense of pesticide residue quantification.

  2. Organochlorine pesticides residue in breast milk: a systematic review

    PubMed Central

    Pirsaheb, Meghdad; Limoee, Mojtaba; Namdari, Farideh; Khamutian, Razieh

    2015-01-01

    Background: Chlorinated pesticides have been used in pest control for several decades in the world. These compounds are still applied in many regions, and their continuous usage has resulted in their bioaccumulation and residue in the food chain. These residues could transfer to food products and accumulate in fat tissues. Undoubtedly, the breast milk could be a significant biomarker for estimation of these residues in the human body. This study was conducted to review and compile the results of the studies undertaken in the world which surveyed the organochlorine pesticides residue in breast milk. Methods: A total of 710 national and international articles and texts related to the focused subject were extracted from the virtual databases using the following key words: Chlorinated pesticides, residue and breast milk. Thirty articles published between 1980 and 2013 were selected and reviewed. Results: The majority of the reviewed articles indicated the presence of two or more organochlorine pesticides in the collected samples of breast milk. Based on the reviewed studies, dichlorodiphenyltrichloroethane (DDT) had the highest level of concentration in the collected samples of breast milk. Moreover, there was a statistically significant positive correlation between mother’s age, her multiparty and concentration of chlorinated pesticides in breast milk. Conclusion: The organochlorine pesticides are still applied in some developing countries including some regions of Iran. Thus, it seems essential to inform the community about the adverse effects of this class of pesticides; and most importantly the governments should also ban the use of such compounds. PMID:26478886

  3. Exposure to the mixture of organophosphorus pesticides is embryotoxic and teratogenic on gestational rats during the sensitive period.

    PubMed

    Yu, Yan; Yang, Yuxuan; Zhao, Xiaodan; Liu, Xiaofei; Xue, Jianjun; Zhang, Jinghua; Yang, Aimin

    2017-01-01

    Mixture of organophosphorus pesticides (MOPs) has been used worldwide to increase food production. The MOPs are harmful, and the exposure to them is both agricultural and nonagricultural through contaminated food. The neurotoxicity of MOPs has received more consideration recently due to the increased cases of malformed fetuses suspected to be caused by the MOPs exposure during gestation; however, relevant studies in animal model are rare. In this study, we performed a comprehensive analysis and demonstrated potential perinatal embryotoxicity and teratogenicity of MOPs exposure. As results, we found that MOPs decreased in utero fetal growth and alter the ratio of organs to whole body weight of the pregnant rats. MOPs also had been shown to disturb the balance of sex hormones and affect the reproduction of rats. Furthermore, we found various significantly elevated deformities in MOPs exposed embryos, confirming the embryotoxic and teratogenic effects of maternal exposure to MOPs. © 2015 Wiley Periodicals, Inc. Environ Toxicol 32: 139-146, 2017.

  4. Genome-wide gene expression analysis in response to organophosphorus pesticide chlorpyrifos and diazinon in C. elegans.

    PubMed

    Viñuela, Ana; Snoek, L Basten; Riksen, Joost A G; Kammenga, Jan E

    2010-08-16

    Organophosphorus pesticides (OPs) were originally designed to affect the nervous system by inhibiting the enzyme acetylcholinesterase, an important regulator of the neurotransmitter acetylcholine. Over the past years evidence is mounting that these compounds affect many other processes. Little is known, however, about gene expression responses against OPs in the nematode Caenorhabditis elegans. This is surprising because C. elegans is extensively used as a model species in toxicity studies. To address this question we performed a microarray study in C. elegans which was exposed for 72 hrs to two widely used Ops, chlorpyrifos and diazinon, and a low dose mixture of these two compounds. Our analysis revealed transcriptional responses related to detoxification, stress, innate immunity, and transport and metabolism of lipids in all treatments. We found that for both compounds as well as in the mixture, these processes were regulated by different gene transcripts. Our results illustrate intense, and unexpected crosstalk between gene pathways in response to chlorpyrifos and diazinon in C. elegans.

  5. Applied clinical pharmacology and public health in rural Asia – preventing deaths from organophosphorus pesticide and yellow oleander poisoning

    PubMed Central

    Eddleston, Michael

    2013-01-01

    Self-poisoning with pesticides or plants is a major clinical problem in rural Asia, killing several hundred thousand people every year. Over the last 17 years, our clinical toxicology and pharmacology group has carried out clinical studies in the North Central Province of Sri Lanka to improve treatment and reduce deaths. Studies have looked at the effectiveness of anti-digoxin Fab in cardiac glycoside plant poisoning, multiple dose activated charcoal in all poisoning, and pralidoxime in moderate toxicity organophosphorus insecticide poisoning. More recently, using a Haddon matrix as a guide, we have started conducting public health and animal studies to find strategies that may work outside of the hospital. Based on the 2009 GSK Research in Clinical Pharmacology prize lecture, this review shows the evolution of the group's research from a clinical pharmacology approach to one that studies possible interventions at multiple levels, including the patient, the community and government legislation. PMID:22943579

  6. Laundering as decontamination of apparel fabrics: residues of pesticides from six chemical classes.

    PubMed

    Nelson, C; Laughlin, J; Kim, C; Rigakis, K; Raheel, M; Scholten, L

    1992-07-01

    Research on reducing the level of pesticide residue on a textile substrate has examined many variables under many different conditions. This study controlled fiber type and the use of prewash product in an examination of residue levels for a number of pesticides in different pesticide classes. For all pesticides examined, the use of prewash lowered pesticide residues regardless of fiber type. Differences in pesticide residue level attributable to fiber type were not consistent.

  7. Pesticide residues in grain from Kazakhstan and potential health risks associated with exposure to detected pesticides.

    PubMed

    Lozowicka, B; Kaczynski, P; Paritova, Capital A Cyrillic Е; Kuzembekova, G B; Abzhalieva, A B; Sarsembayeva, N B; Alihan, K

    2014-02-01

    This paper presents the first study of pesticide residue results in grain from Kazakhstan. A total of 80 samples: barley, oat, rye, and wheat were collected and tested in the accredited laboratory. Among 180 pesticides, 10 active substances were detected. Banned pesticides, such as DDTs, γ-HCH, aldrin and diazinon were found in cereal grain. Chlorpyrifos methyl and pirimiphos methyl were the most frequently detected residues. No residues were found in 77.5% of the samples, 13.75% contained pesticide residues at or below MRLs, and 8.75% above MRLs. The greatest percentage of samples with residues (29%) was noted for wheat, and the lowest for rye (20%). Obtained data were used to estimate potential health risks associated with exposure to these pesticides. The highest estimated daily intakes (EDIs) were as follows: 789% of the ADI for aldrin (wheat) and 49.8% of the ADI for pirimiphos methyl (wheat and rye). The acute risk from aldrin and tebuconazole in wheat was 315.9% and 98.7% ARfD, respectively. The results show that despite the highest EDIs of pesticide residues in cereals, the current situation could not be considered a serious public health problem. Nevertheless, an investigation into continuous monitoring of pesticide residues in grain is recommended.

  8. Residues of organochlorine pesticides in surface soil and raw ...

    EPA Pesticide Factsheets

    The central Asian Republic of Tajikistan has been an area of extensive historical agricultural pesticide use as well as large scale burials of obsolete banned chlorinated insecticides. The current investigation was a four year study of legacy organochlorine pesticides in surface soil and raw foods in four rural areas of Tajikistan. The four study areas included the pesticide burial sites of Konibodom and Vakhsh, and family farms of Garm and Chimbuloq villages. These areas were selected to represent a diversity of pesticide disposal histories and to allow assessment of local pesticide contamination in Tajikistan. Each site was visited multiple times and over 500 samples of surface soil and raw foods were collected and analyzed for twenty legacy organochlorine pesticides. Various local food products were sampled to represent the range of raw foods potentially containing residues of banned pesticides, including dairy products, meat, edible plant and cotton seed products. The pesticide analytes included DDTs (DDT, DDD, DDE), lindane isomers (α, β, γ, δ BHC), endosulfan isomers (endosulfan I, II, sulfate), other cyclodienes (aldrin, α and γ chlordanes, dieldrin, endrin, endrin aldehyde and ketone, heptachlor, heptachlor epoxide), and methoxychlor. Pesticide analytes were selected based on availability of commercial standards and known or suspected historical pesticide use and burial. Pesticide contamination was highest in soil at each of the four sites, and ge

  9. Guidelines for predicting the dietary intake of pesticide residues*

    PubMed Central

    1988-01-01

    These guidelines have been developed to describe procedures for predicting the dietary intake of pesticide residues, and will assist national authorities in their considerations of the acceptability of the Codex maximum residue limits (MRLs). The relevant authorities are invited to consider the basic approaches described in these guidelines, which have been designed to provide reasonable assurance that such MRLs would not result in dietary intakes that exceed the acceptable daily intake (ADI) of a pesticide. PMID:3262445

  10. Dynamic microwave-assisted extraction online coupled with single drop microextraction of organophosphorus pesticides in tea samples.

    PubMed

    Wu, Lijie; Hu, Mingzhu; Li, Zhanchao; Song, Ying; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

    2015-08-14

    A new method for the determination of seven organophosphorus pesticides was developed using dynamic microwave-assisted extraction online coupled with single drop microextraction prior to gas chromatographic mass spectrometry (GC-MS). The method combines the advantages of dynamic microwave-assisted extraction and single-drop microextraction, which could greatly simplify the operation and reduce the whole pretreatment time. In the developed method, tea samples were extracted with 25% ethanol aqueous solution and purified with acidic alumina at the same time, and then the analytes were concentrated into microextraction solvent. When the extraction was completed, the solvent microdrop containing the enriched analytes was retracted into the microsyringe and directly analyzed by GC-MS without any filtration or cleanup step. The method makes extraction, cleanup, separation, and enrichment to be carried out in one step. Several experimental parameters, including type of extraction solvent, type and amount of dispersant, type and volume of microextraction solvent, microwave power, extraction time, and flow rate of extraction solvent were investigated and optimized. Under optimal experimental conditions, good linearity was observed in the range of 2.00-500.00 μg kg(-1). The limits of detection and quantification were in the range of 0.4-1.7 μg kg(-1) and 1.1-5.6 μg kg(-1), respectively. The present method was applied to the analysis of tea samples, and the recoveries of analytes were in the range of 84.9-106.4% with the relative standard deviations ranging from 1.0 to 6.1%. The results showed that the present method was a rapid and feasible method for the determination of organophosphorus pesticides in tea samples.

  11. Presence of pesticide residues on produce cultivated in Suriname.

    PubMed

    Abdoel Wahid, F; Wickliffe, J; Wilson, M; Van Sauers, A; Bond, N; Hawkins, W; Mans, D; Lichtveld, M

    2017-06-01

    Agricultural pesticides are widely used in Suriname, an upper middle-income Caribbean country located in South America. Suriname imported 1.8 million kg of agricultural pesticides in 2015. So far, however, national monitoring of pesticides in crops is absent. Reports from the Netherlands on imported Surinamese produce from 2010 to 2015 consistently showed that samples exceeded plant-specific pesticide maximum residue limits (MRLs) of the European Union (EU). Consumption of produce containing unsafe levels of pesticide residues can cause neurological disorders, and particularly, pregnant women and children may be vulnerable. This pilot study assessed the presence of pesticide residues in commonly consumed produce items cultivated in Suriname. Thirty-two insecticides (organophosphates, organochlorines, carbamates, and pyrethroids) and 12 fungicides were evaluated for their levels in nine types of produce. Pesticide residue levels exceeding MRLs in this study regarded cypermethrin (0.32 μg/g) in tomatoes (USA MRL 0.20 μg/g), lambda-cyhalothrin (1.08 μg/g) in Chinese cabbage (USA MRL 0.40 μg/g), endosulfan (0.07 μg/g) in tannia (EU MRL 0.05 μg/g), and lindane (0.02 and 0.03 μg/g, respectively) in tannia (EU MRL 0.01 μg/g). While only a few pesticide residues were detected in this small pilot study, these residues included two widely banned pesticides (endosulfan and lindane). There is a need to address environmental policy gaps. A more comprehensive sampling and analysis of produce from Suriname is warranted to better understand the scope of the problem. Preliminary assessments, using intake rate, hazard quotient, and level of concern showed that it is unlikely that daily consumption of tannia leads to adverse health effects.

  12. Organochlorine pesticide residues in wheat from Konya region, Turkey.

    PubMed

    Guler, G O; Cakmak, Y S; Dagli, Z; Aktumsek, A; Ozparlak, H

    2010-05-01

    The present study has been carried out to evaluate the organochlorine pesticide contamination in wheat from Konya region. This region is the largest area of cereal production in Turkey. The contamination level has been determined according to the European Community Directives. Different wheat samples (36) were obtained from local farmers and wheat factories in this region. All the wheat samples examined were found to be contaminated by organochlorine pesticide residues of cis-Chlordane and methoxychlor. Chlordane isomers, methoxychlor, DDT and its metabolites, aldrin, beta HCH, heptachlor and lindane have been found to be the highest organochlorine pesticide residues. In some of these samples, various organochlorine pesticide residues have been determined to be higher than European Community maximum residual limits. The residues of aldrin in one sample, trans-Chlordane in one sample, oxy-chlordane in eight samples and methoxychlor in one sample were found to be in excess of EC MRLs. Since most of the samples have been found to be contaminated with residues and some residues exceed EC MRLs, a control of organochlorine pesticide residues in wheat is necessary. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  13. Selective solid-phase extraction using molecularly imprinted polymer for the analysis of polar organophosphorus pesticides in water and soil samples.

    PubMed

    Zhu, Xiaolan; Yang, Jun; Su, Qingde; Cai, Jibao; Gao, Yun

    2005-10-28

    An analytical methodology for the analysis of four polar organophophorus pesticides (monocrotophos, mevinphos, phosphamidon, omethoate) in water and soil samples incorporating a molecularly imprinted solid-phase extraction (MISPE) process using a monocrotophos-imprinted polymer was developed. Binding study demonstrated that the polymer showed excellent affinity and high selectivity to monocrotophos. The MISPE procedure including the clean-up step to remove any interferences was optimized. The accuracy and selectivity of the MISPE process developed were verified using a non-imprinted (blank) polymer and a classical ENVI-18 cartridge as the SPE matrix during control experiments. The use of MISPE improved the accuracy and precision of the GC method and lowered the limit of detection. The recoveries of four polar organophosphorus pesticides (OPPs) extracted from 1 L of river water at a 100 ng/L spike level were in the range of 77.5-99.1%. The recoveries of organophosphorus pesticides extracted from a 5-g soil sample at the 100 microg/kg level were in the range of 79.3-93.5%. The limit of detection varied from 10 to 32 ng/L in water and from 12 to 34 microg/kg in soil samples. The molecularly imprinted polymer (MIP) enabled the selective extraction of four organophosphorus pesticides successfully from water and soil samples, demonstrating the potential of molecularly imprinted solid-phase extraction for rapid, selective, and cost-effective sample pretreatment.

  14. Setting Tolerances for Pesticide Residues in Foods

    EPA Pesticide Factsheets

    Pesticides are widely used in producing food and may remain in small amounts in or on fruits, vegetables, grains, and other foods. EPA ensures the safety of the food supply regulating the amount of pesticide that may remain on food. Learn how we do this.

  15. An estimation of the exposure to organophosphorus pesticides through the simultaneous determination of their main metabolites in urine by liquid chromatography-tandem mass spectrometry.

    PubMed

    Hernández, F; Sancho, J V; Pozo, O J

    2004-09-05

    A rapid method has been developed for the determination of 4-nitrophenol (PNP) (parathion and methyl-parathion metabolite) and 3-methyl-4-nitrophenol (3-Me-PNP) (fenitrothion metabolite) in human urine by coupled-column liquid chromatography combined with tandem mass spectrometry (LC-LC-MS/MS). The LC-LC-MS/MS approach allows the determination at sub-ppb level of free metabolites by injecting the urine directly into the system and the total metabolites after a simple enzymatic hydrolysis. The method has been validated, obtaining limits of detection of 0.1 and 0.2 microg/L for 4-nitrophenol and 3-methyl-4-nitrophenol, respectively. Additionally, a multi-residue LC-MS/MS method is proposed in order to evaluate the levels of other parathion and methyl parathion metabolites. This approach allows the simultaneous determination of dimethyl phosphate (DMP), dimethyl thiophosphate (DMTP), 4-nitrophenolsulphate and 4-nitrophenolglucuronide without tedious sample treatments. The applicability of both methods is demonstrated by applying them to various urine samples from an unexposed population and a grower who applied methyl parathion. The combination of both methods allows a general overview on the presence of different metabolites (free and conjugated) and the concentration ratios between them, giving useful information on organophosphorus pesticides metabolism and excretion.

  16. Application of magnetic solvent bar liquid-phase microextraction for determination of organophosphorus pesticides in fruit juice samples by gas chromatography mass spectrometry.

    PubMed

    Wu, Lijie; Song, Ying; Hu, Mingzhu; Zhang, Hanqi; Yu, Aimin; Yu, Cui; Ma, Qiang; Wang, Ziming

    2015-06-01

    A simple, rapid and sensitive sample pretreatment technique, magnetic solvent bar liquid-phase microextraction (MSB-LPME) was developed for extracting organophosphorus pesticides from fruit juice. The analytes were extracted from the sample to the organic solvent immobilized in the fiber. The magnetic solvent bar not only can be used to stir the samples but also extract the analytes. After extraction, the analyte-adsorbed magnetic solvent bar can be readily isolated from the sample solution by a magnet, which could greatly simplify the operation and reduce the whole pretreatment time. The bar was eluted with methanol. The elute was evaporated to dryness and residue was dissolved in hexane. Several experimental parameters were investigated and optimized, including type of extraction solvent, number of magnetic solvent bar, extraction temperature, extraction time, salt concentration, stirring speed, pH and desorption conditions. The recoveries were in the range of 81.3-104.6%, and good reproducibilities were obtained with relative standard deviation below 6.1%.

  17. 40 CFR 158.2040 - Biochemical pesticides residue data requirements table.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Biochemical pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2040 Biochemical pesticides residue data requirements table. (a) General. Sections 158.100 through 158.130 describe how to...

  18. 40 CFR 158.2040 - Biochemical pesticides residue data requirements table.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Biochemical pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2040 Biochemical pesticides residue data requirements table. (a) General. Sections 158.100 through 158.130 describe how to use...

  19. 40 CFR 158.2040 - Biochemical pesticides residue data requirements table.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Biochemical pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2040 Biochemical pesticides residue data requirements table. (a) General. Sections 158.100 through 158.130 describe how to use...

  20. 40 CFR 158.2082 - Experimental use permit biochemical pesticides residue data requirements table.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... pesticides residue data requirements table. 158.2082 Section 158.2082 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2082 Experimental use permit biochemical pesticides residue data requirements table. (a) General...

  1. 40 CFR 158.2082 - Experimental use permit biochemical pesticides residue data requirements table.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... pesticides residue data requirements table. 158.2082 Section 158.2082 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2082 Experimental use permit biochemical pesticides residue data requirements table. (a) General...

  2. 40 CFR 158.2040 - Biochemical pesticides residue data requirements table.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Biochemical pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2040 Biochemical pesticides residue data requirements table. (a) General. Sections 158.100 through 158.130 describe how to use...

  3. 40 CFR 158.2082 - Experimental use permit biochemical pesticides residue data requirements table.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... pesticides residue data requirements table. 158.2082 Section 158.2082 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2082 Experimental use permit biochemical pesticides residue data requirements table. (a) General...

  4. 40 CFR 158.2082 - Experimental use permit biochemical pesticides residue data requirements table.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... pesticides residue data requirements table. 158.2082 Section 158.2082 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Biochemical Pesticides § 158.2082 Experimental use permit biochemical pesticides residue data requirements table. (a) General...

  5. Pesticide residues in cereal crop grains in Poland in 2013.

    PubMed

    Malinowska, Elżbieta; Jankowski, Kazimierz; Sosnowski, Jacek; Wiśniewska-Kadżajan, Beata

    2015-06-01

    This paper presents the results of the audit on pesticide residues in cereal grains throughout Poland in 2013. The number of all samples of cereal grains was 380. Altogether 292 active substances of plant protection products were checked in the audit. Qualitative and quantative analyses were done according to Polish Standard PN-EN 15562:2008, using the LC-MS/MS technique. The methods (QuEChERS) is based on extraction of residues of plant protection products from a sample using acetonitrile. In the samples analyzed, 62 % of them did not contain any pesticide residues, 34 % of samples of cereal grains contained such residues but below the maximum residue limit, 3 % contained residues over the maximum limit, whereas 1 % of the samples contained illegal substances. The lowest amounts of pesticide residues were found in cereal grains coming from fields with cereal mixtures and in Avena grains, while the highest amounts were in Hordeum and Triticum grains. The substances found most often were fungicide residues. In northern and southern regions of Poland (Silesian, Pomeranian, and Kuyavian-Pomeranian voivodeships), cereal grains with pesticide residues were much more common than in other regions of Poland.

  6. Characterization of P-S bond hydrolysis in organophosphorothioate pesticides by organophosphorus hydrolase.

    PubMed

    Lai, K; Stolowich, N J; Wild, J R

    1995-04-01

    The extensive use of organophosphorothioate insecticides in agriculture has resulted in the risk of environmental contamination with a variety of broadly based neurotoxins that inhibit the acetylcholinesterases of many different animal species. Organophosphorus hydrolase (OPH, EC 3.1.8.1) is a broad-spectrum phosphotriesterase that is capable of detoxifying a variety of organophosphorus neurotoxins by hydrolyzing various phosphorus-ester bonds (P-O, P-F, P-CN, and P-S) between the phosphorus center and an electrophilic leaving group. OPH is capable of hydrolyzing the P-X bond of various organophosphorus compounds at quite different catalytic rates: P-O bonds (kcat = 67-5000 s-1), P-F bonds (kcat = 0.01-500 s-1), and P-S bonds (kcat = 0.0067 to 167 s-1). P-S bond cleavage was readily demonstrated and characterized in these studies by quantifying the released free thiol groups using 5,5'-dithio-bis-2-nitrobenzoic acid or by monitoring an upfield shift of approximately 31 ppm by 31P NMR. A decrease in the toxicity of hydrolyzed products was demonstrated by directly quantifying the loss of inhibition of acetylcholinesterase activity. Phosphorothiolate esters, such as demeton-S, provided noncompetitive inhibition for paraoxon (a P-O triester) hydrolysis, suggesting that the binding of these two different classes of substrates was not identical.

  7. Airborne pesticide residues along the Mississippi River

    USGS Publications Warehouse

    Majewski, M.S.; Foreman, W.T.; Goolsbys, D.A.; Nakagaki, N.

    1998-01-01

    The occurrence, concentration, and geographical distribution of agricultural pesticides were determined in air over the Mississippi River from New Orleans, LA, to St. Paul, MN, during the first 10 days of June 1994. Air samples were collected from a research vessel by pulling air through polyurethane foam plugs at about 100 L/min for up to 24 h. Each sample was analyzed for 42 pesticides and 3 pesticide transformation products. Twenty- five compounds-15 herbicides, 7 insecticides, and 3 pesticide transformation products-were detected in one or more samples with concentrations ranging from 0.05 to 80 ng/m3. Alachlor, chlorpyrifos, diazinon, fonofos, malathion, methyl parathion, metolachlor, metribuzin, pendimethalin, and trifluralin were detected in 80% or more of the samples. The highest concentrations for chlorpyrifos (1.6 ng/m3), diazinon (0.36 ng/m3), and malathion (4.6 ng/m3) all occurred near major metropolitan areas. These samples represent a 'snapshot in time', a spatial and temporal integration of which pesticides were present in the air during each sampling period. The occurrence and atmospheric concentrations of the observed pesticides were most closely related to their use on cropland within 40 km of the river.The occurrence, concentration, and geographical distribution of agricultural pesticides were determined in air over the Mississippi River from New Orleans, LA, to St. Paul, MN, during the first 10 days of June 1994. Air samples were collected from a research vessel by pulling air through polyurethane foam plugs at about 100 L/min for up to 24 h. Each sample was analyzed for 42 pesticides and 3 pesticide transformation products. Twenty-five compounds-15 herbicides, 7 insecticides, and 3 pesticide transformation products-were detected in one or more samples with concentrations ranging from 0.05 to 80 ng/m3. Alachlor, chlorpyrifos, diazinon, fonofos, malathion, methyl parathion, metolachlor, metribuzin, pendimethalin, and trifluralin were detected in

  8. Assessment of pesticide residues in two arable soils from the semi-arid and subtropical regions of China.

    PubMed

    Wang, Ligang; Zhao, Zhenhua; Jiang, Xin; Wu, Jinshui; Martens, Dieter

    2005-10-01

    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 beta-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 beta-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, beta-HCH) > OP (parathion-methyl) > CPs for the semi-arid soil, and as OPs (parathion-methyl and malathion) > CPs > CHCs (beta-HCH) for the subtropical soil.

  9. Development of a passive air sampler to measure airborne organophosphorus pesticides and oxygen analogs in an agricultural community.

    PubMed

    Armstrong, Jenna L; Yost, Michael G; Fenske, Richard A

    2014-09-01

    Organophosphorus pesticides are some of the most widely used insecticides in the US, and spray drift may result in human exposures. We investigate sampling methodologies using the polyurethane foam passive air sampling device to measure cumulative monthly airborne concentrations of OP pesticides chlorpyrifos, azinphos-methyl, and oxygen analogs. Passive sampling rates (m(3)d(-1)) were determined using calculations using chemical properties, loss of depuration compounds, and calibration with side-by-side active air sampling in a dynamic laboratory exposure chamber and in the field. The effects of temperature, relative humidity, and wind velocity on outdoor sampling rates were examined at 23 sites in Yakima Valley, Washington. Indoor sampling rates were significantly lower than outdoors. Outdoor rates significantly increased with average wind velocity, with high rates (>4m(3)d(-1)) observed above 8ms(-1). In exposure chamber studies, very little oxygen analog was observed on the PUF-PAS, yet substantial amounts chlorpyrifos-oxon and azinphos methyl oxon were measured in outdoor samples. PUF-PAS is a practical and useful alternative to AAS because it results in little artificial transformation to the oxygen analog during sampling, it provides cumulative exposure estimates, and the measured sampling rates were comparable to rates for other SVOCs. It is ideal for community based participatory research due to low subject burden and simple deployment in remote areas.

  10. Efficient immobilization of acetylcholinesterase onto amino functionalized carbon nanotubes for the fabrication of high sensitive organophosphorus pesticides biosensors.

    PubMed

    Yu, Guangxia; Wu, Weixiang; Zhao, Qiang; Wei, Xiaoyun; Lu, Qing

    2015-06-15

    This work introduced an efficient immobilization of acetylcholinesterase (AChE) onto amino functionalized carbon nanotubes (CNT-NH2), in order to fabricate high sensitive and practical organophosphorus pesticide (OPs) biosensors. Compared with the pristine, -COOH and -OH decorated CNTs, there were larger amount of enzymes adsorbed on the surface of CNT-NH2 with a favorable orientation and the best amperometric response was obtained on the AChE/CNT-NH2/GC electrode. Furthermore, the biosensor modified with CNT-NH2 showed a high affinity to acetylthiocholine chloride (ATCh) and could catalyze the hydrolysis of ATCh with an apparent Michaelis-Menten constant (Km) value of 67.4 µM. Using paraoxon as a model compound, wide linear ranges from 0.2 nM to 1 nM and 1 nM to 30 nM, and a low detection limit of 0.08 nM were obtained with satisfactory reproducibility and stability. Moreover, the biosensor had also been successfully employed for the determination of low concentrations of pesticides in real vegetable samples. This method could be extended to other functionalized nano-materials for their application in constructing biosensors.

  11. Removal of Organophosphorus Pesticides from Aqueous Solution by Magnetic Fe3O4/Red Mud-Nanoparticles.

    PubMed

    Aydin, Senar

    2016-12-01

      The aim of this study was to investigate the usability of magnetic Fe3O4/red mud nanoparticles (NPs) for the removal of organophosphorus pesticides from water samples. The effect of various experimental parameters such as red mud amount in Fe3O4/red mud-NPs, pH, contact time, initial pesticide concentrations and adsorbent dose was studied in order to find the optimum conditions for their removal in a batch process. The Fe3O4/red mud-NPs were characterized by using TGA, SEM, XRD, VSM, and determination of the BET surface area. After the regenerated Fe3O4/red mud-NPs were used three times, the sorption capacity and the magnetic separability were observed to be unaffected. Freundlich model described the sorption process better than Langmuir isotherm and the pseudo second-order kinetic model was determined as the best-fit model. The film diffusion mechanism was found to be a main rate control mechanism. The Fe3O4/red mud-NPs satisfactorily removed the OPPS from real water samples.

  12. Matrix solid-phase dispersion extraction of organophosphorus pesticide using SiO2-poly(N-vinylimidazole)

    NASA Astrophysics Data System (ADS)

    Gutiérrez-Solís, M. C.; Muñoz-Rodríguez, D.; Medina-Peralta, S.; Carrera-Figueiras, C.; Ávila-Ortega, A.

    2013-06-01

    A sorbent material based on silica particles modified with poly(N-vinylimidazole) (SiO2-PVI) has been evaluated for the treatment of samples by matrix solid-phase dispersion (MSPD). The extraction of four organophosphorus pesticides was done from a spiked tomato and the extracts were analyzed by gas chromatography coupled to mass spectrometry. Six elution solvents were evaluated and acetone was selected due to better recovery of the four pesticides and low background signal in the chromatograms. A factorial design 24 was used for selection of extraction conditions. The factors were contact time, acetone volume, treatment (with or without freeze-drying) and adsorbent (SiO2 or SiO2-PVI). The best recoveries were obtained using 15 minutes of contact, 2 mL of solvent and sorbent without freeze-drying. The recoveries were between 60 and 83% for SiO2-PVI in spiked tomato with 0.2 and 0.8μg/g.

  13. A review of organochlorine pesticide residues in ferruginous hawk eggs

    USGS Publications Warehouse

    Henny, C.J.

    1985-01-01

    Ten Ferruginous Hawk nests in northeast Oregon were studied from 1978 to 1980. Pesticide residues, eggshell thickness, and reproductive success from these nests will be reviewed. In addition, egg residues from other published studies in the Pacific Northwest and elsewhere will be discussed.

  14. An optical instrument to test pesticide residues in agricultural products

    NASA Astrophysics Data System (ADS)

    Qiu, Zhengjun; Zheng, Wenzhong; Fang, Hui; He, Yong

    2005-10-01

    Pesticide is one of the indispensability materials in modern agricultural management, however the excessive use of pesticides has threatened the ecological environment and people's health. This paper introduced an optical instrument to test the pesticide residues in agricultural products based on the inhibition rate of organophosphates against acrtyl-cholinesterase (AchE). The instrument consists mainly of a solid light source with 410nm wavelength, a sampling container, an optical sensor, a temperature sensor, and a MCU based data acquisition board. The light illuminated through the liquid in the sampling container, and the absorptivity was determined by the amount of the pesticide residues in the liquid. This paper involves the design of optical testing system, the data acquisition and calibration of the optical sensor, the design of microcontroller-based electrical board. Tests were done to reveal the affection of temperature and reacting time on AchE, to establish the relationship between the amount of methamidophos and dichlorvos with AchE. The results showed that the absorption rate was related to the pesticide residues and it could be concluded that the pesticide residues exceeded the normal level when the inhibition rate was over 50 percent. The instrument has potential application in vegetable markets.

  15. Pesticide residues in essential oils: evaluation of a database.

    PubMed

    Klier, B; Knödler, M; Peschke, J; Riegert, U; Steinhoff, B

    2015-01-01

    In the context of a revision of the European Pharmacopoeia (Ph. Eur.) general monograph Essential oils (2098), the need to include a test for pesticides is being discussed. According to published literature, some oils, mainly those produced by cold pressing (e.g. citrus oils), can contain relevant amounts of pesticide residues, whereas distilled oils showed positive findings in only a few cases. Recent evaluation of a database containing 127 517 sets of data compiled over 8 years, showed positive results in 1 150 cases (0.90 per cent), and the limits of Ph. Eur. general chapter 2.8.13 Pesticide residues or Regulation (EC) 396/2005, both applicable to herbal drugs, were exceeded in 392 cases (0.31 per cent, equivalent to 34.1 per cent of the positive results), particularly in cases of oils produced by cold pressing. From these results, it can be concluded that a general test on pesticides in the Ph. Eur. general monograph on essential oils is not required for most oils used in medicinal products. Therefore, it is proposed to limit the testing of essential oils for pesticide residues to those cases where potential residues are more of a concern, either due to the type of production process or to those processes where pesticides are actively used during cultivation of the plant (e.g. as documented according to Good Agricultural and Collection Practice (GACP)). Furthermore, in order to assess any potential risk, an approach using the Acceptable Daily Intake (ADI) can be made.

  16. Organochlorine Pesticide Residues in Plankton, Rangsit Agricultural Area, Central Thailand

    PubMed Central

    Siriwong, W.; Thirakhupt, K.; Sitticharoenchai, D.; Borjan, M.; Robson, M.

    2014-01-01

    Few studies have investigated organochlorine pesticide residue content in freshwater plankton communities in Thailand. As a result, this study looks to examine the concentration of organochlorine pesticide residues in plankton collected from Khlong 7 (canal) at Rangsit agricultural area, central Thailand from June 2006 to February 2007. The results from this study show that plankton communities were composed of microphytoplankton, microzooplankton, and mesozooplankton. The average method recoveries varied from 84% to 103% with a relative standard deviation between 0.20% and 3.72%. The concentrations of organochlorine pesticide residues during a one-year-period were in the range of 0.10–3.65 ng/g wet wt and contained DDT and derivatives > Σ endosulfan > Σ HCH > Σ heptachlor > aldrin and dieldrin > endrin and endrin aldehyde > methoxychlor, respectively. Moreover, the residues of Σ HCH, DDT and derivatives, and methoxychlor were higher during wet season than dry season (t-test, p ≤ 0.05). PMID:18777151

  17. Organochlorine pesticide residues in plankton, Rangsit agricultural area, central Thailand.

    PubMed

    Siriwong, W; Thirakhupt, K; Sitticharoenchai, D; Borjan, M; Robson, M

    2008-12-01

    Few studies have investigated organochlorine pesticide residue content in freshwater plankton communities in Thailand. As a result, this study looks to examine the concentration of organochlorine pesticide residues in plankton collected from Khlong 7 (canal) at Rangsit agricultural area, central Thailand from June 2006 to February 2007. The results from this study show that plankton communities were composed of microphytoplankton, microzooplankton, and mesozooplankton. The average method recoveries varied from 84% to 103% with a relative standard deviation between 0.20% and 3.72%. The concentrations of organochlorine pesticide residues during a one-year-period were in the range of 0.10-3.65 ng/g wet wt and contained DDT and derivatives > Sigma endosulfan > Sigma HCH > Sigma heptachlor > aldrin and dieldrin > endrin and endrin aldehyde > methoxychlor, respectively. Moreover, the residues of Sigma HCH, DDT and derivatives, and methoxychlor were higher during wet season than dry season (t-test, p

  18. Poly(phthalazine ether sulfone ketone) as novel stationary phase for stir bar sorptive extraction of organochlorine compounds and organophosphorus pesticides.

    PubMed

    Guan, Wenna; Wang, Yanjuan; Xu, Feng; Guan, Yafeng

    2008-01-04

    A novel poly(phthalazine ether sulfone ketone) (PPESK) film prepared by immersion precipitation technique was coated on stir bars for sorptive extraction. Scanning electron micrographs showed that the coating has a denser porous surface (about 1 microm in thickness) with a sponge-like sublayer, and the thickness of the coating was 250 microm. The PPESK coated stir bar has high thermostability (290 degrees C) and long lifetime (50 times). The extraction properties of this stir bar were evaluated for the extraction of both polar and semi-polar analytes, including organochlorine compounds and organophosphorus pesticides. The PPESK stir bar was proved to show higher affinity towards polar compounds than that of PDMS coated stir bar and higher sample load compared with corresponding PPESK fiber. It was applied to the determination of organochlorine compounds in seawater samples and organophosphorus pesticides in juices by gas chromatographic analysis. The effect of sample matrix was evaluated at optimized condition of extraction temperature, extraction time and salt concentration. Limits of detection were in the range of 0.05-2.53 ng L(-1) for organochlorine compounds in seawater samples using electron capture detector (ECD), with precisions of less than 11% RSD. Limits of detection for organophosphorus pesticides were in the range of 0.17-2.25 ng L(-1) and 2.47-10.3 ng L(-1) in grape and peach juice, respectively, using thermionic specified detector (TSD), with precisions of less than 12% RSD and 20% RSD, respectively.

  19. A novel layer-by-layer assembled multi-enzyme/CNT biosensor for discriminative detection between organophosphorus and non-organophosphrus pesticides.

    PubMed

    Zhang, Yuanyuan; Arugula, Mary A; Wales, Melinda; Wild, James; Simonian, Aleksandr L

    2015-05-15

    Organophosphate compounds are heavily used in agriculture and military activities, while non-organophosphate pesticides are mostly used in agriculture and home defense. Discriminative detection of such toxic compounds is very challenging and requires sophisticated and bulky instrumentation. Meanwhile, multi-enzyme biosensors may offer an effective solution to the problem and may become a versatile analytical tool for discriminative detection of different neurotoxins. In this study, we report for the first time a novel bi-enzyme biosensing system incorporating electrostatically interacted enzyme-armored MWCNT-OPH and MWCNT-AChE along with a set of cushioning bilayers consisting of MWCNT-polyethyleneimine and MWCNT-DNA on glassy carbon electrode for discriminative detection of organophosphorus (OP) and non-organophosphorus (non-OP) pesticides. LbL interfaces were characterized by surface plasmon resonance and electrochemical impedance spectroscopy, demonstrating stepwise assembly and electron conductivity studies. The detection limit was found to be ~0.5 for OP pesticide paraoxon and 1 μM for non-OP pesticide carbaryl, in a wide linear range. The biosensor performance was also validated using apple samples. Remarkable discriminative and straightforward detection between OP and non-OP neurotoxins was successfully achieved with cyclic voltammetry (CV) and UV-vis methods on the MWCNT-(PEI/DNA)2/OPH/AChE biosensor, showing great potential in large screening of OP and non-OP pesticides in practical applications.

  20. Impaired antioxidant gene expression by pesticide residues and its relation with other cellular biomarkers in Nile Tilapia (Oreochromis niloticus) from Lake Burullus.

    PubMed

    El Nahas, Abeer F; Abdel-Razek, Mohamed A S; Helmy, Nashwa M; Mahmoud, Shawky; Ghazy, Haneen A

    2017-03-01

    Organochlorines and Organophosphorus are the most commonly used pesticides. These pesticides constitute a considerable contaminating threat due to their excessive agricultural usage which in turn contaminates the aquatic system through agricultural drainage. The aim of this study was to evaluate water and tissue residues of both pesticides in O. niloticus obtained from three different sections in Lake Burullus, Egypt. Assessment of relative change in mRNA levels of GST and Vtg (oxidative stress indicator) was done and its relation with other cellular biomarkers including apoptosis, which is assessed by Cellular apoptosis susceptibility transcript level (CAS), comet assay and micronucleus assays (genotoxicity indicator). Pesticide residue levels in water are fluctuating. In fish tissues, most residues were higher than those found in water and were associated with down regulation of hepatic GST gene and Vtg expression. CAS gene involved in apoptosis, its transcript is down regulated in middle and western sections of the lake with higher pesticide residues. Different degrees of DNA damages in O. niloticus' liver cells were demonstrated by comet assay. Significant increase in the micronucleated cells in the three sections of the lake was observed; the western section fish showed the highest number. Persistent exposures of fish to pesticide caused impairment of antioxidant gene expression. This negatively affects apoptosis associated with damaging DNA and chromosome fragments. Copyright © 2016. Published by Elsevier Inc.

  1. NEUROTOXICOLOGICAL AND STATISTICAL ANALYSES OF A MIXTURE OF FIVE ORGANOPHOSPHORUS PESTICIDES USING A RAY DESIGN.

    EPA Science Inventory

    Pesticide application patterns generally result in exposure to mixtures instead of single chemicals. Of particular importance in the estimation of pesticide mixture risks is the detection and characterization of their interactions. This research tested for interaction(s) in a mix...

  2. NON-ADDITIVE INTERACTIONS OF AN ORGANOPHOSPHORUS PESTICIDE MIXTURE IN ADULT AND PREWEANLING RATS.

    EPA Science Inventory

    Critical features of risk assessment include the evaluation of risk following exposure to pesticide mixtures as well as the potential for increased sensitivity of the young. The US EPA is required to regulate pesticides acting via a common mechanism of action as a group, e.g.,...

  3. NON-ADDITIVE INTERACTIONS OF AN ORGANOPHOSPHORUS PESTICIDE MIXTURE IN ADULT AND PREWEANLING RATS.

    EPA Science Inventory

    Critical features of risk assessment include the evaluation of risk following exposure to pesticide mixtures as well as the potential for increased sensitivity of the young. The US EPA is required to regulate pesticides acting via a common mechanism of action as a group, e.g.,...

  4. NEUROTOXICOLOGICAL AND STATISTICAL ANALYSES OF A MIXTURE OF FIVE ORGANOPHOSPHORUS PESTICIDES USING A RAY DESIGN.

    EPA Science Inventory

    Pesticide application patterns generally result in exposure to mixtures instead of single chemicals. Of particular importance in the estimation of pesticide mixture risks is the detection and characterization of their interactions. This research tested for interaction(s) in a mix...

  5. Recovery of cholinesterase activity in five avian species exposed to dicrotophos, an organophosphorus pesticide

    USGS Publications Warehouse

    Fleming, W.J.; Grue, C.E.

    1981-01-01

    The responses of brain and plasma cholinesterase (ChE) activities were examined in mallard ducks, bobwhite quail, barn owls, starlings, and common grackles given oral doses of dicrotophos, an organophosphorus insecticide. Up to an eightfold difference in response of brain ChE activity to dicrotophos was found among these species. Brain ChE activity recovered to within 2 SD of normal within 26 days after being depressed 55 to 64%. Recovery of brain ChE activity was similar among species and followed the model Y = a + b (log10X).

  6. Screening and evaluation of fruit samples for four pesticide residues.

    PubMed

    Blasco, Cristina; Font, Guillermina; Mañes, Jordi; Picó, Yolanda

    2005-01-01

    The occurrence of 4 pesticide residues, imidacloprid, carbendazim, methiocarb, and hexythiazox, was assessed in several fruits (oranges, tangerines, watermelons, and date plums) from the Valencian Community (Spain). A total of 227 samples--56 oranges, 134 tangerines, 13 watermelons, and 24 date plums--were taken from an agricultural cooperative representative of the area studied during 2001. The pesticides were determined by liquid chromatography/mass spectrometry after sample extraction with ethyl acetate and anhydrous sodium sulfate. Recoveries of 4 pesticides at 2 fortification levels (0.02 and 0.2 mg/kg), the lower of which was the quantification limit, ranged from 60 to 108%. Concentrations of imidacloprid, carbendazim, methiocarb, and hexythiazox ranged from 0.02 to 0.75 mg/kg in 184 samples (54 oranges, 119 tangerines, 3 watermelons, and 8 date plums). Nineteen samples contained methiocarb or hexythiazox residues that exceeded the maximum residue limits. Calculation of the estimated daily intakes of the 4 pesticides studied and their comparison with the Acceptable Daily Intakes established by the Food and Agriculture Organization of the World Health Organization demonstrated the safety of fruit consumption and showed the importance of monitoring for pesticide residues.

  7. Pesticides

    MedlinePlus

    ... This agency determines how pesticides are applied during farming and how much pesticide residue can remain in ... al, eds. Rosen's Emergency Medicine: Concepts and Clinical Practice . 8th ed. Philadelphia, PA: Elsevier Saunders; 2014:chap ...

  8. Glove accumulation of pesticide residues for strawberry harvester exposure assessment.

    PubMed

    Li, Yanhong; Chen, Li; Chen, Zhenshan; Coehlo, Joe; Cui, Li; Liu, Yu; Lopez, Terry; Sankaran, Gayatri; Vega, Helen; Krieger, Robert

    2011-06-01

    We investigated the accumulation of pesticide residues on rubber latex gloves that are used by strawberry harvesters to protect their skin, reduce pesticide exposure and promote food safety. Gloves accumulated residues of 16 active ingredients including azoxystrobin, bifenthrin, boscalid, captan, cyprodinil, fenhexamid, fenpropathrin, fludioxonil, hexythiazox, malathion, methomyl, naled, propiconazole, pyraclostrobin, quinoline, and quinoxyfen at different times. Glove residue accumulation (t(½) 2.8-3.7 d) was very similar to the dissipation of DFRs (t(½) 2.1-3.0 d) during the first 3 weeks after malathion applications. Dermal malathion dose was 0.2 mg/kg at the preharvest interval and declined to trace levels during the following 3 months. Glove accumulation of malathion indicated trace surface residue availability and was used to assess the relationship between dislodgable foliar residues and potential hand exposure.

  9. Global Harmonization of Maximum Residue Limits for Pesticides.

    PubMed

    Ambrus, Árpád; Yang, Yong Zhen

    2016-01-13

    International trade plays an important role in national economics. The Codex Alimentarius Commission develops harmonized international food standards, guidelines, and codes of practice to protect the health of consumers and to ensure fair practices in the food trade. The Codex maximum residue limits (MRLs) elaborated by the Codex Committee on Pesticide Residues are based on the recommendations of the FAO/WHO Joint Meeting on Pesticides (JMPR). The basic principles applied currently by the JMPR for the evaluation of experimental data and related information are described together with some of the areas in which further developments are needed.

  10. Age-related differences in neurotoxicity produced by organophosphorus and N-methyl carbamate pesticides

    EPA Science Inventory

    Potential pesticide effects in infants and toddlers have received much attention in the scientific literature and the public media, including the concern for increased response to acute or shortterm exposures. Age-related differences in the acute neurotoxicity of acetylcholinest...

  11. Age-related differences in neurotoxicity produced by organophosphorus and N-methyl carbamate pesticides

    EPA Science Inventory

    Potential pesticide effects in infants and toddlers have received much attention in the scientific literature and the public media, including the concern for increased response to acute or shortterm exposures. Age-related differences in the acute neurotoxicity of acetylcholinest...

  12. EPA Method 614: The Determination of Organophosphorus Pesticides in Municipal and Industrial Wastewater

    EPA Pesticide Factsheets

    Method 614 describes procedures for preparation and analysis of samples for determination of organophosphate pesticides in industrial and municipal discharges using a GC with a phosphorus-specific flame photometric detector (FPD).

  13. Sampling and sample processing in pesticide residue analysis.

    PubMed

    Lehotay, Steven J; Cook, Jo Marie

    2015-05-13

    Proper sampling and sample processing in pesticide residue analysis of food and soil have always been essential to obtain accurate results, but the subject is becoming a greater concern as approximately 100 mg test portions are being analyzed with automated high-throughput analytical methods by agrochemical industry and contract laboratories. As global food trade and the importance of monitoring increase, the food industry and regulatory laboratories are also considering miniaturized high-throughput methods. In conjunction with a summary of the symposium "Residues in Food and Feed - Going from Macro to Micro: The Future of Sample Processing in Residue Analytical Methods" held at the 13th IUPAC International Congress of Pesticide Chemistry, this is an opportune time to review sampling theory and sample processing for pesticide residue analysis. If collected samples and test portions do not adequately represent the actual lot from which they came and provide meaningful results, then all costs, time, and efforts involved in implementing programs using sophisticated analytical instruments and techniques are wasted and can actually yield misleading results. This paper is designed to briefly review the often-neglected but crucial topic of sample collection and processing and put the issue into perspective for the future of pesticide residue analysis. It also emphasizes that analysts should demonstrate the validity of their sample processing approaches for the analytes/matrices of interest and encourages further studies on sampling and sample mass reduction to produce a test portion.

  14. Determination of pesticide residues in sewage sludge: a review.

    PubMed

    Tadeo, José L; Sánchez-Brunete, Consuelo; Albero, Beatriz; García-Valcárcel, Ana I

    2010-01-01

    Pesticides are widely applied to protect plants from diseases, weeds, and insect damage, and they usually come into contact with soil where they may undergo a variety of transformations and provide a complex pattern of metabolites. Spreading sewage sludge on agricultural lands has been actively promoted by national authorities as an economic way of recycling. However, as a byproduct of wastewater treatment, sewage sludge may contain pesticides and other toxic substances that could be incorporated into agricultural products or be distributed in the environment. This article reviews the determination of pesticides in sewage sludge samples. Sample preparation including pretreatment, extraction, and cleanup, as well as the subsequent instrumental determination of pesticide residues, are discussed. Extraction techniques such as Soxhlet extraction, ultrasound-assisted extraction, pressurized liquid extraction, supercritical fluid extraction, and matrix solid-phase dispersion and their most recent applications to the determination of pesticides in sewage sludge samples are reviewed. Determination of pesticides, generally carried out by GC and HPLC coupled with different detectors, especially MS for the identification and quantification of residues, is summarized and discussed.

  15. 40 CFR 158.2130 - Microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... health effects or the product characterization indicates the microbial pesticide has a significant... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Microbial pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2130 Microbial...

  16. 40 CFR 158.2130 - Microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... health effects or the product characterization indicates the microbial pesticide has a significant... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Microbial pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2130 Microbial...

  17. 40 CFR 158.2130 - Microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... health effects or the product characterization indicates the microbial pesticide has a significant... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Microbial pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2130 Microbial...

  18. 40 CFR 158.2130 - Microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... health effects or the product characterization indicates the microbial pesticide has a significant... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Microbial pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2130 Microbial...

  19. 40 CFR 158.2130 - Microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... health effects or the product characterization indicates the microbial pesticide has a significant... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Microbial pesticides residue data... (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158.2130 Microbial...

  20. Reduction of pesticide residues in tomatoes and other produce.

    PubMed

    Al-Taher, Fadwa; Chen, Yang; Wylie, Philip; Cappozzo, Jack

    2013-03-01

    There is interest in reducing pesticide residues in fruits and vegetables in order to minimize human exposure. The objectives of this study were to (i) determine the effect of various washing treatments with and without sonication on pesticide removal from tomatoes and (ii) assess the effectiveness of a water wash on select samples using a produce-washing flume. In the first set of experiments, tomatoes were contaminated with acephate, malathion, carbaryl, bifenthrin, cypermethrin, permethrin, cyhalothrin, chlorothalonil, and imidacloprid and were dried overnight. Subsets of the tomatoes were then washed (10°C, 1 min) with one of the following: water, sodium hypochlorite (80 μg/ml, pH 7), peroxyacetic acid (80 μg/ml), or Tween 20 (0.1%) with and without sonication. In general, the effect of sonication depended on the washing treatment and on the pesticide. A separate experiment measured pesticide residues in contaminated samples before and after being washed in a flume (22°C, 1 min). Pesticide residues in contaminated produce were reduced from about 40 to 90% when washed for 1 min in the flume.

  1. Pesticide residues in agricultural drains, southeastern desert area, California

    USGS Publications Warehouse

    Eccles, Lawrence A.

    1979-01-01

    A study is being made to determine the occurrence and distribution of pesticides in the agricultural drains for approximately 3/4 million irrigated acres in the southeastern desert area of California. This report describes the results of the first year of sampling and analyzing (1) water in the drains , (2) bed material in the drains, (3) water from field tile-drainage lines, and (4) irrigation tailwater and water in the drains directly exposed to drift from aerial application of pesticides. Residues of almost all the pesticides selected for monitoring were found in water in the drains. Examination of the data to determine the probable source of pesticides indicated generally slight concentrations from bed material in the drains, usually no detectable concentrations from field tile-drainage lines, and apparently large concentrations from irrigation tailwater and drift from aerial application. (Woodard-USGS)

  2. Determination of organophosphorus pesticides in water samples by single drop microextraction and gas chromatography-flame photometric detector.

    PubMed

    Ahmadi, F; Assadi, Y; Hosseini, S M R Milani; Rezaee, M

    2006-01-06

    In this paper we have developed single drop microextraction (SDME) with modified 1.00 microl microsyringe, followed by gas chromatography with flame photometric detector (GC-FPD) for determination of 13 organophosphorus pesticides (OPPs) in water samples. By using a 1.00 microl microsyringe the repeatability of drop volume and injection were improved, because of using maximum volume of microsyringe and no dead volume. On the other hand, the modification of needle tip caused increasing cross section of needle tip and increasing adhesion force between needle tip and drop, thereby increasing drop stability and achieving a higher stirrer speed (up to 1700 rpm). The method used 0.9 microl of carbon tetrachloride as extractant solvent, 40 min extraction time, stirring at 1300 rpm and no salt addition. The enrichment factor of this method ranged from 540 to 830. The linear ranges were 0.01-100 microg/l (four orders of magnitude) and limits of detection were 0.001-0.005 microg/l for most of analyte. The relative standard deviation (RSD%) for 2 microg/l of OPPs in water by using internal standard was in the range 1.1-8.6% (n = 5). The recoveries of OPPs from farm water at spiking level of 1.0 microg/l were 91-104%.

  3. Highly-sensitive organophosphorus pesticide biosensors based on CdTe quantum dots and bi-enzyme immobilized eggshell membranes.

    PubMed

    Xue, Gao; Yue, Zhao; Bing, Zhang; Yiwei, Tang; Xiuying, Liu; Jianrong, Li

    2016-02-07

    An optical biosensing method using CdTe quantum dots (QDs) and bi-enzyme-immobilized eggshell membranes for the determination of organophosphorus pesticides (OPs) has been developed. Increasing amounts of OPs led to a decrease of the enzymatic activity and thus a decrease in the production of hydrogen peroxide (H2O2), which can quench the fluorescence of the CdTe QDs. Under the optimum conditions, there was a good linear relationship between the enzyme inhibition percentage and the logarithm of paraoxon or parathion concentration in the range of 1.0 × 10(-11)-1.0 × 10(-6) mol L(-1). The detection limit (S/N = 3) of the proposed biosensors were as low as 4.30 × 10(-12) mol L(-1) for paraoxon and 2.47 × 10(-12) mol L(-1) for parathion. The bi-enzyme-immobilized eggshell membrane demonstrated a long shelf-life of at least 2 months and the results showed good repeatability. The proposed method was successfully applied to the determination of the OPs in real fruit samples with satisfactory results.

  4. Innovative approach for the electrochemical detection of non-electroactive organophosphorus pesticides using oxime as electroactive probe.

    PubMed

    Dong, Jing; Hou, Juying; Jiang, Jianxia; Ai, Shiyun

    2015-07-23

    An innovative approach for sensitive and simple electrochemical detection of non-electroactive organophosphorus pesticides (OPs) was described in this report. The novel strategy emphasized the fabrication of an oxime-based sensor via attaching pralidoxime (PAM) on graphene quantum dots (GQDs) modified glassy carbon electrode. The introduction of GQDs significantly increased the effective electrode area, and then enlarged the immobilization quantity of PAM. Thus, the oxidation current of PAM was obviously increased. Relying on the nucleophilic substitution reaction between oxime and OPs, fenthion was detected using PAM as the electroactive probe. Under optimum conditions, the difference of oxidation current of PAM was proportional to fenthion concentration over the range from 1.0×10(-11)M to 5.0×10(-7)M with a detection limit of 6.8×10(-12)M (S/N=3). Moreover, the favorable detection performance in water and soil samples heralded the promising applications in on-site OPs detection.

  5. Ionic liquid-based vortex-assisted dispersive liquid-liquid microextraction of organophosphorus pesticides in apple and pear.

    PubMed

    Zhang, Lijin; Chen, Fang; Liu, Shaowen; Chen, Biyu; Pan, Canping

    2012-09-01

    An ionic liquid-based vortex-assisted dispersive liquid-liquid microextraction (DLLME) was developed for the analysis of trace amounts of six organophosphorus pesticides (OPPs) in apple and pear coupled with high-performance liquid chromatography. During the DLLME, the effect of some experimental factors including extraction solvent and its volume, dispersion solvent and its volume, vortex time, salt addition, and pH on the extraction procedure were investigated. Under the chosen extraction conditions, the analytes were enriched more than 300-fold and the limits of detections were greatly dropped to 0.061-0.73 μg/kg. The linearity relationship was observed in the range of 2-100 μg/kg with the correlation coefficients (R(2)) ranging from 0.9967 to 0.9983. The relative standard deviations varied from 2.3 to 5.7% (n = 6). Mean recovery values of the OPPs were in the range of 69.8-109.1% with a relative standard deviation lower than 7.0%. Based on these above, it could be concluded that 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)MIM][PF(6)]) was a good extraction solvent and the proposed [C(8)MIM][PF(6)]-based vortex-assisted DLLME method was suitable for the effective extraction of the OPPs in apple and pear.

  6. Tolerance of ARPE 19 cells to organophosphorus pesticide chlorpyrifos is limited to concentration and time of exposure.

    PubMed

    Gomathy, Narayanan; Sumantran, Venil N; Shabna, A; Sulochana, K N

    2015-01-01

    Age related macular degeneration is a blinding disease common in elder adults. The prevalence of age related macular degeneration has been found to be 1.8% in the Indian population. Organophosphates are widely used insecticides with well documented neurological effects, and the persistent nature of these compounds in the body results in long term health effects. Farmers exposed to organophosphorus pesticides in USA had an earlier onset of age related macular degeneration when compared to unexposed controls. A recent study found significant levels of an organophosphate, termed chlorpyrifos, in the blood samples of Indian farmers. Therefore, in understanding the link between age related macular degeneration and chlorpyrifos, the need for investigation is important. Our data show that ARPE-19 (retinal pigment epithelial cells) exhibit a cytoprotective response to chlorpyrifos as measured by viability, mitochondrial membrane potential, superoxide dismutase activity, and increased levels of glutathione peroxidase and reduced glutathione, after 24 h exposure to chlorpyrifos. However, this cytoprotective response was absent in ARPE-19 cells exposed to the same range of concentrations of chlorpyrifos for 48 h. These results have physiological significance, since HPLC analysis showed that effects of chlorpyrifos were mediated through its entry into ARPE-19 cells. HPLC analysis also showed that chlorpyrifos remained stable, as we recovered up to 80% of the chlorpyrifos added to 6 different ocular tissues.

  7. In-capillary derivatization and laser-induced fluorescence detection for the analysis of organophosphorus pesticides by micellar electrokinetic chromatography.

    PubMed

    Zhou, Lei; Luo, Zhi; Wang, Shumin; Hui, Yang; Hu, Zhide; Chen, Xingguo

    2007-05-18

    We developed a rapid and sensitive method using in-capillary derivatization and laser-induced fluorescence (LIF) detection for the fully automated analysis of organophosphorus pesticides (OPPs), including glufosinate, aminomethylphosphonic acid (AMPA) and glyphosate by micellar electrokinetic chromatography (MEKC). The potential of 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) as in-capillary derivatization reagent is described for the first time. The unique feature of this MEKC method is the capillary being used as a small reaction chamber. In in-capillary derivatization, the sample and reagent solutions were injected directly into the capillary by tandem mode, followed by an electrokinetic step to enhance the mixing efficiency of analytes and reagent plugs in accordance with their different electrophoretic mobilities. Standing a specified time for reaction, the derivatives were then immediately separated and determined. Careful optimization of the derivatization and separation conditions allowed the determination of glufosinate, AMPA and glyphosate with detection limits of 2.8, 3.6 and 32.2 ng/mL, respectively. These detection limits were comparable to those of 1.4, 1.9 and 23.8 ng/mL obtained from conventional pre-capillary derivatization. Furthermore, repeatability better than 0.40% for migration time and 3.4% for peak area, as well as shorter migration time, was obtained. The method was successfully applied to the analysis of spiked river water sample with satisfactory results.

  8. Enhanced degradation of five organophosphorus pesticides in skimmed milk by lactic acid bacteria and its potential relationship with phosphatase production.

    PubMed

    Zhang, Ying-Hua; Xu, Di; Liu, Jia-Qi; Zhao, Xin-Huai

    2014-12-01

    Skimmed milk spiked with five organophosphorus pesticides (OPPs), chlorpyrifos, diazinon, fenitrothion, malathion and methyl parathion, was fermented by ten lactic acid bacteria (LAB) and four strain combinations at 42°C for 24h. OPPs left in the samples at different times were extracted, purified, detected by gas chromatography and calculated for degradation rate constants, based on a first-order reaction model. OPPs degradation was enhanced by the inoculated LAB, resulting in 0.8-225.4% increase in the rate constants. Diazinon and methyl parathion were more stable whereas chlorpyrifos, fenitrothion and malathion were more labile. Lactobacillus brevis 1.0209 showed the strongest acceleration on OPPs degradation while strain combination could bring about a synergy between the strains of lower ability. Phosphatase production of the strains might be one of the key factors responsible for the enhanced OPPs degradation, as the detected phosphatase activities were positively correlated to the measured degradation rate constants of OPPs (r=0.636-0.970, P<0.05).

  9. Genome-Wide Gene Expression Analysis in Response to Organophosphorus Pesticide Chlorpyrifos and Diazinon in C. elegans

    PubMed Central

    Viñuela, Ana; Snoek, L. Basten; Riksen, Joost A. G.; Kammenga, Jan E.

    2010-01-01

    Organophosphorus pesticides (OPs) were originally designed to affect the nervous system by inhibiting the enzyme acetylcholinesterase, an important regulator of the neurotransmitter acetylcholine. Over the past years evidence is mounting that these compounds affect many other processes. Little is known, however, about gene expression responses against OPs in the nematode Caenorhabditis elegans. This is surprising because C. elegans is extensively used as a model species in toxicity studies. To address this question we performed a microarray study in C. elegans which was exposed for 72 hrs to two widely used Ops, chlorpyrifos and diazinon, and a low dose mixture of these two compounds. Our analysis revealed transcriptional responses related to detoxification, stress, innate immunity, and transport and metabolism of lipids in all treatments. We found that for both compounds as well as in the mixture, these processes were regulated by different gene transcripts. Our results illustrate intense, and unexpected crosstalk between gene pathways in response to chlorpyrifos and diazinon in C. elegans. PMID:20808445

  10. Application of solid-phase microextraction for the determination of organophosphorus pesticides in textiles by gas chromatography with mass spectrometry.

    PubMed

    Zhu, Fang; Ruan, Wenhong; He, Minheng; Zeng, Feng; Luan, Tiangang; Tong, Yexiang; Lu, Tongbu; Ouyang, Gangfeng

    2009-09-21

    A method based on solid-phase microextraction (SPME) and gas chromatography with mass spectrometry (GC/MS) for the determination of 18 organophosphorus pesticides (OPPs) in textiles is described. Commercially available SPME fibers, 100 microm PDMS and 85 microm PA, were compared and 85 microm PA exhibited better performance to the OPPs. Various parameters affecting SPME, including extraction and desorption time, extraction temperature, salinity and pH, were studied. The optimized conditions were: 35 min extraction at 25 degrees C, 5% NaSO4 content, pH 7.0, and 3.5 min desorption in GC injector port at 250 degrees C. The linear ranges of the SPME-GC/MS method were 0.1-500 microg L(-1) for most of the OPPs. The limits of detection (LODs) ranged from 0.01 microg L(-1) (for bromophos-ethyl) to 55 microg L(-1) (for azinphos-methyl) and the RSDs were between 0.66% and 9.22%. The optimized method was then used to analyze 18 OPPs in textile sample, and the determined recoveries were ranged from 76.7% to 126.8%. Moreover, the distribution coefficients of the OPPs between 85 microm PA fiber and simulative sweat solution (K(pa/s)) were determined. The determined K(pa/s) of the OPPs correlated well with their octanol-water partition coefficients (r=0.764 and 0.678) and water solubility (r=-0.892 and -0.863).

  11. Applied clinical pharmacology and public health in rural Asia--preventing deaths from organophosphorus pesticide and yellow oleander poisoning.

    PubMed

    Eddleston, Michael

    2013-05-01

    Self-poisoning with pesticides or plants is a major clinical problem in rural Asia, killing several hundred thousand people every year. Over the last 17 years, our clinical toxicology and pharmacology group has carried out clinical studies in the North Central Province of Sri Lanka to improve treatment and reduce deaths. Studies have looked at the effectiveness of anti-digoxin Fab in cardiac glycoside plant poisoning, multiple dose activated charcoal in all poisoning, and pralidoxime in moderate toxicity organophosphorus insecticide poisoning. More recently, using a Haddon matrix as a guide, we have started conducting public health and animal studies to find strategies that may work outside of the hospital. Based on the 2009 GSK Research in Clinical Pharmacology prize lecture, this review shows the evolution of the group's research from a clinical pharmacology approach to one that studies possible interventions at multiple levels, including the patient, the community and government legislation. © 2012 The Author. British Journal of Clinical Pharmacology © 2012 The British Pharmacological Society.

  12. A review of organochlorine pesticide residues in Swainson's hawk eggs

    USGS Publications Warehouse

    Henny, C.J.

    1985-01-01

    U. s. Fish and Wildlife Service research projects during the last 10 years in the Pacific Northwest resulted in the collecting of a sample egg from 35 Swainson's Hawk nests (Henny and Kaiser, 1979. Murrelet 60:2-5; Henny et al. 1984. Raptor Research 18:41-48). Pesticide residues, eggshell thickness, and reproductive success from these nests will be reviewed. In addition, egg residues from other published studies in the Pacific Northwest and elsewhere will be discussed.

  13. International Harmonization of Food Safety Assessment of Pesticide Residues.

    PubMed

    Ambrus, Árpád

    2016-01-13

    This paper summarizes the development of principles and methods applied within the program of the FAO/WHO Codex Alimentarius during the past 50 years for the safety assessment of pesticide residues in food and feed and establishing maximum residue limits (MRLs) to promote free international trade and assure the safety of consumers. The role of major international organizations in this process, the FAO capacity building activities, and some problematic areas that require special attention are briefly described.

  14. PESTICIDE SURFACE RESIDUE MEASUREMENTS BY A PRESS SAMPLER

    EPA Science Inventory

    Pesticides on household surfaces are a source of exposure to children. Accurate measurements of residues on surfaces are needed to determine amounts available for transfer to foods and other objects handled or eaten by a child. Wiping the surface with a solvent has been the acc...

  15. PESTICIDE SURFACE RESIDUE MEASUREMENTS BY A PRESS SAMPLER

    EPA Science Inventory

    Pesticides on household surfaces are a source of exposure to children. Accurate measurements of residues on surfaces are needed to determine amounts available for transfer to foods and other objects handled or eaten by a child. Wiping the surface with a solvent has been the acc...

  16. CHARACTERIZING PESTICIDE RESIDUE TRANSFER EFFICIENCIES USING FLUORESCENT TRACER IMAGING TECHNIQUES

    EPA Science Inventory

    To reduce the uncertainty associated with current estimates of children's exposure to pesticides by dermal contact and non-dietary ingestion, residue transfer data are required. Prior to conducting exhaustive studies, a screening study was conducted to identify the important pa...

  17. Sampling and sample processing in pesticide residue analysis

    USDA-ARS?s Scientific Manuscript database

    Proper sampling and sample processing in pesticide residue analysis of food and soil has always been essential to obtain accurate results, but the subject is becoming a greater concern as approximately 100 mg test portions are being analyzed with automated high-throughput analytical methods by agroc...

  18. 5th Latin American pesticide residue workshop (LAPRW 2015)

    USDA-ARS?s Scientific Manuscript database

    This invited editorial proceedings article introduces the 6 research papers published in the special topical collection for the 5th Latin American Pesticide Residue Workshop held in Santiago, Chile, May 10-13, 2015. The meeting was a great success with more than 50 talks, 140 posters, 21 vendors, a...

  19. CHARACTERIZING PESTICIDE RESIDUE TRANSFER EFFICIENCIES USING FLUORESCENT TRACER IMAGING TECHNIQUES

    EPA Science Inventory

    To reduce the uncertainty associated with current estimates of children's exposure to pesticides by dermal contact and non-dietary ingestion, residue transfer data are required. Prior to conducting exhaustive studies, a screening study was conducted to identify the important pa...

  20. The status of pesticide residues in the drinking water sources in Meiliangwan Bay, Taihu Lake of China.

    PubMed

    Na, Ta; Fang, Zhou; Zhanqi, Gao; Ming, Zhong; Cheng, Sun

    2006-12-01

    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 microECD 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.

  1. Responses of the iguanid lizard Anolis carolinensis to four organophosphorus pesticides

    USGS Publications Warehouse

    Hall, R.J.; Clark, D.R.

    1982-01-01

    Dose related mortality and cholinesterase effects of parathion, methyl parathion, azinphos-methyl and malathion on Anolis carolinensis were investigated. The comparative effects of the four compounds on fish, birds and mammals are well known, but the effects of organophosphates on reptiles have not been studied critically. Sensitivity and patterns of mortality from exposure to the pesticides resemble those of birds and mammals rather than those of other poikilothermic vertebrates. Possible symptoms of epinephrine accumulation were observed in exposed animals; this side effect is consistent with the known mechanisms of the pesticides. Our findings indicate that brain cholinesterase activity is related to dose, that 50% inhibition of cholinesterase is associated with death and that 40% inhibition indicates sublethal exposure. Anolis lizards are frequently exposed to pesticides in the field and they may be useful in monitoring the hazards posed to a variety of wildlife species.

  2. Pesticide residue analysis of a dietary ingredient by gas chromatography/selected-ion monitoring mass spectrometry using neutral alumina solid-phase extraction cleanup.

    PubMed

    Jeong, Mijeong Lee; Zahn, Michael; Trinh, Thao; Brooke, Fay A; Ma, Wenwen

    2008-01-01

    A sample cleanup procedure has been developed to remove coextractives that interfere with pesticide residue analysis of a dietary ingredient (Product B), an extract consisting of Scutellaria baicalensis and Acacia catechu. Samples were extracted using 1% acetic acid in acetonitrile, followed by solid-phase extraction and analysis by capillary gas chromatography with mass spectrometry in the selective-ion monitoring mode. Neutral alumina (alumina N) was found to be the most effective sorbent to remove coextractives from Product B; other materials that were tested but failed to remove interference were graphitized carbon black/primary-secondary amine (PSA), octadecylsilane (C18), Florisil, Oasis MCX, and strong anion exchange-PSA. The method was specifically developed for Product B, which was spiked with 41 organochlorine and organophosphorus pesticides, and resulted in the recovery of 80 to 120% at U.S. Pharmacopeia limits (0.06 to 4 microg/g) for the majority of the pesticides.

  3. Study on the effect of chain-length compatibility of mixed anionic-cationic surfactants on the cloud-point extraction of selected organophosphorus pesticides.

    PubMed

    Seebunrueng, Ketsarin; Santaladchaiyakit, Yanawath; Srijaranai, Supalax

    2012-09-01

    The chain-length compatibility of mixed anionic-cationic surfactants was investigated for the extraction of organophosphorus pesticides (OPPs). Cationic surfactants with different chain lengths (n = 12 and 16) were mixed with sodium dodecyl sulfate (SDS; n = 12) for the mixed anionic-cationic surfactants-based extraction. Six OPPs were studied including azinphos-methyl, parathion-methyl, fenitrothion, diazinon, chlorpyrifos, and prothiophos. Reversed-phase high-performance liquid chromatography was used for the determination of the studied OPPs. The extraction was performed using mixtures of SDS and cationic surfactants including dodecyltrimethyl ammonium bromide or dodecyltrimethylammonium bromide (DTAB; n = 12) and cetyltrimethyl ammonium bromide or cetyltrimethyl ammonium bromide (CTAB; n = 16). The parameters affecting the extraction efficiencies of two extraction systems were studied and discussed. The optimum condition for SDS-DTAB was 15 mmol L(-1) SDS and 1 mmol L(-1) DTAB in the presence of 15% (w/v) sodium chloride (NaCl). Meanwhile, the condition for SDS-CTAB was 10 mmol L(-1) SDS and 1.0 mmol L(-1) CTAB with 10% (w/v) NaCl. Under the optimum conditions, the extraction efficiency of SDS-DTAB (66-85%) was slightly higher than that of SDS-CTAB (61-82%). In addition, the SDS-DTAB system also gave greater enrichment factor than SDS-CTAB for all the studied OPPs. This result may be due to the compatibility of chain length between SDS and DTAB. The extraction using SDS-DTAB was successfully applied to determine OPPs in fruit samples (i.e., pomelo, apple, and pineapple). No contamination by the studied OPPs in samples was observed. Good accuracy with recoveries ranging from 77 to 105% was obtained. Low limits of detection were in the range of 0.003-0.01 mg kg(-1) which are below the MRLs established by EU-MRLs for the OPPs residues in fruit samples.

  4. 9 CFR 318.16 - Pesticide chemicals and other residues in products.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 9 Animals and Animal Products 2 2012-01-01 2012-01-01 false Pesticide chemicals and other residues... PREPARATION OF PRODUCTS General § 318.16 Pesticide chemicals and other residues in products. (a) Nonmeat ingredients. Residues of pesticide chemicals, food additives and color additives or other substances in or on...

  5. 9 CFR 318.16 - Pesticide chemicals and other residues in products.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 9 Animals and Animal Products 2 2011-01-01 2011-01-01 false Pesticide chemicals and other residues... PREPARATION OF PRODUCTS General § 318.16 Pesticide chemicals and other residues in products. (a) Nonmeat ingredients. Residues of pesticide chemicals, food additives and color additives or other substances in or on...

  6. 9 CFR 318.16 - Pesticide chemicals and other residues in products.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 2 2014-01-01 2014-01-01 false Pesticide chemicals and other residues... PREPARATION OF PRODUCTS General § 318.16 Pesticide chemicals and other residues in products. (a) Nonmeat ingredients. Residues of pesticide chemicals, food additives and color additives or other substances in or on...

  7. 9 CFR 318.16 - Pesticide chemicals and other residues in products.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 9 Animals and Animal Products 2 2013-01-01 2013-01-01 false Pesticide chemicals and other residues... PREPARATION OF PRODUCTS General § 318.16 Pesticide chemicals and other residues in products. (a) Nonmeat ingredients. Residues of pesticide chemicals, food additives and color additives or other substances in or on...

  8. 9 CFR 318.16 - Pesticide chemicals and other residues in products.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 9 Animals and Animal Products 2 2010-01-01 2010-01-01 false Pesticide chemicals and other residues... PREPARATION OF PRODUCTS General § 318.16 Pesticide chemicals and other residues in products. (a) Nonmeat ingredients. Residues of pesticide chemicals, food additives and color additives or other substances in or on...

  9. Age-related differences in acetylcholinesterase inhibition produced by organophosphorus and N-methyl carbamate pesticides

    EPA Science Inventory

    Introduction The concern that infants and children may be more susceptible to the toxic effects of chemicals, including pesticides, has received much attention in the scientific literature and the public media. Greater toxicity may be evident as long-term adverse outcomes, e.g.,...

  10. Age-related differences in acetylcholinesterase inhibition produced by organophosphorus and N-methyl carbamate pesticides

    EPA Science Inventory

    Introduction The concern that infants and children may be more susceptible to the toxic effects of chemicals, including pesticides, has received much attention in the scientific literature and the public media. Greater toxicity may be evident as long-term adverse outcomes, e.g.,...

  11. Glutathione S-transferase conjugation of organophosphorus pesticides yields S-phospho-, S-aryl-, and S-alkylglutathione derivatives.

    PubMed

    Fujioka, Kazutoshi; Casida, John E

    2007-08-01

    Pesticide detoxification is a central feature of selective toxicity and safety evaluation. Two of the principal enzymes involved are GSH S-transferases (GSTs) and cytochrome P450s acting alone and together. More than 100 pesticides are organophosphorus (OP) compounds, but with few exceptions, their GSH conjugates have not been directly observed in vitro or in vivo. The major insecticides chlorpyrifos (CP) and diazinon are of particular interest as multifunctional substrates with diverse metabolites, while ClP(S)(OEt) 2 and the cotton defoliant tribufos are possible precursors of phosphorylated GSH conjugates. Formation of GSH conjugates by GST with GSH was studied in vitro with and without metabolic activation by human liver microsomes or P450 3A4 with NADPH. Metabolites were analyzed by liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS). Five GSH conjugates were identified from CP and chlorpyrifos oxon (CPO), i.e., GSCP and GSCPO in which the 6-chloro substituent of CP and CPO, respectively, is displaced by GSH; S-(3,5,6-trichloropyridin-2-yl)glutathione; S-(3,5-dichloro-6-hydroxypyridin-2-yl)glutathione; and S-ethylglutathione. GST of a human liver microsomal preparation but not P450 3A4 with GSH metabolized CP to GSCP. With GST and GSH, diazinon and diazoxon gave S-(2-isopropyl-4-methylpyrimidin-6-yl)glutathione and ClP(S)(OEt) 2 yielded GSP(S)(OEt) 2. With microsomes, NADPH, GST, and GSH tribufos gave GSP(O)(SBu) 2. The liver of intraperitoneally treated mice contained GSCP from CP, GSP(S)(OEt) 2 from ClP(S)(OEt) 2, and GSP(O)(SBu) 2 from tribufos. GSP(S)(OEt) 2 and GSP(O)(SBu) 2 are the first S-phosphoglutathione metabolites observed in vitro and in vivo directly by LC-ESI-MS. Nine other OP pesticides gave only O-dealkylation in the GST/GSH system. GST-catalyzed metabolism joins P450s and hydrolases as important contributors to OP detoxification.

  12. Exposure to pesticides residues from consumption of Italian blood oranges.

    PubMed

    Fallico, B; D'Urso, M G; Chiappara, E

    2009-07-01

    This paper reports the results of a 5-year study to evaluate pesticide levels, derived from orchard activities, on Italy's most common orange cultivar (Citrus sinensis, L. Osbeck, cv. Tarocco). Using a Bayesian approach, the study allowed both the qualitative (number) and quantitative distributions (amount) of pesticides to be determined with its own probability value. Multi-residue analyses of 460 samples highlighted the presence of ethyl and methyl chlorpyrifos, dicofol, etofenprox, fenazaquin, fenitrothion, imazalil, malathion and metalaxil-m. A total of 30.5% of samples contained just one pesticide, 2.16% two pesticides and 0.65% of samples had three pesticides present simultaneously. The most common residue was ethyl chlorpyrifos followed by methyl chlorpyrifos. Estimated daily intake (EDI) values for ethyl and methyl chlorpyrifos, as well as the distance from the safety level (non-observed adverse effect level, NOAEL), were calculated. The risk was differentiated (1) to take account of the period of actual citrus consumption (180 days) and (2) to discriminate the risk derived from eating oranges containing a certain level of chlorpyrifos from unspecified pesticides. The most likely EDI values for ethyl chlorpyrifos derived from Italian blood orange consumption are 0.01 and 0.006 mg/day calculated for 180 and 365 days, respectively. Considering the probability of the occurrence of ethyl chlorpyrifos, these EDI values are reduced to 2.6 x 10(-3) and 1.3 x 10(-3) mg/day, respectively. For methyl chlorpyrifos, the most likely EDI values are 0.09 and 0.04 mg/day, respectively; considering the probability of its occurrence, the EDI values decrease to 6.7 x 10(-3) and 3.4 x 10(-3) mg/day, respectively. The results confirmed that levels of pesticides in Italian Tarocco oranges derived from a known controlled chain of production are safe.

  13. Mechanism and kinetic properties for OH-initiated atmospheric degradation of the organophosphorus pesticide diazinon

    NASA Astrophysics Data System (ADS)

    Zhou, Qin; Sun, Xiaoyan; Gao, Rui; Hu, Jingtian

    2011-06-01

    Diazinon is a member of the organophosphorus class of insecticides. It has been regarded as an important atmospheric pollutant because of its high detection-frequency in the air and potential adverse effects on humans and wildlife. In this paper, the reaction mechanism and possible degradation products for the OH-initiated atmospheric degradation of diazinon were investigated and the rate constants of crucial elementary steps over the temperature range of 180-370 K were predicted. Present results show that OH addition to C4 atom in the pyrimidyl ring, H abstraction from the -CH- moiety as well as OH addition to P atom are the dominant pathways for the reaction of diazinon with OH radicals. The dominant degradation products are diazoxon, SO 2, P3, CH 3CHO, P4, CH 3CO, P14 as well as CH 3CHCH 3. This work provides a comprehensive investigation of the OH-initiated atmospheric degradation of diazinon and should help to clarify its potential risk to non-targets.

  14. Consumption of fruits and vegetables and probabilistic assessment of the cumulative acute exposure to organophosphorus and carbamate pesticides of schoolchildren in Slovenia.

    PubMed

    Blaznik, Urška; Yngve, Agneta; Eržen, Ivan; Hlastan Ribič, Cirila

    2016-02-01

    Adequate consumption of fruits and vegetables is a part of recommendations for a healthy diet. The aim of the present study was to assess acute cumulative dietary exposure to organophosphorus and carbamate pesticides via fruit and vegetable consumption by the population of schoolchildren aged 11-12 years and the level of risk for their health. Cumulative probabilistic risk assessment methodology with the index compound approach was applied. Slovenia, primary schools. Schoolchildren (n 1145) from thirty-one primary schools in Slovenia. Children were part of the PRO GREENS study 2009/10 which assessed 11-year-olds' consumption of fruit and vegetables in ten European countries. The cumulative acute exposure amounted to 8.3 (95% CI 7.7, 10.6) % of the acute reference dose (ARfD) for acephate as index compound (100 µg/kg body weight per d) at the 99.9th percentile for daily intake and to 4.5 (95% CI 3.5, 4.7) % of the ARfD at the 99.9th percentile for intakes during school time and at lunch. Apples, bananas, oranges and lettuce contributed most to the total acute pesticides intake. The estimations showed that acute dietary exposure to organophosphorus and carbamate pesticides is not a health concern for schoolchildren with the assessed dietary patterns of fruit and vegetable consumption.

  15. Integrating biotinylated polyalkylthiophene thin films with biological macromolecules: biosensing organophosphorus pesticides and metal ions with surface immobilized alkaline phosphatase utilizing chemiluminescence measurements

    NASA Astrophysics Data System (ADS)

    Pande, Rajiv; Kamtekar, S.; Ayyagari, Madhu S. R.; Marx, Kenneth A.; Kumar, Jayant; Tripathy, Sukant K.; Kaplan, David L.

    1995-05-01

    We describe a methodology for immobilizing the enzyme alkaline phosphatase onto a glass surface using a novel biotinylated copolymer poly (3-undecylthiophene-co-3- thiophenecarboxaldehyde) 6-biotinamido hexanohydrazide attached hydrophobically to silanized glass. The biotin-streptavidin protein interaction is used to carry out this immobilization. Alkaline phosphatase catalyzes the dephosphorylation of a class of macrocyclic compounds: including CSPD {chloro 3-[4-methoxy spiro(1,2 dioxetane-3-2-trichloro-(3.3.1.1)-decan]-4 yl}phenyl phosphate to a product species which emits energy by chemiluminescence. We can detect this chemiluminescence signal with a photomultiplier tube for both enzymatic catalysis in solution and the surface immobilized enzyme (streptavidin conjugate). This enzyme is inhibited by the organophosphorus class of pesticides as well as nerve agents. The enzyme is also inhibited by Be(II), Bi(III) as well as excess Zn(II), while the apoenzyme is reactivated by Zn(II). We demonstrate in this study that two representative organophosphorus pesticides inhibit the enzymatic production of chemiluminescent products. This is true for the enzyme conjugate both free in solution and immobilized. We can detect pesticides down to about 50 ppb for the enzyme in solution and 500 ppb for surface immobilized enzyme in a 100 (mu) l capillary. Detection of Zn(II) by apoenzyme reactivation occurs down to 3 ppb. Be(II) and Bi(III) are detected by inhibition down to 1 ppm.

  16. Ultrapreconcentration and determination of organophosphorus pesticides in water by solid-phase extraction combined with dispersive liquid-liquid microextraction and high-performance liquid chromatography.

    PubMed

    Chen, Junhua; Zhou, Guangming; Deng, Yongli; Cheng, Hongmei; Shen, Jie; Gao, Yi; Peng, Guilong

    2016-01-01

    Solid-phase extraction coupled with dispersive liquid-liquid microextraction was developed as an ultra-preconcentration method for the determination of four organophosphorus pesticides (isocarbophos, parathion-methyl, triazophos and fenitrothion) in water samples. The analytes considered in this study were rapidly extracted and concentrated from large volumes of aqueous solutions (100 mL) by solid-phase extraction coupled with dispersive liquid-liquid microextraction and then analyzed using high performance liquid chromatography. Experimental variables including type and volume of elution solvent, volume and flow rate of sample solution, salt concentration, type and volume of extraction solvent and sample solution pH were investigated for the solid-phase extraction coupled with dispersive liquid-liquid microextraction with these analytes, and the best results were obtained using methanol as eluent and ethylene chloride as extraction solvent. Under the optimal conditions, an exhaustive extraction for four analytes (recoveries >86.9%) and high enrichment factors were attained. The limits of detection were between 0.021 and 0.15 μg/L. The relative standard deviations for 0.5 μg/L of the pesticides in water were in the range of 1.9-6.8% (n = 5). The proposed strategy offered the advantages of simple operation, high enrichment factor and sensitivity and was successfully applied to the determination of four organophosphorus pesticides in water samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Interrelation of Glycemic Status and Neuropsychiatric Disturbances in Farmers with Organophosphorus Pesticide Toxicity

    PubMed Central

    Jamal, Farrukh; Haque, Quazi S.; Singh, Sangram

    2016-01-01

    Background: Diverse group of agro-chemicals are indiscriminately sprayed by the farmers for pest control to enhance crop yield. About 25 million agricultural workers in the developing world suffer from at least one episode of poisoning each year, mainly by anticholinesterase- like organophosphates (OPs). Objective: The present study was aimed to establish the OP toxicity in 187 occupationally exposed pesticide sprayers of mango plantation in rural Malihabad, Lucknow, in terms of neuro-cognitive impairment, mental health status, clinical symptoms, diabetes, and hematological factors. Method: The exposed group was compared to 187 pesticides-unexposed normal healthy persons engaged in normal usual agricultural work (age, sex and education corresponding to age group of selected subject group) from Rural Malihabad, Lucknow (India). Neuro-cognitive impairment was measured using the Subjective Neurocognition Inventory and mental health status using the General Health questionnaire-28. The subjects were also tested for biochemical and enzymatic parameters. Results: The exposed farmers showed alterations in enzymatic and clinical parameters. While the rates of anxiety / insomnia and severe depression were also significantly higher in the pesticide sprayers, disorders affecting psychomotor speed, selective attention, divided attention, verbal memory, nonverbal memory, prospective memory, spatial functioning, and initiative/energy were all lower in the sprayers. Pesticide sprayers showed a number of clinical symptoms like eczema, saliva secretion, fatigue, headache, sweating, abdominal pain, nausea, superior distal muscle weakness, inferior distal muscle weakness, hand tingling and etc. which all significantly correlated with the number of working years. Conclusion: These findings suggested that farmers who work with OPs are prone to neuro-psychological disorders and diabetes. PMID:27688820

  18. Parameters affecting the decay of some organophosphorus pesticides: a study by high-performance liquid chromatography.

    PubMed

    Kaur, I; Mathur, R P; Tandon, S N

    1997-01-01

    An HPLC procedure has been developed to follow the decay of malathion and methylparathion under control conditions using an mu-Bondapak C18 column with a mixture of acetonitrile and water to mobile phase and an ultraviolet detector for detection. Studies have been conducted to monitor their degradation in water and soil at different temperatures, pH and organic content. The results show that the persistence of the pesticides decreases with increase in temperature, pH and organic content.

  19. Interrelation of Glycemic Status and Neuropsychiatric Disturbances in Farmers with Organophosphorus Pesticide Toxicity.

    PubMed

    Jamal, Farrukh; Haque, Quazi S; Singh, Sangram

    2016-01-01

    Diverse group of agro-chemicals are indiscriminately sprayed by the farmers for pest control to enhance crop yield. About 25 million agricultural workers in the developing world suffer from at least one episode of poisoning each year, mainly by anticholinesterase- like organophosphates (OPs). The present study was aimed to establish the OP toxicity in 187 occupationally exposed pesticide sprayers of mango plantation in rural Malihabad, Lucknow, in terms of neuro-cognitive impairment, mental health status, clinical symptoms, diabetes, and hematological factors. The exposed group was compared to 187 pesticides-unexposed normal healthy persons engaged in normal usual agricultural work (age, sex and education corresponding to age group of selected subject group) from Rural Malihabad, Lucknow (India). Neuro-cognitive impairment was measured using the Subjective Neurocognition Inventory and mental health status using the General Health questionnaire-28. The subjects were also tested for biochemical and enzymatic parameters. The exposed farmers showed alterations in enzymatic and clinical parameters. While the rates of anxiety / insomnia and severe depression were also significantly higher in the pesticide sprayers, disorders affecting psychomotor speed, selective attention, divided attention, verbal memory, nonverbal memory, prospective memory, spatial functioning, and initiative/energy were all lower in the sprayers. Pesticide sprayers showed a number of clinical symptoms like eczema, saliva secretion, fatigue, headache, sweating, abdominal pain, nausea, superior distal muscle weakness, inferior distal muscle weakness, hand tingling and etc. which all significantly correlated with the number of working years. These findings suggested that farmers who work with OPs are prone to neuro-psychological disorders and diabetes.

  20. Bioenergy residues as novel sorbents to clean up pesticide pollution

    NASA Astrophysics Data System (ADS)

    Mukherjee, Santanu

    2016-04-01

    Worldwide, water contamination from agricultural use of pesticides has received increasing attention within the last decades. In general, sources of pesticide water pollution are categorized into diffuse (stemming from treated fields) and point sources (stemming from farmyards and spillages). Research has demonstrated that 40 to 90% of surface water pesticide contamination is due to point source pollution. To reduce point pollution from farm yards, where the spray equipment is washed, biobed or biofilter systems are used to treat the washing water. The organic material usually used in these systems is often not environmentally sustainable (e.g. peat) and incorporated organic material such as straw leads to a highly heterogeneous water flow, with negative effects on the retention and degradation behavior of the pesticides. Therefore, the objective of this study was to assess the suitability of alternative materials based on bioenergy residues (biochar and digestate) for use in biofilters. To this aim the sorption-desorption potential of three contrasting pesticides (bentazone, boscalid, and pyrimethanil) on mixtures of soil with digestate and/or biochar were investigated in laboratory batch equilibrium experiments. The results indicate that the mixture of digestate and biochar increased pesticide sorption potential, whereby in all cases, the Kd des / Kf des values were lower than the Kd ads / Kf ads values indicating that the retention of the pesticides was weak. Thus, as Kf des were lower than the Kf ads values and H values were below 1, it can be concluded that the biomixtures presented negative desorption (higher hysteresis) in those cases. A higher Kd (>78 L kg-1), Kf (>400 μM1-1/nf L1/nfkg-1) and KL (>40 L kg-1) was obtained for all pesticides for the digestate and biochar based mixtures, which had a higher organic matter content. However, lower sorption of the pesticides was observed in blank soil compared to the other biomixtures, which was attributed to the

  1. Comparison of questionnaire-based estimation of pesticide residue intake from fruits and vegetables with urinary concentrations of pesticide biomarkers.

    PubMed

    Chiu, Yu-Han; Williams, Paige L; Mínguez-Alarcón, Lidia; Gillman, Matthew; Sun, Qi; Ospina, Maria; Calafat, Antonia M; Hauser, Russ; Chavarro, Jorge E

    2017-09-20

    We developed a pesticide residue burden score (PRBS) based on a food frequency questionnaire and surveillance data on food pesticide residues to characterize dietary exposure over the past year. In the present study, we evaluated the association of the PRBS with urinary concentrations of pesticide biomarkers. Fruit and vegetable (FV) intake was classified as having high (PRBS≥4) or low (PRBS<4) pesticide residues for 90 men from the EARTH study. Two urine samples per man were analyzed for seven biomarkers of organophosphate and pyrethroid insecticides, and the herbicide 2,4-dichlorophenoxyacetic acid. We used generalized estimating equations to analyze the association of the PRBS with urinary concentrations of pesticide biomarkers. Urinary concentrations of pesticide biomarkers were positively related to high pesticide FV intake but inversely related to low pesticide FV intake. The molar sum of urinary concentrations of pesticide biomarkers was 21% (95% confidence interval (CI): 2%, 44%) higher for each one serving/day increase in high pesticide FV intake, and 10% (95% CI: 1%, 18%) lower for each one serving/day increase in low pesticide FV intake. Furthermore, intake of high pesticide FVs positively related to most individual urinary biomarkers. Our findings support the usefulness of the PRBS approach to characterize dietary exposure to select pesticides.Journal of Exposure Science and Environmental Epidemiology advance online publication, 20 September 2017; doi:10.1038/jes.2017.22.

  2. Organochlorine pesticide residues in cow's milk and butter in Mexico.

    PubMed

    Waliszewski, S M; Pardío, V T; Waliszewski, K N; Chantiri, J N; Aguirre, A A; Infanzón, R M; Rivera, J

    1997-12-03

    This monitoring study of 355 samples of cow's milk collected from the central region of Veracruz state and 448 samples of national butter brands was conducted to determine the contamination levels of organochlorine pesticides. The results obtained for mean HCH levels were 0.094 and 0.093 mg/kg on fat basis in cow's milk and butter samples, respectively. The mean DDT levels were 0.159 and 0.049 mg/kg, respectively. In relation to cow's milk, the total HCH levels in Veracruz state were higher but total DDT levels were comparable to those reported in other countries. On the other hand, organochlorine levels detected in national brand butter samples were lower than those found in other countries, where these pesticides are still used in sanitary actions. These results confirmed that dairy products in Mexico presented organochlorine pesticide residues (owing to their use in sanitary actions) indicating a human exposure through these food products.

  3. Organochlorine pesticides residue in lakes of Khorezm, Uzbekistan

    USGS Publications Warehouse

    Rosen, Michael R.; Nishonov, Bakhriddin; Fayzieva, Dilorom; Saito, L.; Lamers, J.

    2009-01-01

    The Khorezm province in northwest Uzbekistan is a productive agricultural area within the Aral Sea Basin that produces cotton, rice and wheat. Various organochlorine pesticides were widely used for cotton production before Uzbekistan's independence in 1991. In Khorezm, small lakes have formed in natural depressions that receive inputs mostly from agricultural runoff. Samples from lake waters and sediments, as well as water from the Amu Darya River (which is the source of most of the lake water) have been analyzed to study variations in the concentrations of organochlorine pesticides residues during the year. Low concentrations of DDT, DDD, DDE, a-HCH and y-HCH compounds were found in water and sediment samples. The concentration of persistent organochlorine pesticides (DDT and HCH) in water and sediment is much lower than the maximum permissible concentrations that exist for water and soil. According to these preliminary results, the investigated lakes in Khorezm appear to be suitable for recreation or for aquaculture.

  4. DRY–WET CYCLES INCREASE PESTICIDE RESIDUE RELEASE FROM SOIL

    PubMed Central

    Jablonowski, Nicolai David; Linden, Andreas; Köppchen, Stephan; Thiele, Björn; Hofmann, Diana; Burauel, Peter

    2012-01-01

    Soil drying and rewetting may alter the release and availability of aged pesticide residues in soils. A laboratory experiment was conducted to evaluate the influence of soil drying and wetting on the release of pesticide residues. Soil containing environmentally long-term aged (9–17 years) 14C-labeled residues of the herbicides ethidimuron (ETD) and methabenzthiazuron (MBT) and the fungicide anilazine (ANI) showed a significantly higher release of 14C activity in water extracts of previously dried soil compared to constantly moistened soil throughout all samples (ETD: p < 0.1, MBT and ANI: p < 0.01). The extracted 14C activity accounted for 44% (ETD), 15% (MBT), and 20% (ANI) of total residual 14C activity in the samples after 20 successive dry–wet cycles, in contrast to 15% (ETD), 5% (MBT), and 6% (ANI) in extracts of constantly moistened soils. In the dry–wet soils, the dissolved organic carbon (DOC) content correlated with the measured 14C activity in the aqueous liquids and indicated a potential association of DOC with the pesticide molecules. Liquid chromatography MS/MS analyses of the water extracts of dry–wet soils revealed ETD and MBT in detectable amounts, accounting for 1.83 and 0.01%, respectively, of total applied water-extractable parent compound per soil layer. These findings demonstrate a potential remobilization of environmentally aged pesticide residue fractions from soils due to abiotic stresses such as wet–dry cycles. Environ. Toxicol. Chem. 2012; 31: 1941–1947. © 2012 SETAC PMID:22782855

  5. Novel Double-Potential Electrochemiluminescence Ratiometric Strategy in Enzyme-Based Inhibition Biosensing for Sensitive Detection of Organophosphorus Pesticides.

    PubMed

    Chen, Hongmei; Zhang, Han; Yuan, Ruo; Chen, Shihong

    2017-03-07

    Generally, electrochemiluminescence (ECL) ratiometric assays were based on the energy transfer (ET) between an emitter and a metal nanomaterial or between two different emitters. The choice of suitable energy donor-acceptor pair and the distance dependence of ET would greatly limit the practical application of ratiometric assays. This work explored a novel double-potential ECL ratiometry without the ET for organophosphorus pesticides (OPs) analysis, in which, reduced graphene oxide-CdTe quantum dots (RGO-CdTe QDs) and carboxyl-conjugated polymer dots (PFO dots) were chosen as cathodic and anodic ECL emitters, and the reactant (dissolved O2) and the product (H2O2) in enzymatic reactions served as their coreactants, respectively. With the occurrence of the enzymatic reactions induced by the acetylcholinesterase (AChE) and choline oxidase (ChOx), the cathodic ECL signal from RGO-CdTe QDs was at "signal off" state due to the consumption of dissolved O2. Meanwhile, the anodic ECL signal from PFO dots was at "signal on" state due to the in situ generation of H2O2. In the presence of OPs, the cathodic ECL signal would increase while the anodic ECL signal would decline correspondingly due to the inhibition of OPs on the activity of AChE. Using the reactant and the product in enzymatic reactions as the coreactants of two different ECL emitters, we conveniently achieved the opposite change trend in two ECL signals for the ratiometric detection of OPs, which exhibited a greatly improved accuracy, reliability and sensitivity, thus, showing a great attraction for developing ECL ratiometric systems for the bioanalysis.

  6. An integrated probabilistic framework for cumulative risk assessment of common mechanism chemicals in food: an example with organophosphorus pesticides.

    PubMed

    Bosgra, Sieto; van der Voet, Hilko; Boon, Polly E; Slob, Wout

    2009-07-01

    This paper presents a framework for integrated probabilistic risk assessment of chemicals in the diet which accounts for the possibility of cumulative exposure to chemicals with a common mechanism of action. Variability between individuals in the population with respect to food consumption, concentrations of chemicals in the consumed foods, food processing habits and sensitivity towards the chemicals is addressed by Monte Carlo simulations. A large number of individuals are simulated, for which the individual exposure (iEXP), the individual critical effect dose (iCED) and the ratio between these values (the individual margin of exposure, iMoE) are calculated by drawing random values for all variable parameters from databases or specified distributions. This results in a population distribution of the iMoE, and the fraction of this distribution below 1 indicates the fraction of the population that may be at risk. Uncertainty in the assessment is treated as a separate dimension by repeating the Monte Carlo simulations many times, each time drawing random values for all uncertain parameters. In this framework, the cumulative exposure to common mechanism chemicals is addressed by incorporation of the relative potency factor (RPF) approach. The framework is demonstrated by the cumulative risk assessment of organophosphorus pesticides (OPs). By going through this example, the various choices and assumptions underlying the cumulative risk assessment are made explicit. The problems faced and the solutions chosen may be more generic than the present example with OPs. This demonstration may help to familiarize risk assessors and risk managers with the somewhat more complex output of probabilistic risk assessment.

  7. Sublethal genotoxicity and cell alterations by organophosphorus pesticides in MCF-7 cells: implications for environmentally relevant concentrations.

    PubMed

    Ukpebor, Justina; Llabjani, Valon; Martin, Francis L; Halsall, Crispin J

    2011-03-01

    Organophosphorus pesticide (OPP) toxicity is believed to be mediated through inhibition of acetylcholinesterase (AChE). Given their widespread distribution in aquatic systems and their ability to undergo chemical transformation, their environmental impacts at sublethal concentrations in nontarget organisms have become an important question. We conducted a number of mammalian-cell genotoxic and gene expression assays and examined cellular biochemical changes that followed low-dose exposure of MCF-7 cells to fenitrothion, diazinon, and the aqueous degradate of diazinon, 2-isopropyl-6-methyl-4-pyrimidinol (IMP). After exposure to the OPPs at low concentrations (10(-12) M to 10(-8) M), greater than twofold elevations in micronucleus formation were noted in MCF-7 cell cultures that went on to exhibit greater than 75% clonogenic survival; these levels of chromosomal damage were comparable to those induced by 10(-6) M benzo[a]pyrene, a known genotoxic agent. At this low concentration range, a fenitrothion-induced twofold elevation in B-cell leukemia/lymphoma-2 (BCL-2) and cytochrome P450 isoenzyme (CYP1A1) gene expressions was observed. Principal component analysis-linear discriminant analysis (PCA-LDA) of derived infrared (IR) spectra of vehicle control (nonexposed) and OPP-exposed cells highlighted that both fenitrothion and diazinon induced marked biochemical alterations in the lipid, protein, and DNA/RNA absorbance regions. Our findings demonstrate that the two OPP parent chemicals and IMP degradate can mediate a number of toxic effects or cellular alterations at very low concentrations. These are independent of just selective inhibition of AChE, with potential consequences for nontarget organisms exposed at environmentally relevant concentrations. Further assays on relevant aquatic organism cell lines are now recommended to understand the mechanistic low-dose toxicity of these chemicals present in aquatic systems. Copyright © 2011 SETAC.

  8. Biodegradation and bioremediation potential of diazinon-degrading Serratia marcescens to remove other organophosphorus pesticides from soils.

    PubMed

    Cycoń, Mariusz; Żmijowska, Agnieszka; Wójcik, Marcin; Piotrowska-Seget, Zofia

    2013-03-15

    The ability of diazinon-degrading Serratia marcescens to remove organophosphorus pesticides (OPPs), i.e. chlorpyrifos (CP), fenitrothion (FT), and parathion (PT) was studied in a mineral salt medium (MSM) and in three soils of different characteristics. This strain was capable of using all insecticides at concentration of 50 mg/l as the only carbon source when grown in MSM, and 58.9%, 70.5%, and 82.5% of the initial dosage of CP, FT, and PT, respectively was degraded within 14 days. The biodegradation experiment showed that autochthonous microflora in all soils was characterized by a degradation potential of all tested OPPs; however, the initial lag phases for degradation of CP and FT, especially in sandy soil, were observed. During the 42-day experiment, 45.3%, 61.4% and 72.5% of the initial dose of CP, FT, and PT, respectively, was removed in sandy soil whereas the degradation of CP, FT, and PT in the same period, in sandy loam and silty soils reached 61.4%, 79.7% and 64.2%, and 68.9%, 81.0% and 63.6%, respectively. S. marcescens introduced into sterile soils showed a higher degradation potential (5-13%) for OPPs removal than those observed in non-sterile soil with naturally occurring attenuation. Inoculation of non-sterile soils with S. marcescens enhanced the disappearance rates of all insecticides, and DT50 for CP, FT, and PT was reduced by 20.7, 11.3 and 13.0 days, and 11.9, 7.0 and 8.1 days, and 9.7, 14.5 and 12.6 days in sandy, sandy loam, and silty soils, respectively, in comparison with non-sterile soils with only indigenous microflora. This ability of S. marcescens makes it a suitable strain for bioremediation of soils contaminated with OPPs.

  9. Polyacrylic acid-coated cerium oxide nanoparticles: An oxidase mimic applied for colorimetric assay to organophosphorus pesticides.

    PubMed

    Zhang, Shi-Xiang; Xue, Shi-Fan; Deng, Jingjing; Zhang, Min; Shi, Guoyue; Zhou, Tianshu

    2016-11-15

    It is important and urgent to develop reliable and highly sensitive methods that can provide on-site and rapid detection of extensively used organophosphorus pesticides (OPs) for their neurotoxicity. In this study, we developed a novel colorimetric assay for the detection of OPs based on polyacrylic acid-coated cerium oxide nanoparticles (PAA-CeO2) as an oxidase mimic and OPs as inhibitors to suppress the activity of acetylcholinesterase (AChE). Firstly, highly dispersed PAA-CeO2 was prepared in aqueous solution, which could catalyze the oxidation of TMB to produce a color reaction from colorless to blue. And the enzyme of AChE was used to catalyze the substrate of acetylthiocholine (ATCh) to produce thiocholine (TCh). As a thiol-containing compound with reducibility, TCh can decrease the oxidation of TMB catalyzed by PAA-CeO2. Upon incubated with OPs, the enzymatic activity of AChE was inhibited to produce less TCh, resulting in more TMB catalytically oxidized by PAA-CeO2 to show an increasing blue color. The two representative OPs, dichlorvos and methyl-paraoxon, were tested using our proposed assay. The novel assay showed notable color change in a concentration-dependent manner, and as low as 8.62 ppb dichlorvos and 26.73 ppb methyl-paraoxon can be readily detected. Therefore, taking advantage of such oxidase-like activity of PAA-CeO2, our proposed colorimetric assay can potentially be a screening tool for the precise and rapid evaluation of the neurotoxicity of a wealth of OPs.

  10. Organophosphorus pesticide and ester analysis by using comprehensive two-dimensional gas chromatography with flame photometric detection.

    PubMed

    Liu, Xiangping; Li, Dengkun; Li, Jiequan; Rose, Gavin; Marriott, Philip J

    2013-12-15

    Thirty-seven phosphorus (P)-containing compounds comprising organophosphorus pesticides and organophosphate esters were analyzed by using comprehensive two-dimensional gas chromatography with flame photometric detection in P mode (GC × GC-FPD(P)), with a non-polar/moderately polar column set. A suitable modulation temperature and period was chosen based on experimental observation. A number of co-eluting peak pairs on the (1)D column were well separated in 2D space. Excellent FPD(P) detection selectivity, responding to compounds containing the P atom, produces clear 2D GC × GC plots with little interference from complex hydrocarbon matrices. Limits of detection (LOD) were within the range of 0.0021-0.048 μmol L(-1), and linear calibration correlation coefficients (R(2)) for all 37 P-compounds were at least 0.998. The P-compounds were spiked in 2% diesel and good reproducibility for their response areas and retention times was obtained. Spiked recoveries were 88%-157% for 5 μg L(-1) and 80%-138% for 10 μg L(-1) spiked levels. Both (1)tR and (2)tR shifts were noted when the content of diesel was in excess of 5% in the matrix. Soil samples were analyzed by using the developed method; some P-compounds were positively detected. In general, this study shows that GC × GC-FPD(P) is an accurate, sensitive and simple method for P-compound analysis in complicated environmental samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Fast agitated directly suspended droplet microextraction technique for the rapid analysis of eighteen organophosphorus pesticides in human blood.

    PubMed

    Kumari, Rupender; Patel, Devendra K; Panchal, Smita; Jha, Rakesh R; Satyanarayana, G N V; Asati, Ankita; Ansari, Nasreen G; Pathak, Manoj K; Kesavachandran, C; Murthy, Ramesh C

    2015-01-16

    A new sample preparation technique named as fast agitated directly suspended droplet microextraction (FA-DSDME) was proposed as an improved version of directly suspended droplet microextraction (DSDME) for the extraction and pre-concentration of wide-range organophosphorus pesticides (OPPs) from human blood prior to liquid chromatography tandem mass spectrometric (LC-MS/MS) analysis. In this method, instead of protecting the unwanted rupturing of extraction droplet (organic solvent), it was deliberately splintered into fine droplets by providing automated high-speed agitation to the biphasic extraction system (extraction solvent and sample solution). Fine organic droplets were then recollected into one, not by using a centrifuge machine but just by giving a very slow stirring to the bottom of the extraction system. The present method has surmounted the problem of prolonged extraction time associated with old DSDME. Under optimum extraction conditions, the method showed good sensitivity with low detection limits ranging from 0.0009 to 0.122μgL(-1). Mean recoveries were achieved in the range of 86-109% at three levels of spiking concentration (low, middle and high) from linearity range of individual analyte. Intra-day and inter-day precisions were ≤4.68 and ≤9.57 (%RSD) respectively. Enrichment factor (EF) for each analyte varied from 30 to 132 which prove the ability of this technique to pre-concentrate the extracted analytes up to a good extent. The sample matrices have shown an insignificant influence on method's sensitivity. The proposed method may find immense use in epidemiological, toxicological, regulatory and forensic laboratories. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Pesticide residue in water--a challenging task in India.

    PubMed

    Agarwal, Akriti; Prajapati, Rajmani; Singh, Om Pal; Raza, S K; Thakur, L K

    2015-02-01

    Modern agriculture practices reveal an increase in use of pesticides to meet the food demand of increasing population which results in contamination of the environment. In India, crop production increased to 100 %, but the cropping area has increased marginally by 20 %. Pesticides have played a major role in achieving the maximum crop production but maximum usage and accumulation of pesticide residues is highly detrimental to aquatic and other ecosystem. Pesticide residues in drinking water have become a major challenge over the last few years. It has been monitored in public water supply resources in National capital territory, i.e., Delhi. Organochlorine pesticides (OCPs), mainly isomers of hexachlorohexane (HCH), dichloro-diphenyl-trichloroethane (DDT), endosulphan, endrin, aldrin, dieldrin, and heptachlore, were identified from potable water samples. Results suggested that continuous consumption of contaminated water can pose severe health threats to local residents of this area. Central Pollution Control Board (CPCB), Delhi, had found α and β isomers of endosulphan residues in the Yamuna river. High concentrations of γ-HCH (0.259 μg/l) and malathion (2.618 μg/l) were detected in the surface water samples collected from the river Ganga in Kanpur, Uttar Pradesh (UP). High concentration of methyl parathion, endosulfan, and DDT were observed in water samples collected from the river at Bhagalpur, Bihar. The Industrial Toxicology Research Centre (ITRC), Lucknow (UP) study also found 0.5671 ppb concentrations of endosulfan in the river at Allahabad, UP. Similar results were found in other water samples in India.

  13. The organochlorine pesticides residue levels in karun river water.

    PubMed

    Behfar, Abdolazim; Nazari, Zahra; Rabiee, Mohammad Hassan; Raeesi, Gholamreza; Oveisi, Mohammad Reza; Sadeghi, Nafiseh; Jannat, Behrooz

    2013-01-01

    The organochlorine pesticides (OCPs) are among the most commonly used in water streams around the world. Most of these contaminants are highly hydrophobic and persist in sediments of rivers and lakes. Studies have suggested that OCPs may affect the normal function of the human and wildlife endocrine systems. The aim of this study is to determine the concentrations of selected organochlorine pesticides residues [OP'DDT, PP'DDT, alderin, dieldrin, heptachlor, (α,ß,γ,δ) HCH, (α, ß) endosulfan and metoxychlor] in samples from Karun River water at Khuzestan province in Iran , by GC-µ-ECD. Water was extracted with n-hexane and then purified by passing through a glass column packed with Florisil and Na2SO4, which was then eluted with ether: hexane solution v/v. In general, all of 12 investigated organochlorine pesticides (OCPs) were detected. Regardless of the kind of OCPs, the highest OCP pollution level in Karun River were seen from August to November 2009 ranging 71.43 - 89.34 µg/L, and the lowest were seen from Dec 2010 to March 2011 at levels of 22.25 - 22.64 µg/L. The highest and lowest mean concentrations of 12 investigated pesticides were ß-Endosulfan and pp' DDT with 28.51and 0.01 µg/L respectively. Comparison of total organochlorine pesticides residues concentration with WHO guidelines revealed that the Karun River had total OCPs residues above the probable effect level (0.2-20 µg/L, P < 0.05), which could pose a risk to aquatic life.

  14. The Organochlorine Pesticides Residue Levels in Karun River Water

    PubMed Central

    Behfar, Abdolazim; Nazari, Zahra; Rabiee, Mohammad Hassan; Raeesi, Gholamreza; Oveisi, Mohammad Reza; Sadeghi, Nafiseh; Jannat, Behrooz

    2013-01-01

    Background The organochlorine pesticides (OCPs) are among the most commonly used in water streams around the world. Most of these contaminants are highly hydrophobic and persist in sediments of rivers and lakes. Studies have suggested that OCPs may affect the normal function of the human and wildlife endocrine systems. Objectives The aim of this study is to determine the concentrations of selected organochlorine pesticides residues [OP'DDT, PP'DDT, alderin, dieldrin, heptachlor, (α,ß,γ,δ) HCH, (α, ß) endosulfan and metoxychlor] in samples from Karun River water at Khuzestan province in Iran , by GC-µ-ECD. Materials and Methods Water was extracted with n-hexane and then purified by passing through a glass column packed with Florisil and Na2SO4, which was then eluted with ether: hexane solution v/v. Results In general, all of 12 investigated organochlorine pesticides (OCPs) were detected. Regardless of the kind of OCPs, the highest OCP pollution level in Karun River were seen from August to November 2009 ranging 71.43 – 89.34 µg/L, and the lowest were seen from Dec 2010 to March 2011 at levels of 22.25 - 22.64 µg/L. The highest and lowest mean concentrations of 12 investigated pesticides were ß-Endosulfan and pp' DDT with 28.51and 0.01 µg/L respectively. Conclusions Comparison of total organochlorine pesticides residues concentration with WHO guidelines revealed that the Karun River had total OCPs residues above the probable effect level (0.2-20 µg/L, P < 0.05), which could pose a risk to aquatic life. PMID:24624185

  15. Pesticide residues in fruits and vegetables in Ghana: a review.

    PubMed

    Donkor, Augustine; Osei-Fosu, Paul; Dubey, Brajesh; Kingsford-Adaboh, Robert; Ziwu, Cephas; Asante, Isaac

    2016-10-01

    Pesticides are known to improve agriculture yield considerably leading to an increase in its application over the years. The use of pesticides has shown varying detrimental effects in humans as well as the environment. Presently, enough evidence is available to suggest their misuse and overuse in the last few decades in most developing nations primarily due to lack of education, endangering the lives of farmers as well as the entire population and environment. However, there is paucity of data especially over long durations in Ghana resulting in the absence of effective monitoring programs regarding pesticide application and subsequent contamination in fruits and vegetables. Therefore, this review discusses comprehensively pesticide type and use, importation, presence in fruits and vegetables, human exposure, and poisoning in Ghana. This is to alert the scientific community in Ghana of the need to further research into the potential implications of pesticide residues in food commodities in order to generate a comprehensive and reliable database which is key in drafting policies simultaneous with food regulation, suitable monitoring initiatives, assessment, and education to minimize their effects thereon.

  16. 40 CFR 158.2172 - Experimental use permit microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... results of testing: i. Indicate the potential to cause adverse human health effects or the product... pesticides residue data requirements table. 158.2172 Section 158.2172 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158...

  17. 40 CFR 158.2172 - Experimental use permit microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... results of testing: i. Indicate the potential to cause adverse human health effects or the product... pesticides residue data requirements table. 158.2172 Section 158.2172 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158...

  18. 40 CFR 158.2172 - Experimental use permit microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... results of testing: i. Indicate the potential to cause adverse human health effects or the product... pesticides residue data requirements table. 158.2172 Section 158.2172 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158...

  19. 40 CFR 158.2172 - Experimental use permit microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... results of testing: i. Indicate the potential to cause adverse human health effects or the product... pesticides residue data requirements table. 158.2172 Section 158.2172 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158...

  20. 40 CFR 158.2172 - Experimental use permit microbial pesticides residue data requirements table.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... results of testing: i. Indicate the potential to cause adverse human health effects or the product... pesticides residue data requirements table. 158.2172 Section 158.2172 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) PESTICIDE PROGRAMS DATA REQUIREMENTS FOR PESTICIDES Microbial Pesticides § 158...

  1. Colorimetric sensor array for detection and identification of organophosphorus and carbamate pesticides.

    PubMed

    Qian, Sihua; Lin, Hengwei

    2015-01-01

    Due to relatively low persistence and high effectiveness for insect and pest eradication, organophosphates (OPs) and carbamates are the two major classes of pesticides that broadly used in agriculture. Hence, the sensitive and selective detection of OPs and carbamates is highly significant. In this current study, a colorimetric sensor array comprising five inexpensive and commercially available thiocholine and H2O2 sensitive indicators for the simultaneous detection and identification of OPs and carbamates is developed. The sensing mechanism of this array is based on the irreversible inhibition capability of OPs and carbamates to the activity of acetylcholinesterase (AChE), preventing production of thiocholine and H2O2 from S-acetylthiocholine and acetylcholine and thus resulting in decreased or no color reactions to thiocholine and H2O2 sensitive indicators. Through recognition patterns and standard statistical methods (i.e., hierarchical clustering analysis and principal component analysis), the as-developed array demonstrates not only discrimination of OPs and carbamates from other kinds of pesticides but, more interestingly, identification of them exactly from each other. Moreover, this array is experimentally confirmed to have high selectivity and sensitivity, good anti-interference capability, and potential applications in real samples for OPs and carbamates.

  2. Simultaneous determination of urinary dialkylphosphate metabolites of organophosphorus pesticides using gas chromatography-mass spectrometry.

    PubMed

    Ueyama, Jun; Saito, Isao; Kamijima, Michihiro; Nakajima, Tamie; Gotoh, Masahiro; Suzuki, Takayoshi; Shibata, Eiji; Kondo, Takaaki; Takagi, Kenji; Miyamoto, Ken-ichi; Takamatsu, Junki; Hasegawa, Takaaki; Takagi, Kenzo

    2006-02-17

    In this study, we developed a safe and sensitive method for the simultaneous determination of urinary dialkylphosphates (DAPs), metabolites of organophosphorus insecticides (OPs), including dimethylphosphate (DMP), diethylphosphate (DEP), dimethylthiophosphate (DMTP), and diethylthiophosphate (DETP), using a pentafluorobenzylbromide (PFBBr) derivatization and gas chromatography-mass spectrometry (GC-MS). Several parameters were investigated: pH on evaporation, reaction temperature and time for the derivatization, the use of an antioxidant for preventing oxidation, and a clean-up step. The pH was set at 6, adjusted with K2CO3, and the reaction temperature and time of derivatization were 80 degrees C and 30 min, respectively. Sodium disulfite was chosen as an antioxidant. The clean-up step was performed with a Florisil/PSE mini-column to remove the unreacted PFBBr and sample matrix. This established procedure markedly shortened the sample preparation time to only about 3 h, and completely inhibited the unwanted oxidization of dialkylthiophosphates. The limits of determination (LOD) were approximately 0.3 microg/L for DMP, and 0.1 microg/L for DEP, DMTP, and DETP in 5 mL of human urine. Within-series and between-day imprecision for the present method using pooled urine spiked with DAPs was less than 20.6% in the calibration range of 1-300 microg/L, and the mean recovery was 56.7-60.5% for DMP, 78.5-82.7% for DEP, 88.3-103.9% for DMTP, and 84.2-92.4% for DETP. This method detected geometric mean values of the urinary DAPs in Japanese with and without occupational exposure to OPs, 16.6 or 27.4 for DMP, 1.0 or 0.7 for DEP, 1.3 or 2.3 for DMTP, and 1.0 or 1.1 microg/L for DETP, respectively. The present method, which does not require special equipment except for GC-MS, is quick, safe, and sensitive enough to be adopted in routine biological monitoring of non-occupational as well as occupational exposure to OPs.

  3. Detection of pesticide (Cyantraniliprole) residue on grapes using hyperspectral sensing

    NASA Astrophysics Data System (ADS)

    Mohite, Jayantrao; Karale, Yogita; Pappula, Srinivasu; Shabeer, Ahammed T. P.; Sawant, S. D.; Hingmire, Sandip

    2017-05-01

    Pesticide residues in the fruits, vegetables and agricultural commodities are harmful to humans and are becoming a health concern nowadays. Detection of pesticide residues on various commodities in an open environment is a challenging task. Hyperspectral sensing is one of the recent technologies used to detect the pesticide residues. This paper addresses the problem of detection of pesticide residues of Cyantraniliprole on grapes in open fields using multi temporal hyperspectral remote sensing data. The re ectance data of 686 samples of grapes with no, single and double dose application of Cyantraniliprole has been collected by handheld spectroradiometer (MS- 720) with a wavelength ranging from 350 nm to 1052 nm. The data collection was carried out over a large feature set of 213 spectral bands during the period of March to May 2015. This large feature set may cause model over-fitting problem as well as increase the computational time, so in order to get the most relevant features, various feature selection techniques viz Principle Component Analysis (PCA), LASSO and Elastic Net regularization have been used. Using this selected features, we evaluate the performance of various classifiers such as Artificial Neural Networks (ANN), Support Vector Machine (SVM), Random Forest (RF) and Extreme Gradient Boosting (XGBoost) to classify the grape sample with no, single or double application of Cyantraniliprole. The key finding of this paper is; most of the features selected by the LASSO varies between 350-373nm and 940-990nm consistently for all days. Experimental results also shows that, by using the relevant features selected by LASSO, SVM performs better with average prediction accuracy of 91.98 % among all classifiers, for all days.

  4. Pesticide residues and bees--a risk assessment.

    PubMed

    Sanchez-Bayo, Francisco; Goka, Koichi

    2014-01-01

    Bees are essential pollinators of many plants in natural ecosystems and agricultural crops alike. In recent years the decline and disappearance of bee species in the wild and the collapse of honey bee colonies have concerned ecologists and apiculturalists, who search for causes and solutions to this problem. Whilst biological factors such as viral diseases, mite and parasite infections are undoubtedly involved, it is also evident that pesticides applied to agricultural crops have a negative impact on bees. Most risk assessments have focused on direct acute exposure of bees to agrochemicals from spray drift. However, the large number of pesticide residues found in pollen and honey demand a thorough evaluation of all residual compounds so as to identify those of highest risk to bees. Using data from recent residue surveys and toxicity of pesticides to honey and bumble bees, a comprehensive evaluation of risks under current exposure conditions is presented here. Standard risk assessments are complemented with new approaches that take into account time-cumulative effects over time, especially with dietary exposures. Whilst overall risks appear to be low, our analysis indicates that residues of pyrethroid and neonicotinoid insecticides pose the highest risk by contact exposure of bees with contaminated pollen. However, the synergism of ergosterol inhibiting fungicides with those two classes of insecticides results in much higher risks in spite of the low prevalence of their combined residues. Risks by ingestion of contaminated pollen and honey are of some concern for systemic insecticides, particularly imidacloprid and thiamethoxam, chlorpyrifos and the mixtures of cyhalothrin and ergosterol inhibiting fungicides. More attention should be paid to specific residue mixtures that may result in synergistic toxicity to bees.

  5. Pesticide Residues and Bees – A Risk Assessment

    PubMed Central

    Sanchez-Bayo, Francisco; Goka, Koichi

    2014-01-01

    Bees are essential pollinators of many plants in natural ecosystems and agricultural crops alike. In recent years the decline and disappearance of bee species in the wild and the collapse of honey bee colonies have concerned ecologists and apiculturalists, who search for causes and solutions to this problem. Whilst biological factors such as viral diseases, mite and parasite infections are undoubtedly involved, it is also evident that pesticides applied to agricultural crops have a negative impact on bees. Most risk assessments have focused on direct acute exposure of bees to agrochemicals from spray drift. However, the large number of pesticide residues found in pollen and honey demand a thorough evaluation of all residual compounds so as to identify those of highest risk to bees. Using data from recent residue surveys and toxicity of pesticides to honey and bumble bees, a comprehensive evaluation of risks under current exposure conditions is presented here. Standard risk assessments are complemented with new approaches that take into account time-cumulative effects over time, especially with dietary exposures. Whilst overall risks appear to be low, our analysis indicates that residues of pyrethroid and neonicotinoid insecticides pose the highest risk by contact exposure of bees with contaminated pollen. However, the synergism of ergosterol inhibiting fungicides with those two classes of insecticides results in much higher risks in spite of the low prevalence of their combined residues. Risks by ingestion of contaminated pollen and honey are of some concern for systemic insecticides, particularly imidacloprid and thiamethoxam, chlorpyrifos and the mixtures of cyhalothrin and ergosterol inhibiting fungicides. More attention should be paid to specific residue mixtures that may result in synergistic toxicity to bees. PMID:24718419

  6. Design of a novel noninvasive spectrometer for pesticide residues monitor

    NASA Astrophysics Data System (ADS)

    Ren, Zhong; Liu, Guodong; Huang, Zhen

    2014-11-01

    Although the gas or liquid chromatography had been widely used into pesticide residues monitoring, some drawbacks such as time-consuming, complicated operation and especially the destructivity for samples were existed. To overcome the limits of destructive detection methods, the noninvasive detection method based on spectroscopy was used to detect the pesticide residues in this paper. To overcome low resolution and light-efficiency due to the drawbacks of the classical plane and holography concave gratings, a novel noninvasive spectrometer for pesticide residues monitor (PRM) based on volume holography transmission (VHT) grating was designed. Meanwhile, a custom-built splitting light system for PRM based on the VHT grating was developed. In addition, the linear charge coupled device (CCD) with combined data acquisition (DAQ) card and the virtual-PRM based on LabVIEW were respectively used as the spectral acquisition hardware and software-platform. Experimental results showed that the spectral resolution of this spectrometer reached 2nm, and the VHT grating's diffraction efficiency was gotten via the simulation experiment.

  7. Utilizing a novel sorbent in the solid phase extraction for simultaneous determination of 15 pesticide residues in green tea by GC/MS.

    PubMed

    Huo, Feifei; Tang, Hua; Wu, Xue; Chen, Dazhou; Zhao, Tan; Liu, Pei; Li, Lei

    2016-06-15

    Pesticide residues exceeding standard in green tea is a widespread problem of the world's attention, containing organochlorine pesticides (OCPs), organophosphorus pesticides (OPPs), and pyrethroids. In this research, three dimensionally honeycomb Mg-Al layered double oxide (TDH-Mg-Al-LDO) combined with graphitized carbon black (GCB), packed as a column, was used as a novel solid phase extraction sorbent, applying in simultaneous determination of 15 pesticide residues in green tea coupled with GC-MS. Compared with different type of SPE column, it showed that TDH-Mg-Al-LDO exhibited great advantages in the extraction of 15 pesticide residues from green tea, which was seldom reported before. Different experiment conditions, such as combination order of Mg-Al-LDO and GCB, dosage of sorbents, type and volume of eluting solvent were thoroughly studied and optimized. The limits of detection (LODs) of 15 pesticides ranged from 0.9 to 24.2ng/g and the limits of quantifications (LOQs) were ranging from 3.0 to 80.0ng/g. The recoveries using this method at three spiked concentration levels (10, 100 and 500ng/g for Fenthion, P,P'-DDE, O,P'-DDT, P,P'-DDD and Bifenthrin, 100, 500 and 2000ng/g for the others) range from 71.1 to 119.0%. The relative standard deviation (RSD) was from 0.1 to 7.6% in all case. The result indicated that the proposed analytical method had been successfully applied for the simultaneous determination of 15 pesticide residues in commercial green tea. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Sister-chromatid exchanges and cell-cycle delay in Chinese hamster V79 cells treated with 9 organophosphorus compounds (8 pesticides and 1 defoliant).

    PubMed

    Chen, H H; Sirianni, S R; Huang, C C

    1982-03-01

    Significant increase of sister-chromatid exchanges (SCE) in V79 cells treated with 2 organophosphorus pesticides (OPP), fenthion and oxydemeton-methyl, was observed. The other 7 compounds (6 OPP and 1 defoliant) namely, amaze, azinphos-methyl, bolstar, DEF-defoliant, fensulfothion, monitor and nemacur caused no increase of SCE frequencies at the doses tested. All the compounds except fensulfothion and oxydemeton-methyl induced cell-cycle delay in varying degrees. Cell-cycle delay caused by an OPP was found to be dose-dependent. Based on these data as well as others reported, it would appear that OPP which induce no SCE increase and no or slight cell-cycle delay could be considered as good candidates to substitute the pesticides that have been found to be harmful to the environment.

  9. Simultaneous determination of organophosphorus, organochlorine, pyrethriod and carbamate pesticides in Radix astragali by microwave-assisted extraction/dispersive-solid phase extraction coupled with GC-MS.

    PubMed

    Mao, Xuejin; Wan, Yiqun; Yan, Aiping; Shen, Mingyue; Wei, Yuanlong

    2012-08-15

    A simple, rapid and reliable method was proposed for the simultaneous determination of 27 pesticides (organophosphorus, organochlorine, pyrethroid and carbamate pesticides) in Radix astragali. The pesticides were extracted by acetonitrile and the experimental variables, such as temperature, extraction time and volume of acetonitrile, were optimized through orthogonal array experimental design. Cleanup of extracts was performed with dispersive-solid phase extraction using primary secondary amine (PSA) as the sorbent. The determination of pesticides in the final extracts was carried out by gas chromatography-mass spectrometry in selected ion monitoring mode (GC-MS, SIM). The linearity of the calibration curves is good in matrix-matched standard, and yields the coefficients of determination (R(2))≥0.99 for approximately 96% of the target analytes. Under optimized conditions, the average recoveries (six replicates) for most pesticides (spiked at 0.02, 0.1 and 0.2 mg kg(-1)) range from 70% to 120%, and RSDs are less than 17.2%. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Use of Combined Uncertainty of Pesticide Residue Results for Testing Compliance with Maximum Residue Limits (MRLs).

    PubMed

    Farkas, Zsuzsa; Slate, Andrew; Whitaker, Thomas B; Suszter, Gabriella; Ambrus, Árpád

    2015-05-13

    The uncertainty of pesticide residue levels in crops due to sampling, estimated for 106 individual crops and 24 crop groups from residue data obtained from supervised trials, was adjusted with a factor of 1.3 to accommodate the larger variability of residues under normal field conditions. Further adjustment may be necessary in the case of mixed lots. The combined uncertainty of residue data including the contribution of sampling is used for calculation of an action limit, which should not be exceeded when compliance with maximum residue limits is certified as part of premarketing self-control programs. On the contrary, for testing compliance of marketed commodities the residues measured in composite samples should be greater than or equal to the decision limit calculated only from the combined uncertainty of the laboratory phase of the residue determination. The options of minimizing the combined uncertainty of measured residues are discussed. The principles described are also applicable to other chemical contaminants.

  11. Overall and class-specific scores of pesticide residues from fruits and vegetables as a tool to rank intake of pesticide residues in United States: A validation study.

    PubMed

    Hu, Yang; Chiu, Yu-Han; Hauser, Russ; Chavarro, Jorge; Sun, Qi

    2016-01-01

    Pesticide residues in fruits and vegetables are among the primary sources of pesticide exposure through diet, but the lack of adequate measurements hinder the research on health effects of pesticide residues. Pesticide Residue Burden Score (PRBS) for estimating overall dietary pesticide intake, organochlorine pesticide score (OC-PRBS) and organophosphate pesticide score (OP-PRBS) for estimating organochlorine and organophosphate pesticides-specific intake, respectively, were derived using U.S. Department of Agriculture Pesticide Data Program data and National Health and Nutrition Examination Survey (NHANES) food frequency questionnaire data. We evaluated the performance of these scores by validating the scores against pesticide metabolites measured in urine or serum among 3,679 participants in NHANES using generalized linear regression. The PRBS was positively associated with a score summarizing the ranks of all pesticide metabolites in a linear fashion (p for linear trend <0.001). Furthermore, individuals in the top quintile of this score had urinary pesticide metabolite levels 13.0% (95% CI 8.3%-17.7%) higher than individuals in the lowest quintile. Similarly, we observed significant associations of the OC-PRBS and OP-PRBS with the levels of lipid-adjusted total serum organochlorine pesticides and urinary creatinine-adjusted organophosphate pesticides, respectively. The relative difference (RD) in average pesticide metabolite rank between extreme quintiles was 17.8% (95% CI: 11.1%-24.4%, p for trend <0.001) for the OP-PRBS, whereas the RD was marginally significant at 7.0% (95% CI: -0.5%-14.4%, p for trend 0.07) for the OC-PRBS. The PRBS and OP-PRBS had similar performance when they were derived from fruits and vegetables with high vs. low pesticide residues, respectively (p for trend <0.001 for all associations). The OP-PRBS was associated with all measured organophosphate pesticides, whereas the positive association between OC-PRBS and averaged measured

  12. Organochlorine pesticide residues in biological compartments of healthy mothers.

    PubMed

    Elserougy, Safaa; Beshir, Safia; Saad-Hussein, Amal; Abouarab, Assem

    2013-06-01

    The present study was conducted to detect placental and breast milk (BM) transfer of organochlorine pesticides (OCPs) between biological compartments in healthy lactating mothers. The study explores the effect of parity, breast-feeding and urban/rural residence on body burden of OCP residues. The study included 38 healthy participants submitted to cesarean delivery. Sociodemographic data and specimens of maternal and umbilical sera, adipose tissue (Adp T) and BM were collected. Specimens were analyzed to detect OCP residues. The lindane in BM, o,p'-dichlorodiphenyldichloroethane (DDD) in maternal serum (MS) and total dichlorodiphenyltrichloroethane (DDT) and o,p'-dichlorodiphenyldichloroethylene in umbilical serum were the only detected residues in significantly higher frequencies and/or means in the primigravidae than multigravidae. There was a high risk of detecting o,p'-DDD (odds ratio = 8.3) in umbilical serum of the mothers with o,p'-DDD detected in the MS. Total DDT was detected in about 65% of specimens of BM, MS and Adp T and in about 40% of the umbilical serum specimens. There was only a significant positive correlation between total DDT residues in the BM and Adp T. Total DDT residues in umbilical serum and Adp T were significantly higher in the urban than in the rural mothers. The detection of some OCPs in maternal biological compartments suggests their potential placental and BM transfer to her child during pregnancy and lactation, respectively. Furthermore, it might reflect the persistence or recent use of these pesticides in the environment.

  13. Contamination of liquid milk and butter with pesticide residues in the Ludhiana district of Punjab state, India.

    PubMed

    Battu, R S; Singh, Balwinder; Kang, B K

    2004-11-01

    An analysis of 92 samples of liquid milk from Ludhiana, India, during 1999-2001 revealed the presence of DDT in 6 (7.4%) samples and of these 2 samples were found to exceed the maximum residue limit (MRL) of DDT fixed at 0.05 mg kg(-1) (on a whole milk basis). HCH residues were detected in 49 (53.3%) samples and constituted only gamma-HCH (lindane). The MRL of lindane is fixed at 0.01 mg kg(-1) (whole milk basis), and all 49 liquid milk samples exceeded this value. These results are indicative of contamination of bovine milk with pesticide residues as a result of the ban on the use of DDT and HCH in agriculture and public health programs. Similarly, analysis of 40 samples of butter showed the presence of DDT and HCH in 28 and 8 samples, respectively. However, none of the samples exceeded the MRL value of either DDT or any isomer of HCH. DDT residues comprised mainly p,p-DDE and p,p-TDE, whereas HCH residues were present as lindane in 6 samples, and 2 samples revealed the presence of beta-HCH. The estimated daily intake of lindane through the consumption of contaminated liquid milk exceeded its acceptable daily intake value for children. Interestingly, none of the liquid milk or butter samples revealed the presence of any commonly used organophosphorus or synthetic pyrethroid insecticides at their detection limit of 0.01 mg kg(-1).

  14. Lactobacillus Casei Decreases Organophosphorus Pesticide Diazinon Cytotoxicity in Human HUVEC Cell Line

    PubMed Central

    Bagherpour Shamloo, Hasan; Golkari, Saber; Faghfoori, Zeinab; Movassaghpour, AliAkbar; Lotfi, Hajie; Barzegari, Abolfazl; Yari Khosroushahi, Ahmad

    2016-01-01

    Purpose: Exposure to diazinon can trigger acute and chronic toxicity and significantly induces DNA damage and proapoptotic effects in different human cells. Due to the significance of probiotic bacteria antitoxin effect, this study aimed to investigate the effect of Lactobacillus casei on diazinon (DZN) cytotoxicity in human umbilical vein endothelial cells (HUVEC) in vitro. Methods: The cytotoxicity assessments were performed by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) test, DAPI (4',6-diamidino-2-phenylindole) staining and flow cytometric methodologies. Results: Cytotoxic assessments through flow cytometry/ DAPI staining demonstrated that apoptosis is the main cytotoxic mechanism of diazinon in HUVEC cells and L. casei could decrease the diazinon cytotoxic effects on toxicants. Conclusion: the screen of total bacterial secreted metabolites can be considered as a wealthy source to find the new active compounds to introduce as reducing agricultural remained pesticide cytotoxicity effects on the human food chain. PMID:27478782

  15. Isolation of the opdE gene that encodes for a new hydrolase of Enterobacter sp. capable of degrading organophosphorus pesticides.

    PubMed

    Chino-Flores, Concepción; Dantán-González, Edgar; Vázquez-Ramos, Alejandra; Tinoco-Valencia, Raunel; Díaz-Méndez, Rafael; Sánchez-Salinas, Enrique; Castrejón-Godínez, Maria Luisa; Ramos-Quintana, Fernando; Ortiz-Hernández, Maria Laura

    2012-06-01

    Microbial enzymes that can hydrolyze organophosphorus compounds have been isolated, identified and characterized from different microbial species in order to use them in biodegradation of organophosphorus compounds. We isolated a bacterial strain Cons002 from an agricultural soil bacterial consortium, which can hydrolyze methyl-parathion (MP) and other organophosphate pesticides. HPLC analysis showed that strain Cons002 is capable of degrading pesticides MP, parathion and phorate. Pulsed-field gel electrophoresis and 16S rRNA amplification were performed for strain characterization and identification, respectively, showing that the strain Cons002 is related to the genus Enterobacter sp. which has a single chromosome of 4.6 Mb and has no plasmids. Genomic library was constructed from DNA of Enterobacter sp. Cons002. A gene called opdE (Organophosphate Degradation from Enterobacter) consists of 753 bp and encodes a protein of 25 kDa, which was isolated using activity methods. This gene opdE had no similarity to any genes reported to degrade organophosphates. When kanamycin-resistance cassette was placed in the gene opdE, hydrolase activity was suppressed and Enterobacter sp. Cons002 had no growth with MP as a nutrients source.

  16. Determination of trace organophosphorus pesticides in water samples with TiO2 nanotubes cartridge prior to GC-flame photometric detection.

    PubMed

    Huang, Yunrui; Zhou, Qingxiang; Xiao, Junping; Xie, Guohong

    2010-07-01

    This article described a new method for the sensitive determination of organophosphorus pesticides in water samples using SPE in combination with GC-flame photometric detection. In the procedure of method development, TiO(2) nanotubes were used as SPE adsorbents for the enrichment of organophosphorus pesticides from water samples. Several factors, such as eluent and its volume, sample pH, sample volume, sample flow rate, and concentration of humic acid, were optimized. Under the optimal conditions, the proposed method had good linear ranges as 0.1-40 microg/L for each of them, LOD of 0.11, 0.014, and 0.0025 microg/L, and LOQs of 0.37, 0.047, and 0.0083 microg/L for chlorpyrifos, phorate, and methyl parathion, respectively. The proposed method was validated with real environmental water samples and the spiked recoveries were over the range of 86.5-115.1%. All these results indicated that TiO(2) nanotubes, as a new SPE adsorbent, would be used widespread for the preconcentration and determination of environmental pollutants in the future.

  17. Simultaneous determination of organophosphorus pesticides in fruits and vegetables using atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry.

    PubMed

    Cheng, Zhipeng; Dong, Fengshou; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Chen, Zenglong; Pan, Xinglu; Gan, Jay; Zheng, Yongquan

    2017-09-15

    This paper describes the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for the simultaneous determination of organophosphorus pesticides in apple, pear, tomato, cucumber and cabbage. Soft ionization with atmospheric pressure ionization source was compared with traditional electron impact ionization (EI). The sensitivity of GC coupled to atmospheric pressure ionization (APGC) for all the analytes was enhanced by 1.0-8.2 times. The ionization modes with atmospheric pressure ionization source was studied by comparing the charge-transfer and proton-transfer conditions. The optimized QuEChERs method was used to pretreat the samples. The calibration curves were found linear from 10 to 1000μg/L, obtaining correlation coefficients higher than 0.9845. Satisfactory mean recovery values, in the range of 70.0-115.9%, and satisfactory precision, with all RSDr <19.7% and all RSDR values <19.5% at the three fortified concentration levels for all the fifteen OPPs. The results demonstrate the potential of APGC-QTOF-MS for routine quantitative analysis of organophosphorus pesticide in fruits and vegetables. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Temperature-controlled ultrasound- and vortex-assisted liquid-liquid microextraction combined with GC for the determination of the concentrations of organophosphorus pesticides in beverage samples.

    PubMed

    Wu, Tong; Zhao, Wenting; Yang, Zhonghua; Gao, Haixiang; Zhou, Zhiqiang

    2013-12-01

    The aim of this work was to develop temperature-controlled ultrasound- and vortex-assisted liquid-liquid microextraction as a fast and efficient approach for the extraction of nine organophosphorus pesticides in beverage samples followed by GC with flame photometric detection analysis. The combination of ultrasonication and vortexing were used to assist the microextraction, and the use of a dispersion solvent was avoided. Several variables that could potentially affect the extraction efficiency, namely, the type and volume of extraction solvent, sequence, and time of ultrasonication and vortexing, ultrasonication bath temperature and ionic strength were optimized. Under optimum conditions, the calibration graphs were linear over the range of 0.5-200 μg/L. The LOD (S/N = 3) was between 0.01 and 0.05. The optimized method exhibited a good precision level with RSD values between 4.5 and 9.8%. The enrichment factors for the nine organophosphorus pesticides were between 224 and 339. Four beverage samples were successfully analyzed using the proposed method.

  19. New magnetic graphene-based inorganic-organic sol-gel hybrid nanocomposite for simultaneous analysis of polar and non-polar organophosphorus pesticides from water samples using solid-phase extraction.

    PubMed

    Rashidi Nodeh, Hamid; Wan Ibrahim, Wan Aini; Kamboh, Muhammad Afzal; Sanagi, Mohd Marsin

    2017-01-01

    A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (Fe3O4@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The Fe3O4@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL(-1) for phosphamidon and dimethoate, and 10-100 pg mL(-1) for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL(-1) for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL(-1)) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. Fe3O4@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g(-1)) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised Fe3O4@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.

  20. Washing effects of limonene on pesticide residues in green peppers.

    PubMed

    Lu, Hai-Yan; Shen, Yan; Sun, Xing; Zhu, Hong; Liu, Xian-Jin

    2013-09-01

    The presence of pesticide residues in food has caused much concern. The low health risks and environmental impacts of limonene make it a very interesting solvent for use in green chemistry. Washing effects of limonene on pesticide residues of methyl chlorpyrifos, chlorothalonil, chlorpyrifos, fenpropathrin and deltamethrin were investigated in green pepper. Results showed that washing with a low concentration of limonene for 5 min (where LOQ is limit of quantitation) caused 53.67%, pesticides, respectively, while corresponding values of washing with a high concentration were 84.64%, pesticide residues in green pepper, considering effect and treatment time as well as cost. © 2013 Society of Chemical Industry.

  1. Production and characterization of a single-chain variable fragment linked alkaline phosphatase fusion protein for detection of O,O-diethyl organophosphorus pesticides in a one-step enzyme-linked immunosorbent assay

    USDA-ARS?s Scientific Manuscript database

    A single-chain variable fragment (scFv) and alkaline phosphatase (AP) fusion protein for detection of O, O-diethyl organophosphorus pesticides (OPs) was produced and characterized. The scFv gene was prepared by cloning VL and VH genes from a hybridoma cell secreting monoclonal antibody with broad-s...

  2. Determination of pesticide residues in animal origin baby foods by gas chromatography coupled with triple quadrupole mass spectrometry.

    PubMed

    Amendola, Graziella; Pelosi, Patrizia; Attard Barbini, Danilo

    2015-01-01

    A simple, fast and multiresidue method for the determination of pesticide residues in baby foods of animal origin has been developed in order to check the compliance with the Maximum Residue Levels (MRLs) set at a general value of 0.01 mg/kg by Commission Directive 2006/125/EC for infant foods. The main classes of organochlorine, organophosphorus and pyrethroid compounds have been considered, which are mainly fat soluble pesticides. The analytical procedure consists in the extraction of baby food samples by acetonitrile (ACN) followed by a clean up using C18 solid-phase extraction column eluted with ACN. The compounds were determined by gas chromatography-triple quadrupole mass spectrometry equipped with a Programmed Temperature Vaporizer (PTV) injection and a backflush system. In order to compensate for matrix effects PTV and matrix matched standard calibrations have been used. The method has been fully validated for 57 pesticides according to the Document SANCO/12571/2013. Accuracy and precision (repeatability) have been studied by recoveries at two spiking levels, the Limit of Quantitation (LOQ) (0.003-0.008 mg/kg) and 10 time greater (0.03-0.08 mg/kg), and the results were in the acceptable range of 70-120% with Relative Standards Deviations (RSD) ≤20%. Selectivity, linearity, LOQ and uncertainty of measurement were also determined for all the compounds. The method has been also applied for the analysis of 18 baby food animal origin samples, bought form the local market in Rome (Italy), and no pesticide in the scope of the method has been found above the MRL or the LOQ.

  3. Determination of pesticide residues in fruit-based soft drinks.

    PubMed

    García-Reyes, Juan F; Gilbert-López, Bienvenida; Molina-Díaz, Antonio; Fernández-Alba, Amadeo R

    2008-12-01

    Here we report the first worldwide reconnaissance study of the presence and occurrence of pesticides in fruit-based soft drinks. While there are strict regulations and exhaustive controls for pesticides in fruits, vegetables, and drinking water, scarce attention has been paid to highly consumed derivate products, which may contain these commodities as ingredients. In the case of the fruit-based soft drinks industry, there are no clear regulations, relating to pesticides, which address them, even when there is significant consumption in vulnerable groups such as children. In this work, we have developed a screening method to search automatically for up to 100 pesticides in fruit-based soft drinks extracts based on the application of liquid chromatography-electrospray time-of-flight mass spectrometry (LC-TOF MS). The sample extracts injected were obtained by a preliminary sample treatment step based on solid-phase extraction using hydrophilic-lipophilic balanced polymer-based reverse phase cartridges and methanol as eluting solvent. Subsequent identification, confirmation, and quantitation were carried out by LC-TOF MS analysis: the confirmation of the target species was based on retention time matching and accurate mass measurements of protonated molecules ([M + H]+) and fragment ions (obtaining accuracy errors typically lower than 2 ppm). With the proposed method, we measured over 100 fruit-based soft drink samples, purchased from 15 different countries from companies with brands distributed worldwide and found relatively large concentration levels of pesticides in most of the samples analyzed. The concentration levels detected were of the micrograms per liter level, low when considering the European maximum residue levels (MRLs) set for fruits but very high (i.e., 300 times) when considering the MRLs for drinking or bottled water. The detected pesticides (carbendazim, thiabendazole, imazalil and its main degradate, prochloraz and its main degradate, malathion, and

  4. Spatio-temporal patterns of pesticide residues in the Turia and Júcar Rivers (Spain).

    PubMed

    Ccanccapa, Alexander; Masiá, Ana; Andreu, Vicente; Picó, Yolanda

    2016-01-01

    A study was conducted on the occurrence of 50 pesticides in water and sediments of Turia and Júcar Rivers (Valencian Community, Eastern Spain) for a period of two consecutive years each, 2010/2011 and 2012/2013, respectively to assess the contribution of agriculture and urban activities on pesticide pollution. The results showed that mean concentrations of pesticides ranged from pesticide whereas imazalil, thiabendazole, tolclofos methyl, ethion and carbofuran were those found at higher concentrations. Ubiquitous pesticides are those with long half-lives. The most polluted parts of the rivers were the headwaters and the mouth, which could be related to the agricultural practices and rainfall. Contrarily, in the abrupt part of the rivers of difficult access the contamination is low. Other quality parameters monitored in this study also corroborate the worst water quality in the alluvial plains that coincides with higher anthropic pressure. The temporal variations also indicated a strong relation of pesticide concentrations with hydrology, the higher the river flow, the higher number and frequency of pesticides but at lower concentrations. On the contrary, at lower river flows higher pesticide concentrations were detected. The risk assessment for aquatic biota pointed out that organophosphorus and fungicides are a threat to fish and daphnia and herbicides and fungicides are hazards for algae. Thus, the strict control of pesticide concentrations is important to preserve the aquatic ecosystems health.

  5. Toxicological assessment of isomeric pesticides: a strategy for testing of chiral organophosphorus (OP) compounds for delayed polyneuropathy in a regulatory setting.

    PubMed

    Battershill, Jon M; Edwards, Philippa M; Johnson, Martin K

    2004-08-01

    Many compounds, including some pesticides, contain structural centres of asymmetry, which convey the property of a type of stereoisomerism known as chirality. Such compounds can exist in two or more forms, depending on the number of chiral atoms and are termed stereoisomers or enantiomers. Stereoisomers of a particular compound can have different biological properties; one such of particular importance for toxicological evaluation, is the potential for differences in metabolic disposal of and binding of stereoisomers to molecular targets in the cell. The combination of differential metabolism of chiral organophosphorus (OP) pesticides and opposing stereoselectivity of inhibition of neuropathy target esterase (NTE) and acetylcholinesterase (AChE) can affect the value of the hen test, performed to OECD guidelines, in predicting the potential to cause organophosphate-induced delayed polyneuropathy (OPIDP) in humans. This is a mixed central and sensory and motor neuropathy. The experimental data on structural analogues of the pesticide methamidophos and the evidence for stereoselective OPIDP are reviewed and a model is given demonstrating how the properties of a chiral OP can result in the neuropathic potential not being detected by the standard hen test. A strategy for the assessment of a racemic mixture comprised of two OP enantiomers for the potential to induce OPIDP is outlined. The strategy uses information from structure activity relationships (SAR), in vitro tests and in vivo tests to allow risk assessment decisions to be made. It is suggested that the potential for stereoselective toxicity of pesticides should be routinely considered in regulatory assessments.

  6. Exonuclease I-aided homogeneous electrochemical strategy for organophosphorus pesticide detection based on enzyme inhibition integrated with a DNA conformational switch.

    PubMed

    Wang, Xiuzhong; Dong, Shanshan; Hou, Ting; Liu, Lei; Liu, Xiaojuan; Li, Feng

    2016-03-07

    A novel enzyme inhibition-based homogeneous electrochemical biosensing strategy was designed for an organophosphorus pesticide assay based on exploiting the resistance of a mercury ion-mediated helper probe (HP) toward nuclease-catalyzed digestion and the remarkable diffusivity difference between HPs and the mononucleotides toward a negatively charged indium tin oxide (ITO) electrode. In particular, the mercury ion-mediated T-Hg(2+)-T base pairs facilitate the HP labeled with methylene blue (MB) to fold into a hairpin structure, preventing its digestion by exonuclease I, and thus resulting in a low electrochemical response because of the large electrostatic repulsion between the negatively charged ITO electrode and the HPs. The competitive binding by a thiol group (-SH), produced in the hydrolysis reaction of acetylthiocholine (ACh) chloride with acetylcholinesterase (AChE), removes mercury ions from the base pairs, causing a nuclease-catalyzed digestion, and the subsequent electrochemical response increase due to the weak electrostatic repulsion between the product-mononucleotides and the ITO electrode. Mercury ion-mediated HPs were first designed for pesticide detection and diazinon was chosen as the model target. Under the optimal experimental conditions, the approach exhibited high sensitivity for diazinon detection with a detection limit of 0.25 μg L(-1). The satisfactory results in the determination of diazinon in real samples demonstrate that the method possesses great potential for detecting organophosphorus pesticides. This new approach is expected to promote the exploitation of mercury-mediated base pair-based homogenous electrochemical biosensors in biochemical studies and in the food safety field.

  7. Physiologically Based Pharmacokinetic/Pharmacodynamic Model for the Organophosphorus Pesticide Diazinon

    SciTech Connect

    Poet, Torka S.; Kousba, Ahmed A.; Dennison, Stephanie L.; Timchalk, Chuck

    2004-12-01

    Organophosphate (OP) insecticides like diazinon (DZN) constitute a large class of chemical insecticides that are widely utilized. The potential exists for significant exposures to a combination of OP pesticides from multiple routes. The objective of this research was to develop a physiologically based pharmacokinetic/pharmacodynamic (PBPK/PD) model capable of predicting the relationships between exposure route, bioactivation, detoxification, and acetylcholinesterase (AChE) inhibition. CYP450-mediated metabolism of DZN to the active oxon leads to inhibition of AChE at nerve endings. CYP450s also mediate detoxification of DZN to its pyrimidinol and A-esterase detoxifies the oxon to the pyrimidinol. The ultimate goal is to use this model to quantify systemic dosimetry and biological response from available environmental and personal exposure data. The model structure integrates CYP450 and esterase metabolism, route-dependent absorption, target tissue dosimetry, and dynamic response, to predict circulating blood levels of DZN and esterase inhibition in target organs. Metabolic rate constants for the CYP450-mediated conversion to the active oxon and the inactive pyrimidinol and the esterase-mediated deactivation of the oxon have been measured in vitro. The inhibition of AChE activity is a sensitive and relatively easy measure of exposure and is therefore the preferred descriptive endpoint. Esterase inhibition and regeneration rates have been described using in vitro calculations and parameter optimization to fit the model to AChE inhibition data. This descriptive model for DZN has been developed and has been shown to predict blood levels of the parent chemical and AChE inhibition in animal models. This PBPK/PD model will be linked to a existing PBPK model for chlorpyrifos to estimate the effects of exposures to a mixture of OPs and to describe target tissue dosimetry and effects in humans. These biologically relevant PBPK models will be integral to risk assessments for

  8. Determination of Pesticides Residues in Cucumbers Grown in Greenhouse and the Effect of Some Procedures on Their Residues

    PubMed Central

    LEILI, Mostafa; PIRMOGHANI, Amin; SAMADI, Mohammad Taghi; SHOKOOHI, Reza; ROSHANAEI, Ghodratollah; POORMOHAMMADI, Ali

    2016-01-01

    Background: The objective of this study was to determine the residual concentrations of ethion and imidacloprid in cucumbers grown in greenhouse. The effect of some simple processing procedures on both ethion and imidacloprid residues were also studied. Methods: Ten active greenhouses that produce cucumber were randomly selected. Ethion and imidacloprid as the most widely used pesticides were measured in cucumber samples of studied greenhouses. Moreover, the effect of storing, washing, and peeling as simple processing procedures on both ethion and imidacloprid residues were investigated. Results: One hour after pesticide application; the maximum residue levels (MRLs) of ethion and imidacloprid were higher than that of Codex standard level. One day after pesticide application, the levels of pesticides were decreased about 35 and 31% for ethion and imidacloprid, respectively, which still were higher than the MRL. Washing procedure led to about 51 and 42.5% loss in ethion and imidacloprid residues, respectively. Peeling procedure also led to highest loss of 93.4 and 63.7% in ethion and imidacloprid residues, respectively. The recovery for both target analytes was in the range between 88 and 102%. Conclusion: The residue values in collected samples one hour after pesticides application were higher than standard value. The storing, washing, and peeling procedures lead to the decrease of pesticide residues in greenhouse cucumbers. Among them, the peeling procedure has the greatest impact on residual reduction. Therefore, these procedures can be used as simple and effective processing techniques for reducing and removing pesticides from greenhouse products before their consumption. PMID:28032066

  9. Determination of Pesticides Residues in Cucumbers Grown in Greenhouse and the Effect of Some Procedures on Their Residues.

    PubMed

    Leili, Mostafa; Pirmoghani, Amin; Samadi, Mohammad Taghi; Shokoohi, Reza; Roshanaei, Ghodratollah; Poormohammadi, Ali

    2016-11-01

    The objective of this study was to determine the residual concentrations of ethion and imidacloprid in cucumbers grown in greenhouse. The effect of some simple processing procedures on both ethion and imidacloprid residues were also studied. Ten active greenhouses that produce cucumber were randomly selected. Ethion and imidacloprid as the most widely used pesticides were measured in cucumber samples of studied greenhouses. Moreover, the effect of storing, washing, and peeling as simple processing procedures on both ethion and imidacloprid residues were investigated. One hour after pesticide application; the maximum residue levels (MRLs) of ethion and imidacloprid were higher than that of Codex standard level. One day after pesticide application, the levels of pesticides were decreased about 35 and 31% for ethion and imidacloprid, respectively, which still were higher than the MRL. Washing procedure led to about 51 and 42.5% loss in ethion and imidacloprid residues, respectively. Peeling procedure also led to highest loss of 93.4 and 63.7% in ethion and imidacloprid residues, respectively. The recovery for both target analytes was in the range between 88 and 102%. The residue values in collected samples one hour after pesticides application were higher than standard value. The storing, washing, and peeling procedures lead to the decrease of pesticide residues in greenhouse cucumbers. Among them, the peeling procedure has the greatest impact on residual reduction. Therefore, these procedures can be used as simple and effective processing techniques for reducing and removing pesticides from greenhouse products before their consumption.

  10. LC-MS/MS determination of pesticide residues in fruits and vegetables.

    PubMed

    Stachniuk, Anna; Szmagara, Agnieszka; Czeczko, Renata; Fornal, Emilia

    2017-03-29

    The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non

  11. An efficient cleanup method coupled with gas chromatography and mass spectrometry for multi-pesticides residue analysis in complex plant matrices.

    PubMed

    Wang, Xinquan; Qi, Peipei; Wang, Xiangyun; Zhang, Qian; Wang, Zhiwei; Xu, Xiahong; Xu, Hao; Zhang, Hu; Wang, Qiang

    2017-06-01

    We aimed to develop an efficient cleanup method for multi-pesticides residue analysis in complex plant matrices, shallot, ginger, garlic, onion, leek, and celery. Column chromatography was used as the cleanup method and fabricated with florisil and graphitized carbon black as the adsorbents. The amount of the graphitized carbon black adsorbent and the choice of the elution solvent were systematically investigated for exploring the best combination. The target pesticides covered organochlorine, pyrethroid, and organophosphorus pesticides, and were 38 in total. The method validation and comparison were performed to verify its feasibility and advantages in operation convenience and purification efficiency. The method limit of quantitation varied from 0.01 to 0.03 mg/kg, which depends on the pesticides and the sample matrices. The recoveries of the pesticides ranged from 60.5 to 128% (RSD ≤ 19.0%) at the spiked concentration level of 0.01 (or 0.03) mg/kg and 62.9 to 130% (RSD ≤ 13.0%) at 0.1 mg/kg. Compared with the commercial cleanup solid-phase extraction cartridges, the present adsorbent combination displayed better purification effect and shorter sample pretreatment time, demonstrating potential application prospect in the complex matrix sample analysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. 78 FR 76589 - Notice of Receipt of Several Pesticide Petitions Filed for Residues of Pesticide Chemicals in or...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-18

    ... 25, 2012, and January 16, 2013, concerning a new active ingredient (AI) and several pesticide petitions (PP) filed for residues of pesticide chemicals. The name of an AI was changed during the registration assessment process. This document corrects the name of an AI and also corrects a PP...

  13. Acute organophosphorus poisoning.

    PubMed

    Chowdhary, Sheemona; Bhattacharyya, Rajasri; Banerjee, Dibyajyoti

    2014-04-20

    Acute organophosphorus poisoning continues to be a detrimental problem and a potential cause of mortality especially in developing countries. Inhibition of acetylcholinesterase enzyme is the main mechanism of toxicity of such pesticides and measurement of acetylcholinesterase activity is the commonly used laboratory diagnosis approved for the purpose. It is now proved beyond any doubt that early intervention is beneficial for cases of acute organophosphorus poisoning and, therefore, considerable current interest has been generated for development of point of care testing tool for screening of the same. However, to the best of our knowledge so far the matter is not reviewed from the view of point of care testing tool development. In this paper, this subject is reviewed highlighting the methodological aspects and point of care testing tool development in the context of organophosphorus poisoning.

  14. Pesticide residues in Nile tilapia (Oreochromis niloticus) and Nile perch (Lates niloticus) from Southern Lake Victoria, Tanzania.

    PubMed

    Henry, L; Kishimba, M A

    2006-03-01

    Nile tilapia (Oreochromis niloticus) and Nile perch (Lates niloticus) samples were collected from fish landing stations in nine riparian districts on the Tanzanian side of Lake Victoria and screened for residues of 64 organochlorine, organophosphorus, carbamate, and pyrethroid pesticides. The residue levels in the fish fillet were up to 0.003, 0.03 and 0.2 mg/kg fresh weight (0.7, 3.8 and 42 mg/kg lipid weight) of fenitrothion, DDT and endosulfan, respectively. Mean levels within sites were up to 0.002, 0.02 and 0.1 mg/kg fresh weight (0.5, 0.5 and 16 mg/kg lipid weight), respectively. The detection of higher levels of p,p'-DDT than the degradation products (p,p'-DDD and p,p'-DDE), and higher levels of endosulfan isomers (alpha and beta) than the sulphate, in fish samples, implied recent exposure of fish to DDT and endosulfan, respectively. Generally, most of the fish samples had residue levels above the average method detection limits (MDLs), but were within the calculated ADI.

  15. A Multi Residue GC-MS Method for Determination of 12 Pesticides in Cucumber

    PubMed Central

    Nasiri, Azadeh; Amirahmadi, Maryam; Mousavi, Zahra; Shoeibi, Shahram; Khajeamiri, Alireza; Kobarfard, Farzad

    2016-01-01

    Cucumber is one of the main vegetables in Iranian food basket. A wide range of pesticides are used for crops protection during the cultivation of vegetables such as cucumber due to heavy pest infestation. Analysis of pesticide residues in food and other environmental commodities have become essential requirement for consumers, producers, and food quality control authorities. This study was aimed at determination of pesticides residues in cucumber as a main vegetable in Iranian food basket. A reliable, rapid and accurate method based on spiked calibration curves and modified QuEChERS sample preparation was developed for determination of 12 pesticide residues in cucumber by gas chromatography-mass spectrometry (GC/MS). The use of spiked calibration standards for constructing the calibration curve substantially reduced adverse matrix-related effects. The recovery of pesticides at 5 concentration levels (n = 3) was in the range of 80.6-112.3. The method was proved to be repeatable with RSD lower than 20%. The limits of detection and quantification for all pesticides were <10 ng/g and <25 ng/g, respectively. The developed method was used for simultaneous determination of the selected pesticides in 60 greenhouse and garden cucumber samples. Among the 60 analyzed samples, 41.7% of them were contaminated with pesticide residues which 31.7% of samples had pesticide residues lower than maximum residue limit and 10% of samples had residue higher than maximum residue limit. PMID:28243277

  16. 7 CFR 29.429 - Disposition of imported tobacco exceeding pesticide residue standards.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 2 2013-01-01 2013-01-01 false Disposition of imported tobacco exceeding pesticide... Disposition of imported tobacco exceeding pesticide residue standards. Within 10 days of the receipt of test results from pesticide test samples, the Director shall notify the importer or entity responsible for the...

  17. 7 CFR 29.429 - Disposition of imported tobacco exceeding pesticide residue standards.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 2 2012-01-01 2012-01-01 false Disposition of imported tobacco exceeding pesticide... Disposition of imported tobacco exceeding pesticide residue standards. Within 10 days of the receipt of test results from pesticide test samples, the Director shall notify the importer or entity responsible for the...

  18. 7 CFR 29.429 - Disposition of imported tobacco exceeding pesticide residue standards.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 2 2014-01-01 2014-01-01 false Disposition of imported tobacco exceeding pesticide... Disposition of imported tobacco exceeding pesticide residue standards. Within 10 days of the receipt of test results from pesticide test samples, the Director shall notify the importer or entity responsible for the...

  19. Quantitative 31P NMR for Simultaneous Trace Analysis of Organophosphorus Pesticides in Aqueous Media Using the Stir Bar Sorptive Extraction Method

    NASA Astrophysics Data System (ADS)

    Ansari, S.; Talebpour, Z.; Molaabasi, F.; Bijanzadeh, H. R.; Khazaeli, S.

    2016-09-01

    The analysis of pesticides in water samples is of primary concern for quality control laboratories due to the toxicity of these compounds and their associated public health risk. A novel analytical method based on stir bar sorptive extraction (SBSE), followed by 31P quantitative nuclear magnetic resonance (31P QNMR), has been developed for simultaneously monitoring and determining four organophosphorus pesticides (OPPs) in aqueous media. The effects of factors on the extraction efficiency of OPPs were investigated using a Draper-Lin small composite design. An optimal sample volume of 4.2 mL, extraction time of 96 min, extraction temperature of 42°C, and desorption time of 11 min were obtained. The results showed reasonable linearity ranges for all pesticides with correlation coefficients greater than 0.9920. The limit of quantification (LOQ) ranged from 0.1 to 2.60 mg/L, and the recoveries of spiked river water samples were from 82 to 94% with relative standard deviation (RSD) values less than 4%. The results show that this method is simple, selective, rapid, and can be applied to other sample matrices.

  20. Variation across the agricultural season in organophosphorus pesticide urinary metabolite levels for Latino farmworkers in eastern North Carolina: project design and descriptive results.

    PubMed

    Arcury, Thomas A; Grzywacz, Joseph G; Chen, Haiying; Vallejos, Quirina M; Galván, Leonardo; Whalley, Lara E; Isom, Scott; Barr, Dana B; Quandt, Sara A

    2009-07-01

    Community Participatory Approach to Measuring Farmworker Pesticide Exposure, PACE3, used a longitudinal design to document pesticide biomarkers among farmworkers. This article presents an overview of PACE3 and provides a descriptive analysis of participant characteristics and one set of pesticide biomarkers, the dialkylphosphate (DAP) urinary metabolites of organophosphorus (OP) pesticides. Two hundred eighty seven farmworkers were recruited during 2007 from 44 farmworker camps in 11 eastern North Carolina counties. Participants provided interviews, urine samples, blood samples, and saliva samples up to four times at monthly intervals beginning in May. A total of 939 data points were collected. Farmworkers were largely men (91.3%) from Mexico (94.8%) with a mean age of 33.7 years (SE 0.82); 23.3% spoke an indigenous language. Across all data points, frequencies of detection and median urinary concentrations were 41.3% and 0.96 microg/L for dimethylphosphate (DMP), 78.3% and 3.61 microg/L for dimethylthiophosphate (DMTP), 33.3% and 0.04 microg/L for dimethyldithiophosphate (DMDTP), 40.5% and 0.87 microg/L for diethylphosphate (DEP), 32.3% and 0.17 microg/L for diethylthiophosphate (DETP), and 8.09% and 0.00 microg/L for diethyldithiophosphate (DEDTP). The frequencies of detection and urinary concentrations of the DAP metabolites increased during the season. More PACE3 participants were from Mexico, male, migrant workers, and spoke an indigenous language compared to national data. PACE3 participants had comparable frequencies of detection and urinary metabolite concentrations with participants in other studies. Variability in the frequencies of detection and urinary concentrations of the DAP metabolites indicates the importance of longitudinal studies of biomarkers of currently used pesticides in farmworker populations.

  1. Variation across the Agricultural Season in Organophosphorus Pesticide Urinary Metabolite Levels for Latino Farmworkers in Eastern North Carolina: Project Design and Descriptive Results

    PubMed Central

    Arcury, Thomas A.; Grzywacz, Joseph G.; Chen, Haiying; Vallejos, Quirina M.; Galvan, Leonardo; Whalley, Lara E.; Isom, Scott; Barr, Dana B.; Quandt, Sara A.

    2009-01-01

    Background Community Participatory Approach to Measuring Farmworker Pesticide Exposure, PACE3, used a longitudinal design to document pesticide biomarkers among farmworkers. This paper presents an overview of PACE3 and provides a descriptive analysis of participant characteristics and one set of pesticide biomarkers, the dialkylphosphate (DAP) urinary metabolites of organophosphorus (OP) pesticides. Methods 287 farmworkers were recruited during 2007 from 44 farmworker camps in 11 eastern North Carolina counties. Participants provided interviews, urine samples, blood samples, and saliva samples up to four times at monthly intervals beginning in May. A total of 939 data points were collected. Results Farmworkers were largely men (91.3%) from Mexico (94.8%) with a mean age of 33.7 years (SE 0.82); 23.3% spoke an indigenous language. Across all data points, frequencies of detection and median urinary concentrations were 41.3% and 0.96 μg/L for dimethylphosphate, 78.3% and 3.61 μg/L for dimethylthiophosphate, 33.3% and 0.04 μg/L for dimethyldithiophosphate, 40.5% and 0.87 μg/L for diethylphosphate, 32.3% and 0.17 μg/L for diethylthiophosphate, and 8.09% and 0.00 μg/L for diethyldithiophosphate. The frequencies of detection and urinary concentrations of the DAP metabolites increased during the season. Conclusions More PACE3 participants were from Mexico, male, migrant workers, and spoke an indigenous language compared to national data. PACE3 participants had comparable frequencies of detection and urinary metabolite concentrations with participants in other studies. Variability in the frequencies of detection and urinary concentrations of the DAP metabolites indicates the importance of longitudinal studies of biomarkers of currently used pesticides in farmworker populations. PMID:19517490

  2. Cholinesterase assessment as a result of fenitrothion exposure: a survey in a group of public health workers exposed to an organophosphorus pesticide.

    PubMed

    Fakhri, Z I

    1993-11-01

    Antimalarial spraying activities are very important for the malaria control programme in Central Region, Sudan. Fenitrothion, an organophosphorus pesticide, is used for that purpose. A survey of 17 spraying group workers plus three controls was carried out. Whole blood cholinesterase determination was done using the Tintometric method. The maximum and minimum temperatures recorded on the days of the survey were 99 and 78 degrees F respectively. The relative humidity ranged between 82 and 40 per cent in the morning and afternoon respectively. Cholinesterase levels were measured on two pre-start days and then pre- and post-exposure levels were determined on 13 days of a 42 day spraying campaign. On 11 out of the 13 days, cholinesterase levels showed a significant drop. The cholinesterase levels of some members of the spraying team decreased by 25 per cent, 37.5 per cent or 50 per cent which were considered as slight-moderate, moderate-pronounced and pronounced inhibition, respectively.

  3. Requiring Pollutant Discharge Permits for Pesticide Applications that Deposit Residues in Surface Waters

    PubMed Central

    Centner, Terence; Eberhart, Nicholas

    2014-01-01

    Agricultural producers and public health authorities apply pesticides to control pests that damage crops and carry diseases. Due to the toxic nature of most pesticides, they are regulated by governments. Regulatory provisions require pesticides to be registered and restrictions operate to safeguard human health and the environment. Yet pesticides used near surface waters pose dangers to non-target species and drinking water supplies leading some governments to regulate discharges of pesticides under pollution discharge permits. The dual registration and discharge permitting provisions are burdensome. In the United States, agricultural interest groups are advancing new legislation that would exempt pesticide residues from water permitting requirements. An analysis of the dangers posed by pesticide residues in drinking water leads to a conclusion that both pesticide registration and pollutant discharge permitting provisions are needed to protect human health and aquatic species. PMID:24814945

  4. Requiring pollutant discharge permits for pesticide applications that deposit residues in surface waters.

    PubMed

    Centner, Terence; Eberhart, Nicholas

    2014-05-08

    Agricultural producers and public health authorities apply pesticides to control pests that damage crops and carry diseases. Due to the toxic nature of most pesticides, they are regulated by governments. Regulatory provisions require pesticides to be registered and restrictions operate to safeguard human health and the environment. Yet pesticides used near surface waters pose dangers to non-target species and drinking water supplies leading some governments to regulate discharges of pesticides under pollution discharge permits. The dual registration and discharge permitting provisions are burdensome. In the United States, agricultural interest groups are advancing new legislation that would exempt pesticide residues from water permitting requirements. An analysis of the dangers posed by pesticide residues in drinking water leads to a conclusion that both pesticide registration and pollutant discharge permitting provisions are needed to protect human health and aquatic species.

  5. Optimization of a single-drop microextraction procedure for the determination of organophosphorus pesticides in water and fruit juice with gas chromatography-flame photometric detection.

    PubMed

    Xiao, Qin; Hu, Bin; Yu, Chunhe; Xia, Linbo; Jiang, Zucheng

    2006-06-15

    A single-drop microextraction (SDME) procedure was developed for the analysis of organophosphorus pesticides (OPPs) in water and fruit juice by gas chromatography (GC) with flame photometric detection (GC-FPD). The significant parameters affecting the SDME performance such as selection of microextraction solvent, solvent volume, extraction time, stirring rate, sample pH and temperature, and ionic strength were studied and optimized. Two types of SDME mode, static and cycle-flow SDME, were evaluated. The static SDME procedure provided more sensitive analysis of the target analytes. Therefore, static SDME with tributyl phosphate (TBP) as internal standard was selected for the real sample analysis. The limits of detection (LODs) in water for the six studied compounds were between 0.21 and 0.56ng/mL with the relative standard deviations ranging from 1.7 to 10.0%. Linear response data was obtained in the concentration range of 0.5-50ng/mL (except for dichlorvos 1.0-50ng/mL) with correlation coefficients from 0.9995 to 0.9999. Environmental water sample collected from East Lake and fruit juice samples were successfully analyzed using the proposed method, but none of the analytes in both lake water and fruit juice were detected. The recoveries for the spiked water and juice samples were from 77.7 to 113.6%. Compared with the conventional methods, the proposed method enabled a rapid and simple determination of organophosphorus pesticides in water and fruit juice with minimal solvent consumption and a higher concentration capability.

  6. Effect of handling and processing on pesticide residues in food- a review.

    PubMed

    Bajwa, Usha; Sandhu, Kulwant Singh

    2014-02-01

    Pesticides are one of the major inputs used for increasing agricultural productivity of crops. The pesticide residues, left to variable extent in the food materials after harvesting, are beyond the control of consumer and have deleterious effect on human health. The presence of pesticide residues is a major bottleneck in the international trade of food commodities. The localization of pesticides in foods varies with the nature of pesticide molecule, type and portion of food material and environmental factors. The food crops treated with pesticides invariably contain unpredictable amount of these chemicals, therefore, it becomes imperative to find out some alternatives for decontamination of foods. The washing with water or soaking in solutions of salt and some chemicals e.g. chlorine, chlorine dioxide, hydrogen peroxide, ozone, acetic acid, hydroxy peracetic acid, iprodione and detergents are reported to be highly effective in reducing the level of pesticides. Preparatory steps like peeling, trimming etc. remove the residues from outer portions. Various thermal processing treatments like pasteurization, blanching, boiling, cooking, steaming, canning, scrambling etc. have been found valuable in degradation of various pesticides depending upon the type of pesticide and length of treatment. Preservation techniques like drying or dehydration and concentration increase the pesticide content many folds due to concentration effect. Many other techniques like refining, fermentation and curing have been reported to affect the pesticide level in foods to varied extent. Milling, baking, wine making, malting and brewing resulted in lowering of pesticide residue level in the end products. Post harvest treatments and cold storage have also been found effective. Many of the decontamination techniques bring down the concentration of pesticides below MRL. However, the diminution effect depends upon the initial concentration at the time of harvest, substrate/food and type of

  7. T-REX Version 1.5 User's Guide for Calculating Pesticide Residues on Avian and Mammalian Food Items - Appendix B - Initial Pesticide Residues on Arthropods

    EPA Pesticide Factsheets

    Obtain empirical data from the scientific literature and registrant-submitted studies to refine the initial residue assumptions of pesticides on arthropods that are simulated with TIM, T-REX, and T-HERPS

  8. Influence of pesticide residues on honey bee (Hymenoptera: Apidae) colony health in France.

    PubMed

    Chauzat, Marie-Pierre; Carpentier, Patrice; Martel, Anne-Claire; Bougeard, Stéphanie; Cougoule, Nicolas; Porta, Philippe; Lachaize, Julie; Madec, François; Aubert, Michel; Faucon, Jean-Paul

    2009-06-01

    A 3-yr field survey was carried out in France, from 2002 to 2005, to study honey bee (Apis mellifera L.) colony health in relation to pesticide residues found in the colonies. This study was motivated by recent massive losses of honey bee colonies, and our objective was to examine the possible relationship between low levels of pesticide residues in apicultural matrices (honey, pollen collected by honey bees, beeswax) and colony health as measured by colony mortality and adult and brood population abundance. When all apicultural matrices were pooled together, the number of pesticide residue detected per sampling period (four sampling periods per year) and per apiary ranged from 0 to 9, with the most frequent being two (29.6%). No pesticide residues were detected during 12.7% of the sampling periods. Residues of imidacloprid and 6- chloronicotinic acid were the most frequently detected in pollen loads, honey, and honey bee matrices. Several pairs of active ingredients were present concurrently within honey bees and in pollen loads but not in beeswax and honey samples. No statistical relationship was found between colony mortality and pesticide residues. When pesticide residues from all matrices were pooled together, a mixed model analysis did not show a significant relationship between the presence of pesticide residues and the abundance of brood and adults, and no statistical relationship was found between colony mortality and pesticide residues. Thus, although certain pesticide residues were detected in apicultural matrices and occasionally with another pesticide residual, more work is needed to determine the role these residues play in affecting colony health.

  9. Three years monitoring survey of pesticide residues in Sardinia wines following integrated pest management strategies.

    PubMed

    Angioni, Alberto; Dedola, Fabrizio

    2013-05-01

    This paper reports the results of a pesticide monitoring survey on wine grapes from the 2008-2010 vintage from vineyards grown according to integrated pest management strategies. A multi-residue gas chromatography-mass spectrometry method in electron ionization and chemical ionization mode has been used for the determination of 30 pesticides in wine samples. The analytical method showed good recoveries and allowed a good separation of the selected pesticides. Repeatability and intermediate precision showed good results with CV < 20 %. The instrumental method limits of determination (LOD) and of quantification (LOQ) were below the maximum residue levels set in wine. The analysis of the wines showed that pesticide residues were below the instrumental LOQ, and most of them were undetectable (pesticide applied has been detected in at least one cultivar. Metalaxil, myclobutanil, and penconazole were the pesticides most frequently found, while carignano and vermentino were the cultivars with the higher number of residues.

  10. Organophosphorus (OP) Pesticide Degradation in the Presence of Chlorinated Oxidants: Kinetics, Modeling, and Structure-Activity Relationships

    EPA Science Inventory

    The rates and pathways for pesticide transformation during drinking water treatment are known for only a few pesticides and under limited conditions. The resulting oxons are more toxic than the parent pesticides. The transformation rates and pathways for chlorpyrifos, an OP pest...

  11. Organophosphorus (OP) Pesticide Degradation in the Presence of Chlorinated Oxidants: Kinetics, Modeling, and Structure-Activity Relationships

    EPA Science Inventory

    The rates and pathways for pesticide transformation during drinking water treatment are known for only a few pesticides and under limited conditions. The resulting oxons are more toxic than the parent pesticides. The transformation rates and pathways for chlorpyrifos, an OP pest...

  12. Health risk for children and adults consuming apples with pesticide residue.

    PubMed

    Lozowicka, Bozena

    2015-01-01

    The presence of pesticide residues in apples raises serious health concerns, especially when the fresh fruits are consumed by children, particularly vulnerable to the pesticide hazards. This study demonstrates the results from nine years of investigation (2005-2013) of 696 samples of Polish apples for 182 pesticides using gas and liquid chromatography and spectrophotometric techniques. Only 33.5% of the samples did not contain residues above the limit of detection. In 66.5% of the samples, 34 pesticides were detected, of which maximum residue level (MRL) was exceeded in 3%. Multiple residues were present in 35% of the samples with two to six pesticides, and one sample contained seven compounds. A study of the health risk for children, adults and the general population consuming apples with these pesticides was performed. The pesticide residue data have been combined with the consumption of apples in the 97.5 percentile and the mean diet. A deterministic model was used to assess the chronic and acute exposures that are based on the average and high concentrations of residues. Additionally, the "worst-case scenario" and "optimistic case scenario" were used to assess the chronic risk. In certain cases, the total dietary pesticide intake calculated from the residue levels observed in apples exceeds the toxicological criteria. Children were the group most exposed to the pesticides, and the greatest short-term hazard stemmed from flusilazole at 624%, dimethoate at 312%, tebuconazole at 173%, and chlorpyrifos methyl and captan with 104% Acute Reference Dose (ARfD) each. In the cumulative chronic exposure, among the 17 groups of compounds studied, organophosphate insecticides constituted 99% acceptable daily intake (ADI). The results indicate that the occurrence of pesticide residues in apples could not be considered a serious public health problem. Nevertheless, an investigation into continuous monitoring and tighter regulation of pesticide residues is recommended

  13. Removal of chloropyrifos ethyl, tetradifon and chlorothalonil pesticide residues from citrus by using ozone.

    PubMed

    Kusvuran, Erdal; Yildirim, Deniz; Mavruk, Funda; Ceyhan, Mehmet

    2012-11-30

    The removal of chloropyrifos ethyl, tetradifon and chlorothalonil pesticide residues from the lemon, orange and grapefruit matrices were achieved by ozonation. All of chlorothalonil residues adsorbed onto the orange matrix were completely removed after 5 min ozonation. The highest removal percentages of tetradifon and chloropyrifos ethyl were achieved as 98.6 and 94.2%, respectively for the lemon and grapefruit matrices. All of diffused chlorothalonil and chloropyrifos ethyl residues were completely removed from both orange and grapefruit matrices after 5 min ozonation. Increasing of applied ozone dosage was not significantly effect on the removal percentages of pesticides whereas increasing of ozonation temperature caused a negative effect on the removal percentages of pesticides. The washing of the matrices with tap water was not as effective as ozonation in the removal of residual pesticides. Our results show that ozone treatment has a great potential for removing of residual pesticides from lemon, orange and grapefruit matrices.

  14. Cloning and expression of ophB gene encoding organophosphorus hydrolase from endophytic Pseudomonas sp. BF1-3 degrades organophosphorus pesticide chlorpyrifos.

    PubMed

    Barman, Dhirendra Nath; Haque, Md Azizul; Islam, Shah Md Asraful; Yun, Han Dae; Kim, Min Keun

    2014-10-01

    Chlorpyrifos is an organophosphate pesticide that has adverse effect on animals and plants. We isolated endophytic bacterial strain, Pseudomonas sp. BF1-3, from balloon flower root which can hydrolyze chlorpyrifos. A gene (ophB) encoding a protein involved in chlorpyrifos degradation from this strain was cloned into Escherichia coli DH5α for confirming enzyme activity. After sequencing, total 1024bp nucleotide sequences were found in the open reading frame of ophB. The chlorpyrifos degradation patterns by E. coli DH5α (ophB) were observed. During incubation in minimal salt (M9) medium supplemented with chlorpyrifos (100mgL(-1)), the E. coli DH5α harboring ophB degraded about 97% initial chlorpyrifos (100mgL(-1)) and accumulated 86mgL(-1) 3,5,6-trichloro-2-pyridinol (TCP) within 9 days. In addition, optical density (OD) of E. coli DH5α (ophB) culture at 600nm was increased from 0.172 to 1.118 within 2 days of inoculation in the chlorpyrifos supplemented M9 medium. The estimated molecular weight of purified OphB protein was determined to be 31.4kDa by SDS-PAGE. The OphB enzyme was most active at pH 8 and an optimal temperature around 35°C. These results indicate that endophytic bacteria are supposed to be useful for biological control of environments contaminated with pesticides.

  15. Effect of ultraviolet-absorbing vinyl film on organophosphorus insecticides dichlorvos and fenitrothion residues in spinach.

    PubMed

    Amano, Shoko; Katami, Takeo; Shibamoto, Takayuki

    2002-07-01

    Dichlorvos and fenitrothion residues found in spinach grown in greenhouse covered either by regular vinyl film or UV-absorbing vinyl film (UV-A) were analyzed by gas chromatography. After one day, dichlorvos residues in spinach covered with regular vinyl film and UV-A degraded by 97% and 80%, respectively, and degraded 100% after three days covered with regular vinyl film and six days covered with UV-A. After three days, fenitrothion residue in spinach covered with regular vinyl film degraded by 72% and then by 97% after six days; residue in spinach covered with UV-A degraded by 50% after three days and by 95% after six days. These results indicate that UV-A used to prevent the occurrence of insects and fungi in greenhouses reduced the degradation rates of dichlorvos and fenitrothion.

  16. Streamlined pretreatment and GC-FPD analysis of multi-pesticide residues in perennial Morinda roots: a tropical or subtropical plant.

    PubMed

    Liu, Hongmei; Kong, Weijun; Qi, Yun; Gong, Bao; Miao, Qing; Wei, Jianhe; Yang, Meihua

    2014-01-01

    In this study, a simple and rapid multi-pesticide residues analytical method has been developed and evaluated for simultaneous identification and quantification of 30 organophosphorus pesticides (OPPs) present at trace levels in perennial Morinda roots. Samples were firstly extracted and cleaned up with a streamlined method (modified QuEChERS), and then detected by gas chromatography with flame photometric detector (GC-FPD). For accurate quantification, representative matrix-matched calibration curves were applied to compensate matrix effects. Reasonable linearity was found in the concentration ranges of 0.04 and 1.28 μg mL(-1), with correlation coefficients r better than 0.9921 (0.9921-0.9998). The limits of detection (LODs) were between 0.005 and 0.02 μg mL(-1) for all investigated pesticides, while the limits of quantification (LOQs) were in the range of 0.01-0.04 μg mL(-1), below the regulatory maximum residue limits (MRL) suggested. Acceptable quantitative recoveries of 75.01-118.89% (96.0% on average) were achieved with relative standard deviations (RSD) varying from 0.89% to 9.80% (5.39% on average) at three different concentration levels of 0.05, 0.1 and 1.0 mg kg(-1). Out of all 40 batches of real samples, only fenitrothion was found in two samples, which was successfully confirmed by GC-MS. Based on these results, this analytical method has been proven to be fast, robust, accurate, selective, sensitive and easy to operate in the analysis of multiple pesticide residues in Morinda roots. Meanwhile, it also draws attention to the need of pesticide monitoring programs in local soils.

  17. A survey of organochlorine pesticide residues in cheese samples from three Mexican regions.

    PubMed

    Albert, L A; Alpuche, L; Bárcenas, C; Rendón, J

    1990-01-01

    Organochlorine pesticide residues were determined in cheese samples from three Mexican regions. All samples were found to be contaminated by these residues: p,p'-DDE was present in 100% of the samples. Other pesticides found with high frequencies were HCB, three of the BHC isomers, as well as heptachlor and its epoxide. Also found, although less frequently, were residues of p,p'-DDD, p,p'-DDT, aldrin, dieldrin and endrin. Samples from the region known as Comarca Lagunera had the highest number of pesticides per sample. The highest concentrations of residues were found in cheese samples from the Soconusco and the Comarca Lagunera regions.

  18. Automated determination of pesticide residues in olive oil by on-line reversed-phase liquid chromatography-gas chromatography using the through oven transfer adsorption desorption interface with electron-capture and nitrogen-phosphorus detectors operating simultaneously.

    PubMed

    Díaz-Plaza, Eva M; Cortés, Jose M; Vázquez, Ana; Villén, Jesús

    2007-12-07

    A rapid method for the multiresidue analysis of pesticides in olive oil is presented. Pesticides are analyzed by on-line coupling reversed-phase liquid chromatography-gas chromatography using the through oven transfer adsorption desorption (TOTAD) interface with subsequent simultaneous electron-capture and nitrogen-phosphorus detection by post-column splitter. An autosampler is employed and the olive oil is simply filtered before the chromatographic analysis. Organophosphorus, organochlorine and triazine pesticides are determined in one run. The limits of detection are below the required maximum residue levels and calibration curves are linear in the range tested. Repeatabilities (intra-day and inter-days) are good. The method was satisfactory applied to the routine analysis of numerous olive oil samples.

  19. [Simultaneous determination of pesticide residues in agricultural products by LC-MS/MS].

    PubMed

    Watanabe, Minae; Ueno, Eiji; Inoue, Tomomi; Ohno, Haruka; Ikai, Yoshitomo; Morishita, Toshio; Oshima, Harumi; Hayashi, Rumiko

    2013-01-01

    A method for the simultaneous determination of multiple pesticide residues in agricultural products was developed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The sample was extracted with acetonitrile. Co-extractives were removed by GPC/graphitized carbon column SPE, and silica gel/PSA cartridge column SPE. Pesticides in the test solution were determined by LC-MS/MS using scheduled MRM. Recoveries of 124 pesticides from spinach, brown rice, soybean, orange and tomato were tested at the level of 0.1 µg/g, and those of 121 pesticides ranged from 70 to 120% (RSD≤15%). Pesticide residues in 239 agricultural products were investigated by this method, and residues of 49 pesticides were detected in 98 agricultural products.

  20. Assessment of pesticide residues in commonly used vegetables in Hyderabad, Pakistan.

    PubMed

    Latif, Yawar; Sherazi, S T H; Bhanger, M I

    2011-11-01

    The aim of present study was to assess pesticide residues in vegetables in the Hyderabad region of Pakistan. The concentrations of six pesticides were determined by gas chromatography coupled with mass selective detector (GC-MSD) in locally produced vegetables purchased from wholesale markets. A total of 200 samples of eight vegetables viz. cauliflower, green chilli, eggplant, tomato, peas, bitter gourd, spinach and apple gourd were analyzed for pesticide residues. The results indicated that almost all samples were contained pesticides, only 39% contained pesticide residues at or below maximum residue limits (MRLs), and 61% contained pesticide residues above MRLs. From the six analyzed pesticides, carbofuran and chlorpyrifos were found above to MRLs with concentrations ranging from 0.01-0.39 and 0.05-0.96 mg/kg, respectively. The results provided important information on the current pesticide contamination status of some commonly used vegetables and pointed an urgent need to control the use of some excessively applied and potentially persistent pesticides, such as carbofuran and chlorpyrifos. Copyright © 2011 Elsevier Inc. All rights reserved.

  1. 7 CFR 29.425 - Submission and disposition of pesticide residues and end user(s) certification.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 7 Agriculture 2 2011-01-01 2011-01-01 false Submission and disposition of pesticide residues and... Miscellaneous § 29.425 Submission and disposition of pesticide residues and end user(s) certification. (a) Completion of certification: The importer shall complete a pesticide residue and end user(s) certification on...

  2. 7 CFR 29.425 - Submission and disposition of pesticide residues and end user(s) certification.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 7 Agriculture 2 2010-01-01 2010-01-01 false Submission and disposition of pesticide residues and... Miscellaneous § 29.425 Submission and disposition of pesticide residues and end user(s) certification. (a) Completion of certification: The importer shall complete a pesticide residue and end user(s) certification on...

  3. 7 CFR 29.425 - Submission and disposition of pesticide residues and end user(s) certification.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 7 Agriculture 2 2014-01-01 2014-01-01 false Submission and disposition of pesticide residues and... Miscellaneous § 29.425 Submission and disposition of pesticide residues and end user(s) certification. (a) Completion of certification: The importer shall complete a pesticide residue and end user(s) certification on...

  4. 7 CFR 29.425 - Submission and disposition of pesticide residues and end user(s) certification.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 7 Agriculture 2 2012-01-01 2012-01-01 false Submission and disposition of pesticide residues and... Miscellaneous § 29.425 Submission and disposition of pesticide residues and end user(s) certification. (a) Completion of certification: The importer shall complete a pesticide residue and end user(s) certification on...

  5. 7 CFR 29.425 - Submission and disposition of pesticide residues and end user(s) certification.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 7 Agriculture 2 2013-01-01 2013-01-01 false Submission and disposition of pesticide residues and... Miscellaneous § 29.425 Submission and disposition of pesticide residues and end user(s) certification. (a) Completion of certification: The importer shall complete a pesticide residue and end user(s) certification on...

  6. Determination of dialkyl phosphate metabolites of organophosphorus pesticides in human urine by automated solid-phase extraction, derivatization, and gas chromatography-mass spectrometry.

    PubMed

    Hemakanthi De Alwis, G K; Needham, Larry L; Barr, Dana B

    2008-01-01

    Organophosphorus (OP) pesticides are highly toxic but used commonly worldwide, nevertheless. Their urinary dialkylphosphate (DAP) metabolites are widely used for exposure assessment of OP pesticides in humans. We previously developed an analytical method to measure urinary DAPs utilizing solid-phase extraction (SPE)-derivatization-gas chromatography-tandem mass spectrometry (GC-MS-MS) with quantification using isotope-dilution technique. We now present a more cost-effective yet highly accurate method that can be easily adaptable to many laboratories for routine OP exposure assessment. This method is simple and fast and involves automated SPE of the metabolites followed by derivatization with pentafluorobenzyl bromide and quantification by GC-MS. Dibutyl phosphate (DBP) serves as the internal standard. The detection limits for the six metabolites ranged from 0.1 to 0.15 ng/mL. Depending on the metabolite the relative standard deviation of the analytical procedure was 2-15% for the metabolites. We compared performance of DBP as an internal standard with that of isotope-labeled compounds and found that DBP gives reliable results for the analytical procedure. We also optimized reaction parameters of pentafluorobenzylation.

  7. Limitations in the determination of maximum residue limits and highest residues of pesticides: Part I.

    PubMed

    Horváth, Zsuzsanna; Sali, Judit; Zentai, Andrea; Dorogházi, Enikő; Farkas, Zsuzsa; Kerekes, Kata; Ambrus, Árpád

    2014-01-01

    The pesticide usages are controlled by comparing residue concentrations in treated commodities to legally permitted maximum levels (MRLs) determined based on supervised trials designed to reflect likely maximum residues occurring in practice following authorised use. The number of trials available may significantly affect the accuracy of estimated maximum residues. We conducted a study with synthetic lognormal distributions with mean of 1 and standard deviations of 0.8 and 1.0, which reflect the residue distributions observed in practice. The likely residues in samples were modelled by drawing random samples of size 3, 5, 10 and 25 from the synthetic populations. The results indicate that the estimations of highest residues (HR), used for calculation of short-term intake, and the MRLs, serving as legal limits, are very uncertain based on 3-5 trials indicated by the calculated HR0.975/HR0.025 and MRL0.975/MRL0.025 ratios of 12 and 9, and 13 and 10, respectively, which question the suitability of such trials for the intended purpose. As the 95% range of HR and MRL rapidly decreases with number of trials, ideally ≥15 but minimum 6-8 trials should be used for estimation of HR and MRL according to the current typical practice of Codex Alimentarius.

  8. Cumulative risk assessment of pesticide residues in food.

    PubMed

    Boobis, Alan R; Ossendorp, Bernadette C; Banasiak, Ursula; Hamey, Paul Y; Sebestyen, Istvan; Moretto, Angelo

    2008-08-15

    There is increasing need to address the potential risks of combined exposures to multiple residues from pesticides in the diet. The available evidence suggests that the main concern is from dose addition of those compounds that act by the same mode of action. The possibility of synergy needs to be addressed on a case-by-case basis, where there is a biologically plausible hypothesis that it may occur at the levels of residues occurring in the diet. Cumulative risk assessment is a resource-intense activity and hence a tiered approach to both toxicological evaluation and intake estimation is recommended, and the European Food Safety Authority (EFSA) has recently published such a proposal. Where assessments have already been undertaken by some other authority, full advantage should be taken of these, subject of course to considerations of quality and relevance. Inclusion of compounds in a cumulative assessment group (CAG) should be based on defined criteria, which allow for refinement in a tiered approach. These criteria should include chemical structure, mechanism of pesticidal action, target organ and toxic mode of action. A number of methods are available for cumulating toxicity. These are all inter-related, but some are mathematically more complex than others. The most useful methods, in increasing levels of complexity and refinement, are the hazard index, the reference point index, the Relative Potency Factor method and physiologically based toxicokinetic modelling, although this last method would only be considered should a highly refined assessment be necessary. Four possible exposure scenarios are of relevance for cumulative risk assessment, acute and chronic exposure in the context of maximum residue level (MRL)-setting, and in relation to exposures from the actual use patterns, respectively. Each can be addressed either deterministically or probabilistically. Strategies for dealing with residues below the limit of detection, limit of quantification or limit

  9. Determination of selected pesticides in water samples adjacent to agricultural fields and removal of organophosphorus insecticide chlorpyrifos using soil bacterial isolates

    NASA Astrophysics Data System (ADS)

    Hossain, M. S.; Chowdhury, M. Alamgir Zaman; Pramanik, Md. Kamruzzaman; Rahman, M. A.; Fakhruddin, A. N. M.; Alam, M. Khorshed

    2015-06-01

    The use of pesticide for crops leads to serious environmental pollution, therefore, it is essential to monitor and develop approaches to remove pesticide from contaminated environment. In this study, water samples were collected to monitor pesticide residues, and degradation of chlorpyrifos was also performed using soil bacteria. Identification of pesticide residues and determination of their levels were performed by high-performance liquid chromatography with photodiode array detector. Among 12 samples, 10 samples were found contaminated with pesticides. Chlorpyrifos was detected in four tested samples and concentrations ranged from 3.27 to 9.31 μg/l whereas fenitrothion ranging from (Below Detection Limit, <0.1 μg/l) to 33.41 μg/l in the tested samples. Parathion was found in two tested samples at the concentration of 0.73 and 6.23 μg/l. None of the tested samples was found contaminated with Methoxychlor, DDT and Ethion. Three soil bacterial isolates, Pseudomonas peli BG1, Burkholderia caryophylli BG4 and Brevundimonas diminuta PD6 degraded chlorpyrifos completely in 8, 10 and 10 days, respectively, when 20 mg/l chlorpyrifos was supplied as sole source of carbon. Whereas, BG1, BG4 and PD6 took 14, 16 and 16 days, respectively, for complete removal of 50 mg/l chlorpyrifos. Chlorpyrifos degradation rates were found maximum by all three isolates at 2nd day of incubation for both tested concentrations. The results of the present study suggest the need for regular monitoring of pesticide residues in water, to protect the aquatic environment. Chlorpyrifos degrading bacterial isolates can be used to clean up environmental samples contaminated with the organophosphate pesticides.

  10. Food safety in Thailand. 3: Pesticide residues detected in mangosteen (Garcinia mangostana L.), queen of fruits.

    PubMed

    Phopin, Kamonrat; Wanwimolruk, Sompon; Prachayasittikul, Virapong

    2017-02-01

    For developing countries like Thailand, regulation of pesticide usage exists, but it is not fully enforced. Therefore, pesticide residues in vegetables and fruits have not been well monitored. This study aimed to determine the pesticide residues in mangosteen fruits sold in Thailand. The mangosteen samples (n = 111) were purchased and the contents of 28 pesticides were analysed by GC-MS/MS method. Of the pesticides tested, eight were found in 100% of the mangosteen samples. However, in 97% of these samples, either chlorothalonil, chlorpyrifos, diazinon, dimethoate, metalaxyl or profenofos was detected exceeding their maximum residue limits (MRLs), representing a 97% rate of pesticide detection above the MRL. This rate is much higher than those found in other fruits sold in developed countries. However, this conclusion excludes the fresh Thai mangosteens grown for export, as these are generally cultivated and harvested to GAP standards. Since the edible part of the mangosteen is the pulp, washing the fruits with running water can reduce the risk of pesticide residues contaminating the pulp which would be eaten by the consumer. The findings strongly suggest that routine monitoring of pesticide residues in fruits and vegetables is required to reduce the health risks associated with consuming contaminated food. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  11. Pesticide Residue Monitoring on South African Fresh Produce Exported over a 6-Year Period.

    PubMed

    Mutengwe, M T; Chidamba, L; Korsten, L

    2016-10-01

    Six years of pesticide residue data from fresh produce destined for the export market were analyzed for the period 2009 to 2014. A total of 37,838 fruit (99.27%) and vegetable (0.73%) data sets analyzed for the presence of 73 pesticides were compared. Pesticides were detected on 56.46% of samples, of which 0.78% had multiple residues. Noncompliances detected were because of the use of unregistered pesticides (0.73%), values that exceeded established maximum residue levels (MRLs) (0.32%), or the combination of values that exceeded MRLs and the use of unregistered pesticide residues (0.003%). The most commonly detected pesticides that exceeded established MRLs were imazalil (37.71%), prochloraz (28.69%), and iprodione (5.74%). The unregistered pesticide most often found on grapes and avocados was also imazalil (62.23%) and, on nectarines and avocados, diphenylamine (11.15%). Exceedances of MRL values were mostly associated with oranges (43.44%), avocados (27.87%), grapefruits (7.38%), and lemons (6.56%). Residual pesticide monitoring on fruits and vegetables is a key tool to ensure conformity with regulatory requirements and compliance with good agricultural practices and the trade requirements set by the importing country.

  12. Multi pesticide and PCB residues in Nile tilapia and catfish in Assiut city, Egypt.

    PubMed

    Yahia, Doha; Elsharkawy, Eman E

    2014-01-01

    The current study investigated the levels of multi pesticide residues in the highly consumed types of Nile fish in Egypt: tilapia and cat fish. A total of 50 Nile tilapia (Oreochromis niloticus) and 50 African catfish (Clarias gariepinus) were collected from two areas in Assiut city, where most industries are situated and where agricultural activities and raising of farm animals are the main activities. In the first area, Elwasta, there is an electrical power station, and the second area, Mankbad, there is a cement factory. Fish samples were analyzed by High Resolution Gas Chromatography/Mass Spectrometry. Average pesticide residue concentrations±SE in muscle of tilapia and catfish (n = 10 pooled samples with five fish each) were determined. The results indicated the presence of different types of organophosphorous (OPs), organochlorine (OC), polychlorinated biphenyles (PCBs), hexachlorobenzene (HCB) and trifluralin pesticides in Elwasta and Mankbad in varying degrees. Diazenon was the only OP pesticide which exceeded the permissible limit in both investigated areas with the two types of fish. On the other hand, OCs, PCBs, HCB and trifluralin pesticide residue levels have not exceeded the maximum allowable concentration limit. In general, a higher pesticide residue level was obtained in Mankbad than Elwasta. In addition, higher values are realized for the detected pesticide residues in cat fish than tilapia. The results of the study have shown the extensive and recent use of these types of pesticides in the present time in Egypt. © 2013 Elsevier B.V. All rights reserved.

  13. Pesticide residues in orange fruit from citrus orchards in Nuevo Leon State, Mexico.

    PubMed

    Suárez-Jacobo, A; Alcantar-Rosales, V M; Alonso, D; Heras-Ramírez, M E; Elizarragaz-De La Rosa, D; Lugo-Melchor, O Y; Gaspar-Ramirez, O

    2017-04-04

    Some international organizations established Maximum Residue Limits (MRLs) in food to protect human health. Mexico lacks regulations in this matter, affecting national and international trade from agroindustry. The aim of this study was to diagnose pesticide residues in oranges from Nuevo Leon, México, in citrus orchards. In May 2014, 100 orange fruit samples were taken randomly from orchards and subjected to analysis for 93 pesticides at residual level by GC/QQQ-MS and LCQ-TOF-MS. Results showed presence of 15 pesticide residues in the samples. The comparison of the residual levels of pesticides found in orange samples among the MRLs allowed by USA, EU and Japanese regulations demonstrated that all samples were below MRLs issued by USA and Japan. Some orange samples were above MRLs issued by the EU. This provides a basis to establish strategies in order to satisfy International Standards to protect human health and encourage Food Safety in Mexico.

  14. Decontamination of spills and residues of some pesticides and of protective clothing worn during the handling of the pesticides

    SciTech Connect

    Armour, M.A.; Nelson, C.; Sather, P. Briker, Y.

    1996-12-31

    Users of pesticides may have waste or surplus quantities or spills for disposal. One alternative is to deactivate the pesticide at the handling site by using a straightforward chemical reaction. This option can be practical for those who use relatively small quantities of a large variety of pesticides, for example, greenhouse workers, small farmers, and agricultural researchers. This paper describes practical on-site methods for the disposal of spills or small waste quantities of five commonly used pesticides, Diazinon, Chlorpyrifos, Iprodione, 2,4-D, and Captan. These have been tested in the laboratory for the rate of disappearance of the pesticide, the degree of conversion to nontoxic products, the nature and identity of the products, the practicality of the method, and the ease of reproducibility. Methods selected were shown to be safe for the operator, reliable, and reproducible. Greater than 99% of the starting material had to be reacted under reasonable conditions and length of time. Detailed descriptions of the reactions are presented, so that they can be performed with reproducible results. Protective clothing worn during the handling and application of pesticides may become contaminated. Simple laundering does not always remove all of the pesticide residues. Thus, chronic dermal exposure may result from the pesticide-contaminated clothing. Appropriate methods of laundering using specific pretreatments have been determined. 7 refs.

  15. Adverse Effects of Pesticides Residues on Biochemical Markers in Pakistani Tobacco Farmers

    PubMed Central

    Khan, Dilshad A; Bhatti, Mahwish M; Khan, Farooq A; Naqvi, Syed T; Karam, A

    2008-01-01

    Tobacco is an important cash crop of Pakistan and tremendous amount of irrational pesticides are being used to control insect growth. The frequency of plasma pesticide residues above acceptable daily intake (ADI) and its correlation with biochemical markers for assessment of adverse health effects in the tobacco farmers at district Sawabi, Pakistan was determined. Total 109 adult males consisting of 55 tobacco farmers exposed to pesticides and 54 controls were included. Pesticides residues in blood were analyzed on HPLC and GC-NPD. Plasma butyrylcholinesterase (BChE) was analyzed by Ellman's method. Biochemical markers including serum calcium, phosphorus, urea, creatinine, bilirubin and liver enzymes were measured on Selectra-E auto analyzer. The tobacco farmers had multiple pesticides residues above ADI in their blood consisting of 35 (63%) methomyl; 31 (56%) thiodicarb; 34(62%) cypermethrin; 27 (49%) Imidacloprid; 18 (32%) Methamidophos and 15 (27%) endosulfan. BChE activity was significantly decreased in the pesticides exposed farmers as compared to controls (P<0.001). Plasma biochemical markers including ALT, AST, CK, LDH and phosphate were significantly raised in the pesticides exposed farmers as compared to control group (P<0.001). Total pesticides residues revealed a significant positive correlation with AST (r=0.42), LDH(r= 0.47), ALT (r=0.20) and phosphorus (r=0.51). Excessive exposure to pesticide caused cytotoxic changes in the hepatic and renal biochemical markers which were positively correlated with pesticide residue. Hence these biomarkers might be used in addition to BChE activity for monitoring of adverse effects of pesticides on the health of farm workers. PMID:19079663

  16. Multiple pesticide residues in live and poisoned honeybees - Preliminary exposure assessment.

    PubMed

    Kiljanek, Tomasz; Niewiadowska, Alicja; Gaweł, Marta; Semeniuk, Stanisław; Borzęcka, Milena; Posyniak, Andrzej; Pohorecka, Krystyna

    2017-02-08

    Study combines data about the exposure of honeybees to pesticides from plant protection products and veterinary medicinal products. Residues of 200 pesticide and pesticide metabolites in 343 live and 74 poisoned honeybee samples, obtained during the years of 2014-2015, were determined by LC-MS/MS and GC-MS/MS. In 44% of live honeybee 48 different pesticide residues were found, mainly amitraz metabolites (DMF, DMPF) and chlorpyrifos. In 98% of poisoned honeybee 57 pesticides and metabolites were detected, mainly chlorpyrifos, dimethoate and clothianidin. In total 84 different pesticides were detected both in live and poisoned honeybees, they indicate 30 various modes of action. Differences between mean number of pesticide residues detected in live and poisoned honeybees clearly indicate the impact of multiple pesticides on honeybee health. Possible impact of systemic fungicides on the health of honeybees was studied. Applicability of hazard quotient counted as ratio between concentration of pesticides in honeybees and lethal dose in the interpretation whether detected concentration indicates acute toxic effects was shown.

  17. Occurrence of non extractable pesticide residues in physical and chemical fractions of two soils

    NASA Astrophysics Data System (ADS)

    Andreou, Kostas; Semple, Kirk; Jones, Kevin

    2010-05-01

    Soils are considered to be a significant sink for organic contaminants, including pesticides, in the environment. Understanding the distribution and localisation of aged pesticide residues in soil is of great importance for assessing the mobility and availability of these chemicals in the environment. This study aimed to characterise the distribution of radiolabeled herbicide isoproturon and the radiolabeled insecticides diazinon and cypermethrin in two organically managed soils. The soils were spiked and aged under laboratory conditions for 17 months. The labile fraction of the pesticides residues was recovered in CaCl2 (0.01M) and then subjected to physical size fractionation using sedimentation and centrifugation steps, with >20μm, 20-2μm and 2-0.1μm soil factions collected. Further, the distribution of the pesticide residues in the organic matter of the fractionated soil was investigated using a sequential alkaline extraction (0.1N NaOH) into humic and fulvic acid and humin. Soil fractions of 20-2μm and 2-0.1μm had the largest burden of the 14C-residues. Different soil constituents have different capacities to form non-extractable residues. Soil solid fractions of 20-2 µm and <2 µm had far greater affinity to the 14C-pesticide residues than the coarser fraction (>20 µm). Fulvic acid showed to play a vital role in the formation and stabilisation of non-extractable 14C-pesticide residues in most cases.Assessment of the likelihood of the pesticide residues to become available to soil biota requires an understanding of the structure of the SOM matrix and the definition of the kinetics of the pesticide residues in different SOM pools as a function of the time.

  18. Environmental impact and remediation of residual lead and arsenic pesticides in soil

    USDA-ARS?s Scientific Manuscript database

    Lead arsenate (PbHAsO4) was used as a pesticide for over 50 years in orchards throughout the world, and residual lead and arsenic have been found in high concentrations in these orchard soils long after the pesticide use ended. These high concentrations of lead and arsenic may create a potential ri...

  19. Sample preparation approaches for the analysis of pesticide residues in olives and olive oils

    USDA-ARS?s Scientific Manuscript database

    Agricultural practices generally require the use of pesticides by olive growers for the best olive and olive oil production. Thus, analytical methods are needed to identify and quantify the pesticide residues that may be present, and ensure that the product complies with regulatory requirements. I...

  20. MONITORING THE TRANSFER OF PESTICIDE RESIDUES FROM SOFT SURFACES TO FOODS

    EPA Science Inventory

    The Food Quality Protection Act of 1996 requires assessing pesticide residue exposures to children. Contact of soft surfaces by foods and the ingestion of the food represents a pesticide exposure pathway. Chlorpyrifos has widespread use indoors and would be protected from envir...