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Implementation of cost-effective, reliable, and efficient technologies for the sensitive, rapid, and accurate detection of pesticide residues in agriproducts presents a promising solution to the escalating food safety concerns. Herein, a high-performance surface-enhanced Raman scattering (SERS) aptasensor based on nanotag (AuNS@4-MBN@Ag-aptamer) was introduced for ultrasensitive, reliable, and interference-free detection of chlorpyrifos (CPF). This aptasensor featured star-shaped bimetallic nanotag as the principal Raman signal enhancement material and 4-mercaptobenzonitrile (4-MBN) as "biological-silent"-window reporter (at 2228 cm -1 ). Moreover, cDNA-linked Fe 3 O 4 @AuNPs (FA-cDNA) served as magnetic substrates to simplify the separation process of FA-cDNA-combined nanotags. In the aptasensor, the formation of FA-cDNA-aptamer-AuNS@4-MBN@Ag hybrids was hindered by CPF, and its Raman intensity decreased with increasing CPF concentration. Under optimal SERS conditions, the aptasensor exhibited a broad linear detection range from 2.5 × 10 2 to 5.0 × 10 4  pg⋅mL -1 , with an impressively low limit of detection of 220.35 pg⋅mL -1 (signal-to-noise ratio = 3). The selectivity and reproducibility assessments highlighted its exceptional sensitivity and interference-free capabilities. Furthermore, practical applications on wheat and apples demonstrated satisfactory spiked recovery rates, ranging from 89.61% to 107.33% (relative standard deviation ≤ 14.55%). Consequently, the high-performance "biological-silent"-window nanotag-based aptasensor is a promising tool for monitoring trace CPF in complex matrices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

This study investigates the behaviour of gold nanoparticles (AuNPs) when exposed to chlorpyrifos, an agricultural pesticide, and its application in detecting the pesticide via surface-enhanced Raman spectroscopy (SERS). Under synergistic addition of NaCl, AuNPs undergo agglomeration at lower chlorpyrifos concentrations but aggregation at higher concentrations, resulting in a distinctive nonlinear SERS response. A linear relationship is obtained between 0.001 and 1 ppm with detection limit (LOD) of 0.009 ppm, while an inverse response is observed at higher concentrations (1-1000 ppm) with a LOD of 1 ppm. Combining the colorimetric response of AuNP solutions, their absorbance spectra, and principal component analysis can improve detection reliability. The assay, coupled with a simple recovery method using acetonitrile swabbing, achieves high reproducibility in detecting chlorpyrifos in cucumber, even at concentrations as low as 0.11 ppm. This approach can be tailored for various chlorpyrifos concentrations not only in cucumbers but also in different food matrices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

This study evaluated the presence of the three pesticides methomyl (MET), carbendazim (CBZ) and chlorpyrifos-ethyl (CPE), as well as the degradation product of CPE (3,5,6-trichloro-2-pyridinol; TCP), in 44 honey samples from all 12 regions of Morocco. With a validated HPLC-UV method occurrence frequencies of 63.6% for MET, 54.5% for CBZ, 95.1% for CPE and 34.1% for TCP were obtained, even at concentrations higher than the maximum residue limits for MET, CPE and TCP. Based on the predominant pesticide, principal component analysis separated sampling regions into three groups. Risk assessment indicated that ingestion of these pesticides, alone or in combination, in honey did not pose a risk to consumers (HQ and HI < 1).

Chlorpyrifos (CPF) residues in food pose a serious threat to ecosystems and human health. Herein, we propose a three-dimensional folded paper-based microfluidic analysis device (3D-μPAD) based on multifunctional metal-organic frameworks, which can achieve rapid quantitative detection of CPF by fluorescence-colorimetric dual-mode readout. Upconversion nanomaterials were first coupled with a bimetal organic framework possessing peroxidase activity to create a fluorescence-quenched nanoprobe. After that, the 3D-μPAD was finished by loading the nanoprobe onto the paper-based detection zone and spraying it with a color-developing solution. With CPF present, the fluorescence intensity of the detection zone gradually recovers, the color changes from colorless to blue. This showed a good linear relationship with the concentration of CPF, and the limits of detection were 0.028 (fluorescence) and 0.043 (colorimetric) ng/mL, respectively. Moreover, the 3D-μPAD was well applied in detecting real samples with no significant difference compared with the high-performance liquid chromatography method. We believe it has huge potential for application in the on-site detection of food hazardous substance residues.

Pesticides are used in vegetable farming to control pests and diseases, reduce crop losses and improve yield. The study examined pesticide residues in irrigation waters and leafy green vegetables grown in some farming areas in Accra, Ghana. Three types of irrigation water sources ( n  = 23) and two exotic and four indigenous Ghanaian leafy vegetables ( n  = 34) from 10 farming areas in Accra, Ghana were collected and examined for 15 organochlorines, 13 organophosphorus and 9 synthetic pyrethroids pesticide residues using the modified QuEChERS procedure. Pesticide residues were detected on 50% (17/34) of the leafy vegetable and 52% (12/23) of the irrigation water samples analysed. Chlorpyrifos and deltamethrin were the most detected pesticide residues in the vegetables and irrigation water. About 26.5% of the vegetables contained pesticide residues exceeding the EU maximum residue limits, so vegetable farmers should be encouraged to comply with appropriate measures on pesticide use to enhance food safety.

Organophosphate pesticides (OPs) are often used as insecticides and acaricides in agriculture, thus improving yields. OP residues may pose a serious threat, duetoinhibitionof the enzymeacetylcholinesterase(AChE). Therefore, a competitive bio-barcode immunoassay was designed for simultaneous quantification of organophosphate pesticide residues using AuNP signal amplification technology and Au@Pt catalysis. The AuNP probes were labelled with antibodies and corresponding bio-barcodes (ssDNAs), MNP probes coated with ovalbumin pesticide haptens and Au@Pt probes functionalized with the complementary ssDNAs were then prepared. Subsequently, pesticides competed with MNP probes to bind the AuNP probes. The recoveries of the developed assay were ranged from 71.26 to 117.47% with RSDs from 2.52 to 14.52%. The LODs were 9.88, 3.91, and 1.47 ng·kg -1 , for parathion, triazophos, and chlorpyrifos, respectively. The assay was closely correlated with the data obtained from LC-MS/MS. Therefore, the developed method has the potential to be used as an alternative approach for detection of multiple pesticides., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

A visible-light-responsive azobenzene derivative, 3,5-dichloro-4-((2,6-dichloro-4-(methacryloyloxy)phenyl)diazenyl)benzoic acid, was synthesized and used as the functional monomer to fabricate a visible-light-responsive core-shell structured surface molecularly imprinted polymer (PS-co-PMAA@VSMIP). After removal of the sacrificial PS-co-PMAA core, a hollow structured surface molecularly imprinted polymer (HVSMIP) was obtained. Both the PS-co-PMAA@VSMIP and HVSMIP were used for the detection of chlorpyrifos, a moderately toxic organophosphate pesticide. They exhibited good visible-light-responsive properties (550 nm for trans→cis and 440 nm for cis→trans isomerization for an azobenzene chromophore) in ethanol/water (9:1, v/v). Compared with the PS-co-PMAA@VSMIP, the HVSMIP had a larger surface area, pore volume, binding capacity, imprinting effect, maximum chemical binding capacity, dissociation constant, and photo-isomerization rate. The HVSMIP was applied to detect trace chlorpyrifos in fruit and vegetable samples. This was achieved by measuring the trans→cis rate constant of the HVSMIP in the sample solution, with good recoveries, low relative standard deviations, and a low detection limit., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Background: Variability of pesticide residues in food item plays a key role for the evaluation of consumer food safety. However, variability factors (VFs) derived from the large size fruit crops are still scarce. Therefore, the present work was aimed to quantify pesticide residues and to estimate VFs in large size fruit crops of mango and guava., Results: A total of 140 mango and 130 guava samples from different marketplaces in Bangladesh were collected to estimate the variability of pesticide residues (acephate, diazinon, malathion, fenitrothion, chlorpyrifos, quinalphos, dimethoate and cypermethrin) by in-house validated methods based on modified QuEChERS extraction and gas chromatography coupled with electron capture detector (ECD) and flame thermionic detector (FTD). The method was validated at three fortification levels (0.01, 0.10 and 0.30 mg kg -1 ) and satisfactory recoveries (80-111%) with relative standard deviation (RSD r ) ≤ 13% were achieved. A wide variation of residues was found in the analyzed samples. In the case of mango, the ranges of residues were 0.011-0.314, 0.015-0.04, and 0.05-0.291 mg kg -1 , respectively, for cypermethrin, chlorpyrifos, and dimethoate, while in the case of guava, the ranges were 0.04-0.113, and 0.03-0.290 mg kg -1 , respectively, for cypermethrin and acephate. The average VF for mango was 4.06 and it was 5.70 for guava., Conclusion: VFs originating from the marketed samples of mango and guava are reported in this study for the first time. The estimated VFs were higher than the default value of 3, therefore, the default VFs should be reconsidered when more data are obtained regarding large size crops. © 2021 Society of Chemical Industry., (© 2021 Society of Chemical Industry.)

The feasibility of sugarcane bagasse to be employed as an alternative solid support for clean-up is presented during the development and validation of an analytical method to determine chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate) (CP) in tomato by HPLC-DAD. The efficiency of the method consisting of ultrasonic assisted extraction with acetonitrile and dispersion with salts, followed by dispersive phase extraction with powdered sugarcane bagasse is presented for three spiking levels relating to the established CP maximum residue limit (MRL) for industrial tomato in Brazil, 0.5 mg kg -1 (½ MRL, MRL and 2 MRL). Satisfactory results were obtained in terms of trueness (recovery range: 76.5-120.1%), intermediate precision (1.0-5.2%) and repeatability (4.7-12.8%), expressed as relative standard deviation. The proposed method has a limit of quantification of 0.25 mg kg -1 and could be deployed as cost effective routine analysis to monitor CP in tomato samples in processed food industries., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The aims of this research were 1) to find out the possible microbiological contamination and residues of pesticides (chlorpyrifos and cypermethrin) in lettuce grown in Bahía Blanca's horticultural belt, and bacteriological quality of waters used for irrigation and post-harvest washing, 2) to investigate and compare the internalization capacity of a strain of Escherichia coli isolated from irrigation water with another hospital uropathogenic strain. Some strains of bacteria can internalize into the plant tissue. This capability presents food safety threats as they cannot be removed with standard sanitation practices. To determine bacteriological quality of lettuce, E. coli , Salmonella spp and E. coli O157: H7/NM (n = 10) were investigated. Bacteriological quality of water was determined by quantification of fecal coliforms/100 mL (n = 20). Pesticides were determined by using an improved and validated QuEChERS method combined with GC-MSD. Irrigation water in 19/20 samples did not present health risk. Bacteriological quality of lettuce met demands in 9/10 samples. Pesticides were detected in half of the samples, values exceeding the FAO recommendations. An effort is strongly recommended to implement both, best phytosanitary practices and monitoring programmes. Uropathogenic strain was able to internalize into plant tissue, while the nonpathogenic one was not.

The influence of some additives, including metal ions, antioxidants, enzyme inhibitors and organic solvents, on the storage stability of four organophosphorus pesticides in cucumber samples were investigated. It was found that metal ions, including Al 3+ , Fe 3+ , and Co 2+ , increased the stability of dichlorvos, malathion, and chlorpyrifos. Conversely, Al 3+ , Fe 3+ , Fe 2+ , and Co 2+ caused catalytic degradation of diazinon. With the addition of organic solvents (CH 2 Cl 2 , CHCl 3 , CCl 4 , CH 3 OH and CH 3 COCH 3 ), remaining of diazinon residues was higher (16-54%) after storage for seven days. CCl 4 was associated with the highest retention of malathion, diazinon, and chlorpyrifos (33%, 48% and 44%, respectively) in samples. SDS also stabilized the pesticides since residues were, again, higher (13-38%) after seven days storage. Furthermore, addition of Al 3+ and Fe 3+ decreased peroxidase (POD) activity and inhibited degradation of dichlorvos and malathion. After 14 days, lyophilization increased the pesticide residues remaining by 36%, 29%, and 58% for diazinon, malathion and chlorpyrifos, respectively. Overall, the stability of these pesticides during storage is impacted by water content and addition of exogenous substances. This could ensure higher quality of pesticide residue data in samples., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Fengmao Liu has received the Special Found for Agro-scientific Research in the Public Interest. Other authors are students of China Agricultural University. The authors have no conflicts of interest to declare. Fengmao Liu declares that he has no conflict of interest. Yanli Bian, Yihan Wang, Xiaohan Li and Boning Wang declare that they have no conflict of interests., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

A QuEChERS multi-residue GC-MS/MS method was developed for determining 160 pesticides in fresh edible snails. The method was validated according to the EU guidance SANTE/12682/2019. Twenty-seven different pesticides were quantified in the 824 samples analysed. Of these, 22.09% contained pesticide residues; in one case six different pesticides. The most frequently quantified pesticides were chlorpyrifos (108 samples), cypermethrin (50), difenoconazole (24), oxyfluorfen (13), lambda-cyhalothrin (12), tetraconazole and azoxystrobin (7). Other pesticides were found in <5 samples. Of the samples containing residues, 154 exceeded the EU legal limit. However, the estimated daily intake of pesticide residues showed that snail consumption does not represent appreciable risks to consumer health.

The organophosphorus pesticides (OPPs) commonly used in agricultural practices can pose a risk of potential exposure to humans via food consumption. We describe an analytical method for solid-phase extraction coupled with high-performance liquid chromatography-diode array detector (SPE-HPLC-DAD) for the detection of OPPs (quinalphos, diazinon, and chlorpyrifos) in rice grains. The isolation of targeted residues was initiated with double extraction before SPE-HPLC-DAD, crucially reducing matrix interferences and detecting a wide range of multiple residues in rice grains. Coefficients of 0.9968 to 0.9991 showed a strong linearity, with limits of detection and quantification ranging from 0.36 to 0.68 µg/kg and from 1.20 to 2.28 µg/kg, respectively. High recoveries (80.4-110.3%) were observed at 3 spiking levels (50, 100, and 200 µg/kg), indicating good accuracy. The relative standard deviations of all residues (0.19-8.66%) validated the method precision. Sample analysis of 10 rice grain types (n = 30) available in the Asian market revealed that quinalphos, diazinon, and chlorpyrifos at concentrations of 1.08, 1.11, and 1.79 µg/kg, respectively, remained far below the maximum residue limits (0.01-0.5 mg/kg). However, regular monitoring is necessary to confirm that multiresidue occurrence remains below permissible limits while controlling pests. Environ Toxicol Chem 2020;39:1908-1917. © 2020 SETAC., (© 2020 SETAC.)

A paper-based device (PBD) for the detection of chlorpyrifos pesticide at field application was fabricated based on the principles of enzyme inhibition and image processing. Rhizopus niveus lipase, p-nitrophenol palmitate and Whatman No.1 paper were used as an enzyme, substrate and support matrix, respectively. The performance of functionalized PBD was tested for lateral flow assay reaction in pure water (negative control), artificial pesticide water (positive control) and selected fruits and vegetables wash water (test). The digital image of the PBD after the test was captured using an android smartphone and analyzed in MATLAB software. Different colour space models such as, grey, RGB, HSV and YCbCr were studied and the Cb coordinate was chosen for its higher linearity (R 2  = 0.988) with pesticide concentration. Experimental variations such as paper length, relative concentration ratio of the substrate and enzyme were investigated to minimize the product cost and analysis time. The developed PBD showed a significant response over wide range of sample solution's pH and operational temperature. Further, a long-term storage stability was measured for developed PBD. The LOD and LOQ were found to be 0.065 mgL -1 and 0.198 mgL -1 . The results obtained from newly developed image processing method showed 92.8% accuracy with microtiter plate assay. Higher MRL was determined in the wash water of cauliflower, grapes, coriander leaves, brinjal and bitter guard. Overall, the developed paper biosensor was precise, cost effective and most suitable for field applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Due to the concern over food safety, it is important to detect the pesticides residues in agricultural products. Here, a highly sensitive and low background fluorescent strategy for the detection of pesticides residues has been developed. The fluorescence intensity of N-methyl mesoporphyrin IX (NMM) binding G-quadruplex could be turn off because of inhibiting effect of the pesticides on the acetylcholinesterase (AChE) activity. For that, four single-stranded DNAs (named linker, trigger, H1 and H2, respectively) are rational designed and T-Hg-T mismatches duplex DNAs as a recognizer combined with the separation of magnetic beads. The design of hybridization chain reaction (HCR) amplification strategy assisted by magnetic separation has been adopted to improve the detection sensitivity. In the presence of pesticides, the amount of the thiol group generated by hydrolysis reaction of acetylcholine (ACh) is reduced, lead to release of less trigger DNA. Therefor subsequent HCR process is retarded with decreased fluorescence intensity. The reduced fluorescence intensity has a quantitative relationship with the pesticide concentration. The limit of detection of chlorpyrifos was estimated to be 2.0 ng ml -1 . It has been applied to detect the pesticides residues in real samples.

This paper presents, for the first time, results for chlorpyrifos (CHLP) in Polish fruits and vegetables over the course of a long period of research, 2007-2016, with toxicological aspects. The challenge of this study was to re-evaluate the impact of chlorpyrifos residues in fruit and vegetables on health risk assessed via acute and chronic exposure based on old and new, lower, established values of: Average Daily Intakes (ADIs)/Acute Reference Doses (ARfDs) and Maximum Residue Levels (MRLs). A total of 3 530 samples were collected, and CHLP in the range of 0.005-1.514 mg/kg was present in 10.2% of all samples. The MRL was exceeded in 0.7% of all samples (MRL established in 2009-2015), and recalculation yielded a much greater number of violations for the new MRL (2016), which exceeded 2.9% of all samples. Acute exposure to CHLP calculated according to the old, higher toxicological data (0.10 mg/kg bw/day), does not exceed 14% of its respective ARfDs for adults and both groups of children, but when calculated for incidental cases according to the current value (ARfD 0.005 mg/kg bw) for infants and toddlers, was above 100% of its respective ARfDs in: white cabbage (263.65% and 108.24%), broccoli (216.80% and 194.72%) and apples (153.20% and 167.70%). The chronic exposure calculated for both newly established ADI values (0.001 mg/kg bw/day and 0.100 mg/kg bw/day) appears to be relatively low for adults and children., (Copyright © 2018 Elsevier Inc. All rights reserved.)

A solid-phase microextraction probe was prepared on the surface of a stainless-steel wire through molecular sol-gel imprinting technology using chlorpyrifos as a template molecule, tetraethoxysilane as a sol-gel precursor, and acrylamide and β-cyclodextrin as functional monomers. The polymer was characterized by infrared spectrometry and scanning electron microscopy. Moreover, the selectivity and the parameters including the type and volume of the extraction solvents, ionic strength, pH, temperature, extraction time, stirring speed, and desorption time affecting extraction performance were evaluated. Under the optimum solid-phase microextraction and gas chromatography conditions, the linear ranges were 0.25-25.0 μg/L for chlorpyrifos, quinalphos, triazophos, pirimiphos-methyl, and chlorpyrifos-methyl with the correlation coefficient above 0.99. The detection limits (S/N = 3) were in the range of 0.02-0.07 μg/L and the RSDs were <7.3%. The developed method was successfully used to determine the multi-residues of chlorpyrifos, quinalphos, triazophos, pirimiphos-methyl, and chlorpyrifos-methyl in green peppers and cinnamon with satisfactory recoveries., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The goal of this work is to study the presence of 17 different pyrethroids and chlorpyrifos in animal origin food samples, including chicken, beef, fish, eggs and milk. The samples were analyzed by GC/NCI-MS/MS in order to determine their insecticide concentration levels, the relation between the amount of insecticides and the lipid content, as well as their isomeric composition. Bifenthrin, cypermethrin, cyhalothrin, permethrin, deltamethrin and chlorpyrifos have been detected in real samples. The highest levels find were verified for chlorpyrifos (45.7 μg L -1 , 17.5 μg kg -1 ww) and cypermethrin (2.75 μg L -1 , 14.7 μg kg -1 ww) in milk and beef, respectively. The estimate of daily intake showed that none of these insecticides exceeded the safety limits of the acceptable daily intake values. A strong correlation between the amount of pesticides and lipid content was found for beef, fish and chicken samples. Regarding the isomers, a predominance of cis isomers in samples contaminated with cypermethrin was verified., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The active ingredients (a.i.) used as pesticides vary across regions. Diet represents the main source of chronic exposure to these chemicals. The aim of this study was to look at the pesticides applied in fruit, vegetable, and beef cattle productions in Mendoza (Argentina), to identify those that were simultaneously used by the three production systems. Local individuals (n = 160), involved in these productions, were interviewed. Glyphosate was the a.i. most often used by fruit-vegetable producers, and ivermectin by beef cattle producers. Chlorpyrifos (CPF) and cypermethrin (CYP) were the only a.i. used by the three production systems. The survey revealed that CPF, CYP, alpha CYP, and CPF+CYP were used by 22, 16, 4, and 20% of the fruit and vegetable producers, respectively. Regarding beef cattle, CYP was used by 90% of producers, CYP + CPF formulation by 8%, and alpha CYP by 2%. The second approach of this study was to search the occurrence of CYP and CPF residues in food commodities analyzed under the National Plan for Residue Control (2012-2015). CYP residues found above the LOD were reported in 4.0% and CPF in 13.4% of the vegetable samples tested, as well as in 1.2 and 28.8%, respectively, of the fruit samples tested. Regarding beef cattle, CYP residues were reported in 2.3% and organophosphates (as a general pesticide class) in 13.5% of samples tested. In conclusion, consumers may be exposed simultaneously to CPF and CYP, from fruits, vegetables, and beef intake. Accordingly, the policy for pesticide residues in food and human risk assessment should account for the combined exposure to CPF and CYP. Moreover, appropriate toxicological studies of this mixture (including genotoxicity) are warranted.

It is important to detect pesticides residues due to the concern over food safety. In this work, the burning ash of waste paper was used as carbon source to synthesize carbon dots (C-dots). The fluorescence of obtained C-dots could been turn off by Fe 3+ which was from Fe 2+ oxidized by H 2 O 2 , organophosphorus pesticides could effectively inhibit the production of H 2 O 2 by destroying the acetylcholinesterase activity, so the fluorescence of C-dots hold turning on in the presence of organophosphorus pesticides. Based on above principle that the fluorescence intensity of C-dots was proportional to the pesticides concentration, take chlorpyrifos for example, a universal method for pesticides detection was established. The linear range was 0.01-1.0 μg/mL with detection limit of 3 ng/mL. The method was reliable and sensitive to actual samples. The imaging of chlorpyrifos on cabbages leaves indicated this method could be used for visualization detection of organophosphorus pesticides in vegetables., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

We measured the concentrations of organophosphorus pesticide （chlorpyrifos-methyl, pirimiphos-methyl and fenitrothion） residues in domestic and imported commercial wheat products （flour, noodles, cookies） collected from 2008 to 2016. Chlorpyrifos-methyl and fenitrothion in domestic flour samples were detected in 16 out of 34 samples at levels of ＜0.001 to 0.016 ppm, and in 14 out of 34 samples at levels of ＜0.001 to 0.004 ppm. Chlorpyrifos-methyl was detected in 22 out of 38 domestic cookies at levels of ＜0.001 to 0.054 ppm （median: 0.001 ppm）. Relatively high concentrations of chlorpyrifos-methyl （0.005 to 0.054 ppm） were found in six domestic cookies containing wheat bran. Pirimiphos-methyl was detected in 32 out of 68 cookies from foreign countries at levels of ＜0.001 to 0.11 ppm. Pirimiphos-methyl was detected frequently in products imported from Europe.

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.

The present study was undertaken to monitor organochlorine, organophosphate, and synthetic pyrethroid pesticide residues in butter (n = 55) and ghee (n = 56) samples collected from three different regions of Punjab. The estimation of pesticide residues was done by multiple residue analytical technique using gas chromatography equipped with GC-ECD and GC-FTD. The confirmation of residues was done on gas chromatography mass spectrometry in both selective ion monitoring (SIM) and scan mode. Results indicated the presence of hexacholorocyclohexane (HCH) and p,p' DDE as predominant contaminant in both butter and ghee. Residues of HCH were detected in 25 and 23% samples of butter and ghee, respectively, while residues of p,p' DDE were recorded in 29 and 25% of butter and ghee samples, respectively. None of the butter and ghee sample violated the MRL values of 200 ng g(-1) for HCH and 1250 ng g(-1) for dichorodiphenyl tricholorethane (DDT). The presence of endosulfan, cypermethrin, fenvalerate, deltamethrin, and chlorpyrifos were observed in a few butter and ghee samples at traces. The spatial variation for comparative occurrence of pesticide residues indicated higher levels in the south-western region of Punjab. Additionally, the temporal variation indicated the significant reduction of HCH and DDT levels in butter and ghee in Punjab.

The present studies were carried out to observe the dissipation pattern of chlorpyrifos on apple in Kashmir Valley. Persistence of chlorpyrifos in apple was studied following two applications rates of chlorpyrifos (Dursban 20 EC) at 200 g a.i. ha(-1) (single dose T 1) and 400 g a.i. ha(-1) (double dose T 2). The average initial deposit of chlorpyrifos was found to be 1.61 and 1.98 μg g(-1) for T 1 and T 2 application rates respectively on apple. The residues dissipated to 0.09 and 0.06 μg g(-1) after 15- and 30-day post treatment with half-life periods of 3.34 and 5.47 days in T 1 and T 2 application rates, respectively. The residues of chlorpyrifos dissipated to below limit of quantification (LOQ) of 0.04 μg g(-1) after 30 day at T 1 application rate. A waiting period of 6 days must be observed for chlorpyrifos on apple at recommended application rate for the safety of consumers. Theoretical maximum residue contribution (TMRC) values were found to be far less than maximum permissible intake (MPI) at 0 day in both the dosages suggesting chlorpyrifos on apple in Kashmir is unlikely to cause health risks.

The present study describes chlorpyrifos residues in duck commodities through the duck food chain, transfer factors, and dietary risks to Chinese consumers. After duck feeding experiments with pellet feed that lasted for 42 days, chlorpyrifos residues found in all samples collected from the ducks on maximum estimated dose group (3.20 mg/kg level) were from <0.0005 to 0.019 mg/kg. The residue levels of the fat, intestine, and tongue were obviously higher than those of the meat and other edible tissues. The transfer factors of all duck commodities were from 0.0001 to 0.0049 among different contamination levels, which indicated that chlorpyrifos had a low persistency in duck meat and metabolism organs. The chronic exposure assessment revealed that only 0.034-0.150% of the acceptable daily intake (ADI; 0-0.01 mg/kg/bw/day) of chlorpyrifos was consumed via the duck commodities for different age and gender groups in China. The acute exposure assessments of different age and gender groups were only 0.019-0.082% of the acute reference dose (ARfD; 0-0.1 mg/kg/bw). The results show that the single dietary exposure risk of chlorpyrifos raised by the intake of duck commodities was quite low in China.

The field studies on the residue levels of the fungicides and insecticides used in commercial raspberry (Rubus idaeus L.) plantation have been performed. Starting on the first day of harvesting (on June 19), 20 laboratory samples of fruit, 10 laboratory samples of leaves and 4 samples of soil were analyzed and the residue levels were compared to the Maximum Residue Limits (MRL) and Acceptable Daily Intakes (ADI). All analyses were carried out using extraction method and gas chromatography technique. Esfenwalerate (Sumi-alpha 050 EC) and beta-cyfluthrin (Bulldock 025 EC), the insecticides belonging to the group of synthetic pyrethroids, were not found in harvested ripe fruits, while cypermethrin residues (Cyperkill 25 EC) applied on May 24, 25 days later was still found on low levels in fruits (0.026 mg kg(-1)) and in leaves (2.58 mg kg(-1)). In turn, residues of chlorpyrifos (Dursban 480 EC), applied to the soil on May 15 against the cockchafers Melolontha melolontha and Otiorhynchus sp., were found at the level 0.004 mg kg(-1). The content of pesticides in ripe fruits depended mainly on the dose and on the time that has elapsed from the date of their application and were as follows: boscalid -0.950, pyrimethanil -0.917, pyraclostrobin -0.253 cypermethrin -0.026 and chlorpyrifos -0.004 mg kg(-1) while in leaves: boscalid -30.64, pyrimethanil -8.13, pyraclostrobin -15.82, cypermethrin -2.58 and chlorpyrifos -0.15 mg kg(-1). The highest average daily intake was in the case of boscalid, and in fruits and leaves reached the levels 0.205 and 6.63, in total 0.33% and 12.18% of ADI, respectively.

Although jujube is a minor crop and very few pesticides are registered on it, the application of pesticides during the growth stage of jujube is inevitable to control the pests or diseases. This situation has led to pesticide misuse. A modified quick, easy, cheap, effective, rugged, and safe method using a novel sorbent, multiwalled carbon nanotubes, as a dispersive solid-phase extraction sorbent combined with gas chromatography with mass spectrometry, was developed for the determination of 16 pesticides in jujube. Under the optimized conditions, recoveries of 76.7-112.4% were obtained for the target analytes at three spiked concentration levels. The relative standard deviations ranged from 1.2 to 12.3%. Limits of detection and limits of quantification for 16 pesticides ranged from 1 to 10 and 3 to 30 μg/kg, respectively. The residues of chlorpyrifos, hexaconazole, tebuconazole, and cyhalothrin were detected from samples obtained from the market., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Chlorpyrifos is a widely used organophosphorus pesticide in agricultural crops (including food) and animal feeds in China, resulting in heavy contamination. Many studies have focused on the food-processing effects on chlorpyrifos removal, but sufficient information is not observed for feed-processing steps. Here, chlorpyrifos residual behaviors in field crops and its transfers in duck pellet feed-processing steps were evaluated. In field trials, the highest residues for rice grain, shelled corn, and soybean seed were 12.0, 0.605, and 0.220 mg/kg, respectively. Residues of all rice grain and about half of shelled corn exceeded the maximum residue limits (MRLs) of China, and five soybean seeds exceeded the MRL of China. Chlorpyrifos residue was reduced 38.2% in brown rice after the raw rice grain was hulled. The residue in bran increased 71.2% after milling from brown rice. During the squashing step, the residue reduced 73.8% in soybean meal. The residues reduced significantly (23.7-36.8%) during the process of granulating for rice, maize, and soybean products. Comparatively, the grinding process showed only limited influence on chlorpyrifos removal (<10%). The residues of duck pellet feeds produced from highly contaminated raw materials of this study were 1.01 mg/kg (maize-soybean feed) and 3.20 mg/kg (rice-soybean feed), which were much higher than the generally accepted value (>0.1 mg/kg) for animal feeding. Chlorpyrifos residues were removed significantly by processing steps of pellet feeds, but the residue of raw materials was the determining factor for the safety of duck feeding.

In this study, a novel acetylcholinesterase-based biosensor was fabricated. Acetylcholinesterase (AChE) was immobilized onto a glassy carbon electrode (GCE) with the aid of Cu-Mg-Al calcined layered double hydroxide (CLDH). CLDH can provide a bigger effective surface area for AChE loading, which could improve the precision and stability of AChE biosensor. However, the poor electroconductibility of CLDHs could lead to the low sensitivity of AChE biosensor. In order to effectively compensate the disadvantages of CLDHs, graphene-gold nanocomposites were used for improving the electron transfer rate. Thus, the graphene-gold nanocomposite (GN-AuNPs) was firstly modified onto the GCE, and then the prepared CLDH-AChE composite was immobilized onto the modified GCE to construct a sensitive AChE biosensor for pesticides detection. Relevant parameters were studied in detail and optimized, including the pH of the acetylthiocholine chloride (ATCl) solution, the amount of AChE immobilized on the biosensor and the inhibition time governing the analytical performance of the biosensor. The biosensor detected chlorpyrifos at concentrations ranging from 0.05 to 150μg/L. The detection limit for chlorpyrifos was 0.05μg/L., (Copyright © 2014 Elsevier Inc. All rights reserved.)

A total of 162 samples of different varieties of mango: Deshehari, Langra, Safeda in three growing stages (Pre-mature, Unripe and Ripe) were collected from Lucknow, India, and analyzed for the presence of seventeen organophosphate pesticide residues. The QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method of extraction coupled with gas chromatography was validated for pesticides and qualitatively confirmed by gas chromatography-mass spectrometry. The method was validated with different concentrations of mixture of seventeen organophosphate pesticides (0.05, 0.10, 0.50 mg kg(-1)) in mango. The average recovery varied from 70.20% to 95.25% with less than 10% relative standard deviation. The limit of quantification of different pesticides ranged from 0.007 to 0.033 mg kg(-1). Out of seventeen organophosphate pesticides only malathion and chlorpyriphos were detected. Approximately 20% of the mango samples have shown the presence of these two pesticides. The malathion residues ranged from ND-1.407 mg kg(-1) and chlorpyriphos ND-0.313 mg kg(-1) which is well below the maximum residues limit (PFA-1954). In three varieties of mango at different stages from unpeeled to peeled sample reduction of malathion and chlorpyriphos ranged from 35.48%-100% and 46.66%-100% respectively. The estimated daily intake of malathion ranged from 0.032 to 0.121 µg kg(-1) and chlorpyriphos ranged from zero to 0.022 µg kg(-1) body weight from three different stages of mango. The hazard indices ranged from 0.0015 to 0.0060 for malathion and zero to 0.0022 for chlorpyriphos. It is therefore indicated that seasonal consumption of these three varieties of mango may not pose any health hazards for the population of Lucknow, city, India because the hazard indices for malathion and chlorpyriphos residues were below to one.

A rapid, specific, and sensitive method based on modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) coupled to gas chromatography tandem mass spectrometry (GC-MS/MS) was developed and validated for simultaneous determination of chlorpyrifos (CP) and its metabolite 3,5,6-trichloro-2-pyridinol (TCP) in duck muscle. The residues of CP and TCP were extracted by acidified acetonitrile. The fat layer of the extract was removed under -20 °C, then the organic layer was evaporated. The analytes were derivatized by N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) and cleaned up by a mixture of 150 mg MgSO4, 25 mg graphitized carbon black (GCB), and 50 mg N-propylethylenediamine (PSA) to remove interference. The final extract was analyzed by GC-MS/MS. Recovery values at the spiking concentrations ranged from 86.2 to 92.3 % for CP and from 74.8 to 81.8 % for TCP, with relative standard deviations (RSDs) lower than 9.5 and 12.3, respectively. The correlation coefficients of CP (from 2 to 2,000 μg/kg) and TCP (from 1 to 1,000 μg/kg) were equal to or higher than 0.998. The limits of detection (LODs) were 0.3 and 0.15 μg/kg, and the limits of quantification (LOQs) were 1.0 and 0.5 μg/kg for CP and TCP in duck muscle, respectively. The average intra- and inter-day accuracy ranged from 84.6 to 91.2 % for CP and 75.6 to 82.3 % for TCP, and the intra- and inter-day precisions were from 5.8 to 8.2 % for CP and 6.5 to 11.9 % for TCP. Furthermore, the CP and TCP residues in duck muscle samples were detected for dietary risk assessment using the validated method.

The residues of four insecticides belonging to different families were studied on head lettuce (Lactuca sativa L. var. capitata L.), cabbage (Brassica oleracea Linn. var. capitata DC.), Chinese cabbage (Brassica pekinensis Skeels), and broccoli (Brassica oleracea var. italica) after pesticide application. To reduce application variability, a tank mix of acetamiprid 20% SP, chlorpyrifos 22.5% EC, deltamethrin 2.4% SC, and methomyl 40% SP was applied at recommended and double doses. Initial deposits of all pesticides on head lettuce were higher than those of the other three crops. The residues of chlorpyrifos and deltamethrin were higher than the maximum residue limits (MRLs) at recommended preharvest intervals (PHIs) on head lettuce and Chinese broccoli treated with higher doses. The residues of methomyl on head lettuce also showed the same phenomenon.

Background: 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: Results showed that washing with a low concentration of limonene for 5 min (where LOQ is limit of quantitation) caused 53.67%,

The epidemiological studies demonstrate that the residues of pesticides in plant food, increases the impact of cancers on the professionally populations. The effect of the residues of pesticides can also be at the origin of dysfunction of the reproductive systems, endocrinal and immune systems, ague attack and column of the nervous system and the deterioration of lungs. In this study, Chlorpyrifos residues in the samples were detected and quantified by employing high performance liquid chromatography (HPLC). The presence of these wastes in fruits and vegetables are confirmed. Acquired results revealed concentration in residue of chlorpyrifos in the apples, tomatoes, green and red pepper cultivated in the country as well as at the level of the cucumber. Our results showed that 61% of the analyzed samples introduce stocks of residues of pesticides which are broadly superior to the accepted maximum limit.

Extraction and clean-up constitute important steps in pesticide residue analysis. For the correct interpretation of analytical results, uncertainties of extraction and clean-up steps should be taken into account when the combined uncertainty of the analytical result is estimated. In the scope of this study, uncertainties of extraction and clean-up steps were investigated by spiking (14)C-labelled chlorpyrifos to analytical portions of tomato, orange, apple, green bean, cucumber, jackfruit, papaya and starfruit. After each step, replicate measurements were carried out with a liquid scintillation counter. Uncertainties in extraction and clean-up steps were estimated separately for every matrix and method combination by using within-laboratory reproducibility standard deviation and were characterised with the CV of recoveries. It was observed that the uncertainty of the ethyl acetate extraction step varied between 0.8% and 5.9%. The relative standard uncertainty of the clean-up step with dispersive SPE used in the method known as QuEChERS was estimated to be around 1.5% for tomato, apple and green beans. The highest variation of 4.8% was observed in cucumber. The uncertainty of the clean-up step with gel permeation chromatography ranged between 5.3% and 13.1%, and it was relatively higher than that obtained with the dispersive SPE method.

Chronic dietary exposure to pesticide residues was assessed for the French population using a total diet study (TDS) to take into account realistic levels in foods as consumed at home (table-ready). Three hundred and twenty-five pesticides and their transformation products, grouped into 283 pesticides according to their residue definition, were sought in 1235 composite samples corresponding to 194 individual food items that cover 90% of the adult and child diet. To make up the composite samples, about 19,000 food products were bought during different seasons from 2007 to 2009 in 36 French cities and prepared according to the food preparation practices recorded in the individual and national consumption survey (INCA2). The results showed that 37% of the samples contained one or more residues. Seventy-three pesticides were detected and 55 quantified at levels ranging from 0.003 to 8.7mg/kg. The most frequently detected pesticides, identified as monitoring priorities in 2006, were the post-harvest insecticides pirimiphos-methyl and chlorpyrifos-methyl-particularly in wheat-based products-together with chlorpyrifos, iprodione, carbendazim and imazalil, mainly in fruit and fruit juices. Dietary intakes were estimated for each subject of INCA2 survey, under two contamination scenarios to handle left-censored data: lower-bound scenario (LB) where undetected results were set to zero, and upper-bound (UB) scenario where undetected results were set to the detection limit. For 90% of the pesticides, exposure levels were below the acceptable daily intake (ADI) under the two scenarios. Under the LB scenario, which tends to underestimate exposure levels, only dimethoate intakes exceeded the ADI for high level consumers of cherry (0.6% of children and 0.4% of adults). This pesticide, authorised in Europe, and its metabolite were detected in both cherries and endives. Under the UB scenario, that overestimates exposure, a chronic risk could not be excluded for nine other pesticides (dithiocarbamates, ethoprophos, carbofuran, diazinon, methamidophos, disulfoton, dieldrin, endrin and heptachlor). For these pesticides, more sensitive analyses of the main food contributors are needed in order to refine exposure assessment., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate) was applied with three different formulations on oranges, peaches, tomatoes, wine and table grapes, and its behaviour was evaluated after field treatment. The formulations applied were emulsifiable concentrates (EC), microencapsulates (ME), and wettable granules (WG). The residues were similar in all crops studied in the EC and WG experiments, except peaches with WG treatment, the residue amount was lower than EC values. Tomatoes which were grown in greenhouse showed similar residues in all treatments just after treatment. Wine and table grapes showed different decline curves in the EC experiments ascribable to the different growing technology. Instrumental limit of determination (LOD) and limit of quantification (LOQ) for all matrices were 0.01, and 0.03 mg kg⁻¹, respectively. Repeated treatments showed that Chlorpyrifos can accumulate leading to residue levels at the preharvest interval (PHI) over the maximum residue level (MRL), especially on oranges and peaches. Among the formulates used ME showed the higher risk of residues over the MRL at harvest.

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

Protocol for the determination of pesticides residues in honey samples have been standardized using a simple technique of liquid–liquid extraction. The method is sensitive to detect low levels of pesticides in honey. Honey sample was fortified with pesticides, namely, cypermethrin, fenvalerate, alphamethrin, lamba–cyhalothrin, endosulfan (α, β and sulfate) and chlorpyrifos. The method of extraction and clean up was optimized and validated in the laboratory. The method was applied to screen six samples of honey locally available for pesticides residues. Recoveries ranged from 60% to 90.6% with RSDs from 2% to 10%. Low recoveries were recorded for α and β -endosulfan in the range of 60%–71%. The LOQs, varied from 0.05 to 1.0 mg kg−1.

Cardboard boxes used to transport crops are often reused in the distribution process, and therefore transfer of pesticides between crops might occur. So, we designed model experiments to investigate whether or not transfer of pesticide residues from crops to other crops via cardboard boxes occurs. Under severe experimental conditions, 6.2% of the pesticide residues of grapefruit was found to be transferred to spinach via cardboard boxes. In the case of the mandarin orange, 0.57% was transferred. The actual amount of transferred pesticides in the market may be less than that in these model experiments, but it is clear that transfer of pesticide residues to other crops via cardboard boxes can occur. Therefore more attention must be given to reuse of cardboard boxes in the distribution process.

The effects of the cuticle and epicuticular waxes of grapefruit, strawberry and apple on the photodegradation and penetration of chlorpyrifos-methyl were studied. Photodegradation experiments were conducted by exposing the insecticide to the light of a xenon lamp in the presence of a film of wax extracted from the fruit surface. The half-life of chlorpyrifos-methyl irradiated in absence of waxes was 9.6 min. The half-lives of pesticide irradiated in the presence of wax extracts of apple, grapefruit and strawberry were 83, 34 and 26 min, respectively. In penetration studies, fruit with and without wax layers were treated with an aqueous suspension of pesticide. The penetration of the pesticide from the cuticle to the pulp was measured after 24 h. Samples without wax contained a higher total amount of insecticide than those with wax. No pesticide was detected in samples of apple and grapefruit pulp. Residues were detected in all fractions of strawberry. The waxes and cuticle appear to have some effect on the photodegradation and penetration of chlorpyrifos-methyl in fruit samples.

The assessment of consumer exposure to pesticides is an important part of pesticide regulation. Probabilistic modelling allows analysis of uncertainty and variability in risk assessments. The output of any assessment will be influenced by the characteristics and uncertainty of the inputs, model structure and assumptions. While the use of probabilistic models is well established in the United States, in Europe problems of low acceptance, sparse data and lack of guidelines are slowing the development. The analyses in the current paper focused on the dietary pathway and the exposure of UK toddlers. Three single food, single pesticide case studies were used to parameterize a simple probabilistic model built in Crystal Ball. Data on dietary consumption patterns were extracted from National Diet and Nutrition Surveys, and levels of pesticide active ingredients in foods were collected from Pesticide Residues Committee monitoring. The effect of uncertainty on the exposure estimate was analysed using scenarios, reflecting different assumptions related to sources of uncertainty. The most influential uncertainty issue was the distribution type used to represent input variables. Other sources that most affected model output were non-detects, unit-to-unit variability and processing. Specifying correlation between variables was found to have little effect on exposure estimates. The findings have important implications for how probabilistic modelling should be conducted, communicated and used by policy and decision makers as part of consumer risk assessment of pesticides.

Forty-six samples each of vegetarian and nonvegetarian total diet consumed from March 1999 to December 2002 by male subjects in the age group of 19-24 years were analyzed to assess their risk through dietary intake with respect to pesticide residues. The results revealed low dietary intake of levels of Sigma-dichlorodiphenyltrichloroethane (DDT) and which were almost comparable to levels reported in developed countries. The results are indicative of contamination of total diet with pesticide residues despite a ban on the use of DDT and restricted use of lindane in agriculture only. Predominance of lindane residues indicates that liquid milk was a main contributory source as it comprises almost 21% to the total diet consumed per day. Concerted efforts by regulatory authorities and emphasis on judicious use of agrochemicals in pest control are required to decrease the burden of these chemicals in food stuffs to levels safe for dietary intake.

The frequency and severity of crop protection product (pesticide) contamination of peaches grown conventionally were compared with those of peaches grown by integrated crop management (ICM). The peach samples (n = 150) were collected preharvest (June-August 2001) from both conventional (n = 55) and ICM (n = 95) cultivations from the Pella and Imathia districts of Macedonia, Northern Greece. The residue levels of selected insecticides, fungicides and acaricides in peach samples were determined by gas chromatography-mass spectrometry following solid-phase extraction. The concentrations of all detected pesticides were lower than the maximum residue limits (MRLs) in all peach samples grown with the ICM system (p<0.001). However, chlorpyrifos residues at levels higher than the MRLs were detected in four peach samples (i.e. 7% of the total samples) grown by the conventional system. Comparing the results for both cultivation methods with the reported average percentage (3.6%) of fruit samples with pesticide residues above the MRLs (European Union report for Greece in 2001), it was concluded that the initial implementation of the ICM in Greece was successful. The present study indicates that ICM cultivation has a higher efficiency in terms of product safety and quality. Furthermore, the results suggest that the application of conventional cultivation requires continuous monitoring of various crop protection product levels.

A novel enzymatic in vitro activation method for phosphorothionates has been developed to allow their detection with acetylcholinesterase (AChE) biosensors. Activation is necessary because this group of insecticides shows nearly no inhibitory effect toward AChE in their pure nonmetabolized form. In contrast, they exert a strong inhibitory effect on AChE after oxidation as it takes place by metabolic activation in higher organisms. Standard chemical methods to oxidize phosphorothionates showed inherent disadvantages that impede their direct use in food analysis. In contrast, a genetically engineered triple mutant of P450 BM-3 (CYP102 A1) could convert the two frequently used insecticides parathion and chlorpyrifos into their oxo variants as was confirmed by GC/MS measurements. The wild-type protein was unable to do so. In the case of chlorpyrifos, the enzymatic activation was as good as the chemical oxidation. In the case of parathion, the P450 activation was more efficient than the oxidation by NBS but neither activation method yielded an AChE inhibition that was as high as with paraoxon. The application of the method to infant food in combination with a disposable AChE biosensor enabled detection of chlorpyrifos and parathion at concentrations down to 20 microg/kg within an overall assay time of 95 min.

Two 10-day field residue studies were conducted to measure the amount of chlorpyrifos residue found in typical avian food following applications of a commercial 480 g liter(-1) EC (Lorsban 4E) at 1.1 kg AI ha(-1) (1 lb AI acre(-1)) to alfalfa and at 2.3 kg Al ha(-1) (2.0 lb AI acre(-1)) to citrus. Avian food items used in these studies included: crickets (Acheta domestica (L)), earthworms (Lumbricus terrestris L), darkling ground beetle larvae (Tenebrio molitor L), seed heads (Triticum sp), and naturally occurring flying and ground-dwelling insects. The studies incorporated a design involving three main study plots placed within larger treated areas of an alfalfa crop and a mature orange grove. The three main study plots represented three replications and each contained four sub-plots. One sub-plot, on each study plot, was sampled on day 0 (2-h post-application), day 1, day 5 and day 10 post-application. Chlorpyrifos residues were present in all avian food sampled following the application; however, residue levels were lower than estimated residue values typically used by the US EPA to establish expected environmental concentration (EEC) used in screening assessments of risk to terrestrial wildlife.

Food pesticide residue data are used by the U.S. Environmental Protection Agency (EPA) to determine potential dietary risk from chronic and acute exposures. An acute dietary risk assessment determines the pesticide exposure resulting from a single-day consumption of food, and uses stepwise refinement of residue estimates to better judge actual exposures. All exposure refinements use estimates of the fraction of crops treated and food residues measured increasingly closer to the point of actual food consumption, without changes in the pesticide uses. Exposure distributions at all levels of data refinement were extremely right skewed. At the highest level evaluated, estimated exposures at the 99.9th percentile were 0.00087 mg/kgBW/day compared to 0.2648 mg/kgBW/day at the tolerance level for children 1-6 years, theoretically the highest-exposed population sub-group. The estimated exposure at the 99.9th percentile of the U.S. population was approximately twice the exposure at the 99th percentile and 33 times the exposure at the 90th percentile. This evaluation showed the calculated exposure at the highest tier of assessment was 300 times lower than the tolerance level assessment for children 1-6 years at the 99.9th percentile. Reduction in exposure estimates between these tiers was due to a combination of the following factors: food residue measurements in a specially designed market-basket study, government-sponsored monitoring data, probabilistic methodologies, market share information, and food processing data. This case study demonstrates that an improved understanding of the uncertainties of acute dietary exposure from pesticides is possible by using well-established statistical tools and applying them to comprehensive exposure information, including residue monitoring data, consumption data, and pesticide use information.

Information on associations between chlorpyrifos residues in food and personal exposure to chlorpyrifos would be valuable for evaluating the relationship between personal exposure and possible health effects. We used food consumption records, chlorpyrifos levels in duplicate plates, and measures of 3,5,6-trichloro-2-pyridinol (TCPy) in urine obtained from human volunteers in the National Human Exposure Assessment Survey in Maryland (NHEXAS-MD) to evaluate a food consumption-chemical residue model for estimating dietary intake of chlorpyrifos. Model inputs were the NHEXAS-MD food consumption records and chlorpyrifos residues in specific foods measured in the U.S. Food and Drug Administration Total Diet Study (TDS) market baskets from 1993 to 1997. The estimated mean and standard deviation of chlorpyrifos concentration (microg/kg) in duplicate plates (n=203) were within 20% and 50%, respectively, of the corresponding parameters of measured chlorpyrifos levels. However, predicted and measured concentrations in the 78 duplicate plates with detectable levels of chlorpyrifos were not significantly associated according to Spearman correlation analysis (r=0.04, p=0.7667) and linear regression (p=0.2726). Measured and estimated chlorpyrifos intakes for observations with non-zero values for each intake measure (n=71) were moderately associated on a rank (Spearman's r=0.24, p=0.0462) and linear basis (regression r(2)=0.07, p=0.0242). Measured intakes of chlorpyrifos from food and urinary TCPy were significantly correlated in rank order (n=87, Spearman's r=0.30, p=0.0041) and linear (n=87, Pearson's r=0.22, p=0.0409) analyses. Correlation coefficients between estimated intake of chlorpyrifos from food and TCPy were significantly different from zero (n=87; Spearman's r=0.22, p=0.0393; Pearson's r=0.21, p=0.0479). Comparing mean measured chlorpyrifos intake from food (0.46 microg/day) to mean estimated TCPy excretion via urine (6.3 microg/day), dietary intake of chlorpyrifos accounted for approximately 7% of TCPy in this population. These findings suggest the food consumption-chemical residue model can yield reasonably accurate estimates of the population distribution of dietary chlorpyrifos intake, but has little ability to predict dietary exposure for individuals; and that intake of chlorpyrifos from food is a minor contributor to TCPy in urine.

Current USEPA Office of Pesticide Program approaches to acute dietary risk assessment do not adequately address uncertainty in the distributional analysis of exposure. This is especially true with respect to regulatory decision points (bright lines) located at the far extreme of the cumulative output distribution. Use of the 99.9th centile as a risk assessment endpoint necessitates confidence in food consumption and residue input distributions that cannot be demonstrated with currently available data and analysis approaches. Even for a pesticide with a rich residue database, data limitations are sufficient to skew results to significantly overestimate exposure. This is compounded when extremes in food consumption are used that go beyond the stated error bounds for the database used. Risk management decision making need not consider endpoints at extremes of exposure output distributions in order for mitigation to be protective of sensitive populations. In fact, such decision making is better informed by utilizing more statistically reliable endpoint selection in the risk assessment process. The richest data content in cumulative exposure distributions occurs in regions well removed from output tails, where the pattern of exposure distribution is driven by the effects of residue concentrations. In contrast, the extreme upper tail of the exposure distribution is data poor and is characterized by high uncertainty reflecting extremes in food consumption patterns. At present, risk managers are better served with exposure endpoints removed from the highly uncertain tails of exposure distributions such as the 99.9th centile bright line. The selection of more appropriate risk management decision points should consider the nature of the distribution, the severity of the effect being assessed, and robustness of the data available for assessing acute dietary risk., (Copyright 1999 Academic Press.)