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The increased concern on the consequence of exposure to multiple chemical combinations has led national regulatory authorities to develop different concepts to conduct risk assessments on chemical mixtures. Pesticide residues were identified as "problem formulation" in the respective European regulations and in this context, the European Food and Safety Authority has suggested to group pesticidal active ingredients (AIs) into cumulative assessment groups (CAGs) based on the toxicological properties of each AI. One proposed CAG, on the liver, currently consists of 15 subgroups, each representing a specific hepatotoxic effect observed in toxicity studies. Dietary cumulative risk assessments would then have to be conducted assuming dose additivity of all members of each CAG subgroup. The purpose of this publication is to group AIs based upon the knowledge of the pathogenesis of liver effects to discriminate between primary end points (direct consequence of chemical interaction with a biological target) and secondary end points (which are a consequence of, or that arise out of, a previous pathological change). Focusing on the relevant primary end points strengthens and simplifies the selection of compounds for cumulative risk assessment regarding the liver and better rationalizes the basis for chemical grouping. Relevant dose additivity is to be expected at the level of the primary/leading pathological end points and not at the level of the secondary end points. We recognize, however, that special consideration is needed for substances provoking neoplasia, and this category is included in the group of primary end points for which chemicals inducing them are grouped for risk assessment. Using the pathological basis for defining the respective CAGs, 6 liver subgroups and 2 gallbladder/bile duct groups are proposed. This approach simplifies the cumulative assessment calculation without obviously affecting consumer safety.

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A multi-residue method for the determination of 107 pesticide residues in wolfberry has been developed and validated. Similar pretreatment approaches were compared, and the linearity, matrix effect, analysis limits, precision, stability and accuracy were validated, which verifies the satisfactory performance of this new method. The LODs and LOQs were in the range of 0.14-1.91 µg/kg and 0.46-6.37 µg/kg, respectively. The recovery of analytes at three fortification levels (10 µg/kg, 50 µg/kg, 100 µg/kg) ranged from 63.3-123.0%, 72.0-118.6% and 67.0-118.3%, respectively, with relative standard deviations (RSDs) below 15.0%. The proposed method was applied to the analysis of fifty wolfberry samples collected from supermarkets, pharmacies and farmers' markets in different cities of Shandong Province. One hundred percent of the samples analyzed included at least one pesticide, and a total of 26 pesticide residues was detected in fifty samples, which mainly were insecticides and bactericide. Several pesticides with higher detection rates were 96% for acetamiprid, 82% for imidacloprid, 54% for thiophanate-methyl, 50% for blasticidin-S, 42% for carbendazim, 42% for tebuconazole and 36% for difenoconazole in wolfberry samples. This study proved the adaptability of the developed method to the detection of multiple pesticide residues in wolfberry and provided basis for the research on the risks to wolfberry health.

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The European Food Safety Authority (EFSA) is developing approaches to cumulative risk assessment of pesticides by assigning individual pesticides to cumulative assessment groups (CAGs). For assignment to CAGs, EFSA recommended to rely on adverse effects on the specific target system. Contractors to EFSA have proposed to allocate individual pesticides into CAGs relying on NOAELs for effects on target organs. This manuscript evaluates the assignments by applying EFSAs criteria to the CAGs "Toxicity to the nervous system" and "Toxicity to the thyroid hormone system (gland or hormones)". Assignment to the CAG "Toxicity to the nervous system" based, for example, on neurochemical effects like choline esterase inhibition is well supported, whereas assignment to the CAG "Toxicity to the thyroid hormone system (gland or hormones)" has been based in the examined case studies on non-reproducible effects seen in single studies or on observations that are not adverse. Therefore, a more detailed effects evaluation is required to assign a pesticide to a CAG for a target organ where many confounders regarding effects are present. Relative potency factors in cumulative risk assessment should be based on benchmark doses from studies in one species with identical study design and human relevance of effects on specific target organs should be analyzed to define minimal margins of exposure.

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GC-MS, GC-tandem MS (MS/MS), and LC-MS/MS were used to mathematically define the degradation profiles of pesticide residues in two field trials. Nineteen pesticides were studied in the first field trial and 11 in the second. The results of the field trials demonstrated that the degradation profiles of pesticide residues in green tea can be described with power functions to successfully estimate the amount of time, following pesticide application, pesticide residues appearing in tea in concentrations at and/or above the maximum residue limit (MRL) decrease to concentrations below the MRL. Stability tests on green tea samples stored at room temperature were conducted to determine whether pesticide-incurred green tea samples prepared according to the method used in the field trials would be suitable for the preparation of reference standards for laboratory-proficiency testing trials. This paper reports the results of a GC-MS, GC-MS/MS, and LC-MS/MS study, as well as the suitability of the samples prepared under these conditions for use as pesticide reference standards in tea analysis.

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Thirty laboratories from fom North and South America, Europe, and Asia participated in this AOAC collaborative study (15 from China; five from Germany; two each from Italy and the United States; and one each from the Republic of Korea, Canada, Spain, Japan, Belgium, and India). Participants represented government regulatory, commercial testing, university, research institute, and private laboratories. The single-laboratory validated (SLV) tea method was evaluated in the collaborative study to determine the recovery and reproducibility of the method under multilaboratory conditions. Since there were no restrictions regarding the type of analytical instrumentation to use for the analyses, laboratories used a combination of equipment that included GC/MS, GC/MS/MS, and LC/MS/MS instruments from 22 different manufacturers, 21 brands of GC and LC columns, 13 different GC temperature programming profiles, 11 LC gradient elution programs, and six different vendor manufactured SPE cartridges. Even though all the analytical performance parameters for all the 653 compounds had been determined in the SLV study, guidance was obtained from an expert review panel of the AOAC Method-Centric Committee on Pesticide Residues to conduct the multilaboratory collaborative study based on 20 selected compounds that can be analyzed by GC/MS and 20 compounds that can be analyzed by LC/MS/MS. Altogether, 560 samples covering the 40 selected pesticides were analyzed in the study. These samples included green tea and oolong tea samples fortified typically at the European Union maximum residue limit for regulatory guidance and compliance, aged tea samples incurred with 20 pesticides, and green tea and oolong tea samples incurred with five pesticides. The analysis of the 560 samples generated a total of 82 459 test results by the 30 participating laboratories. One laboratory failed to meet the proficiency requirements in the precollaborative study. Therefore, its data submitted for the collaborative study were excluded from further analysis and interpretation. The results presented are therefore the 6638 analytical results obtained from the 29 remaining laboratories, which included 1977 results generated by GC/MS, 1704 results by GC/MS/MS, and 2957 results by LC/MS/MS. It was determined after application of the Grubbs and Dixon tests for outliers to the data sets that there were 65 outlier results from the 1977 GC/MS results (3.3%), 65 outlier results from the 1704 GC/MS/MS results (3.8%), and 57 outlier results out of 2957 LC/MS/MS results (1.9%), representing 0.98, 0.98, and 0.86%, respectively, of the 6638 results generated in the study. Analysis with the AOAC statistical software package also confirmed that the method is rugged, and average recovery, average concentration, RSDr, RSDR, and HorRat values all meet recovery and reproducibility criteria for use in multiple laboratories. The Study Director is recommending this method for adoption as an AOAC First Action Official MethodSM.

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A high-throughput, rapid, and efficient modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method with a simple cleanup procedure has been developed for simultaneously determining 227 pesticides in pepper samples by liquid chromatography with tandem mass spectrometry (running time: 10 min). Pesticide residues were extracted/partitioned with an acetonitrile/DisQuE QuEChERS pouch, and the resulting samples were cleaned up with different methods: dispersive solid-phase extraction with primary secondary amines or multiwalled carbon nanotubes and graphitized carbon solid mini cartridge column. The results indicated that multiwalled carbon nanotubes dispersive sorbents achieved the best recoveries and had less matrix interference. The numbers of pesticides with a recovery in the range of 70-120% were 199 at a spiked level of 40 µg/kg. The correlation coefficients (r(2)) for 227 pesticides were above 0.99, while the limits of quantitation of pesticides in pepper samples ranged from 0.13 to 13.51 µg/kg (S/N = 10), and the limits of detection ranged from 0.04 to 4.05 µg/kg (S/N = 3). The relative standard deviations of approximately 197 pesticides were below 20% at spiked levels of 40 µg/kg. Based on these results, the proposed method was chosen as the most suitable cleanup procedure for the determination of multiresidue pesticides in pepper samples.

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The cost effective monitoring of hundreds of pesticide residues in foodstuffs of vegetable origin involves the definition of groups of analytes associated with homogeneous performance parameters of the used analytical method. The performance of the analytical method only needs to be tested on a daily base for some of these group's compounds. This work proposes a strategy for defining groups of compounds with homogeneous physical-chemical properties based on the evaluation of the similarity of the multivariate pattern of five of these properties namely: molar mass, melting point, vapour pressure at 20 °C, n-octanol-water partition coefficient and solubility in water at 20 or 25 °C. Three independent and competing multivariate analysis tools, namely Principal Component Analysis, Hierarchical Clustering and K-Mean Clustering were used. This strategy was successfully used to group 100 pesticides into nine clusters, with 1-40 pesticides, represented by a compound with within group average properties. The developed grouping method was validated using physical-chemical data from other references or compounds and produced groups consistent with the performance of the studied determination of pesticide residues in dried red bean. The mean analyte recoveries of groups with larger dimension are statistically different for a confidence level of 95%. The within group coefficients of variance of mean analyte recoveries of larger groups ranged from 6.7% to 8.5%. This grouping method can reduce the number of recovery tests performed for the validation of the analytical method or test quality control.

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In this paper we describe the development of the first multiclass pesticide residue method applied to essential oils. A total of 70 pesticides covering a wide range of polarity and currently used on essential oil crops have been included in the method. The procedure consists of a 10-fold dilution of lavandin essential oil followed by a direct injection analysis by liquid chromatography/tandem mass spectrometry. The system used is an API 4000 QTrap equipped with an electrospray ionization interface and operating in scheduled selected reaction monitoring acquisition mode. Matrix effects were evaluated by comparing the slopes of matrix-matched and solvent-based calibration curves. Weak signal suppression or enhancement (<20%) was observed for most of the compounds. Method sensitivity was determined statistically by the injection of five matrix-matched calibration curves with the distribution's normality and the variance's homogeneity checked before establishment of a suitable regression model. Limits of detection (LODs) and quantification (LOQs) were then determined using the blank standard's deviation and the slope of the mean curve. The analytical method has been validated for 67 of the 70 pesticides and meets the following LOQs: ≤1 µg/L for 9 pesticides, ≤5 µg/L for 44, ≤10 µg/L for 9, and ≤20 µg/L for 5.

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Data on pesticide body load in the south China region are scarce. Here, we report the concentrations of 24 persistent organic pollutants (POPs), in 10 pools of human milk samples, collected at 2-6weeks postpartum from 238 primiparous women living in Hong Kong and south China, who participated in the 2002-2003 WHO exposure study. Residues were determined by gas chromatography with electron capture detector and confirmed by gas chromatography with mass spectrometry. The mean levels of alpha-HCH (mean 0.6ngg(-1) fat), beta-HCH (940ngg(-1) fat), gamma-HCH (1.8ngg(-1) fat), dieldrin (1.0ngg(-1) fat) and HCB (21.8ngg(-1) fat) were much lower than the 1985 estimates. Mean levels of alpha-HCH, gamma-HCH, dieldrin, cis-heptachlor-epoxide (0.7ngg(-1) fat), sum-chlordane (6.1ngg(-1) fat), trans-nonachlor (12.0ngg(-1) fat), BDE 47 (1.9ngg(-1) fat) and sum PBDE (3.4ngg(-1) fat) were comparable to the international median levels of the 15 other countries participating in the 2002-03 WHO exposure study. Hong Kong had the highest level of beta-HCH, possibly a residual effect of previous high exposures in the 1970s. Body loads of beta-HCH and chlordane were lower among mothers with younger age while mothers born in mainland China had lower levels of beta-HCH, cis-heptachlor-epoxide, oxy-chlordane and trans-nonachlor. Levels of toxaphene, endrin, endosulfan, bromcyclene and nitrofen were not detected in all or almost all of the milk pools. Continuous monitoring of POPs in human milk, especially beta-HCH, is needed for surveillance and interpretation of time trends, and for linkage to strict enforcement of agricultural regulations.

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A new material based on poly(methyltetradecylsiloxane) (PMTDS) thermally immobilized onto a silica support has been tested as a sorbent for the solid-phase extraction (SPE) from water of several pesticides used in soybean cultivation. The SPE methodology was developed and validated for six of these pesticides (imazethapyr, imazaquin, metsulfuron-methyl, bentazone, chlorimuron-ethyl and tebuconazole) according to the International Conference on Harmonization directives and the results were compared with those obtained with a commercial C18 SPE cartridge. The PMTDS-based sorbent gives results similar to the commercial sorbent with recoveries and precisions in agreement with directives for residue analysis. The quantification limits, after concentration, of all the pesticides evaluated were 1.0 microg L(-1), below the levels imposed by the principal regulatory agencies. The PMTDS-based sorbent preparation is fast, easy and reproducible and the cartridges are less expensive than similar commercial SPE materials.

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This study presents two GC-MS SIM methods, in combination with large-volume injection programmed-temperature vaporization (LVI-PTV) injection, for the determination of 141 pesticide residues in apple juice. The sample was extracted with ACN, and coextractives were removed with primary/secondary amine sorbent. ACN extract (20 microL) was injected into a PTV injection port in solvent vent mode, and the pesticides were determined by GC-MS using retention time locking software. Deuterium-labeled pesticides (surrogate standards) were used for analytical quality control. In the validation experiments, pesticides recoveries were found to be 70-121% with RSDs of 4.6-21% (n = 6).

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A rapid multiresidue method for the analysis of 72 pesticides has been developed using a single injection with low-pressure gas chromatography/tandem mass spectrometry (LP-GC/MS/MS). The LP-GC/MS/MS method used a short capillary column of 10 m x 0.53 mm i.d. x 0.25 microm film thickness coupled with a 0.6 m x 0.10 mm i.d. restriction at the inlet end. Optimal LP-GC conditions were determined which achieved the fastest separation in MS/MS detection mode. Also MS/MS conditions were optimized in order to increase sensitivity and selectivity. The analytical parameters of the LP-GC/MS/MS method were compared with those obtained by GC/MS/MS using a conventional capillary column (30 m x 0.25 mm i.d. x 0.25 microm film thickness). Better precision and sensitivity values were obtained with the LP-GC/MS/MS approach. The limits of detection (LOD) of the compounds ranged from 0.1 to 14.1 microg L(-1) for LP-GC/MS/MS, lower than those obtained for conventional GC/MS/MS that ranged from 0.1 to 17.5 microg L(-1). The peak widths obtained with the short column in LP-GC are similar to those obtained using conventional capillary GC columns, and the peaks can be successfully identified by MS/MS detection with the conventional scan speed of ion-trap instruments. In addition, the analysis time was significantly reduced with LP-GC/MS/MS (32 min) versus GC/MS/MS (72 min), allowing the number of samples analyzed per day in a routine laboratory to be doubled.

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A rapid multiresidue method has been developed for the analysis of nine insecticides (organochlorines, pyrethroids and organophosphorus) in soil. The method is based on the sonication extraction of residues from a certain amount of soil placed in a small column, using ethyl acetate. The effect of the residence time of insecticides in soil, the material of the columns used (glass or plastic columns) and the soil moisture content on the recovery of these compounds was also studied. Residues were determined by gas chromatography with electron-capture detection. The average recovery through the method obtained for these compounds varied from 90 to 108% with a relative standard deviation between 1 and 11%. The results of this study pointed out that the recoveries of insecticide residues obtained with plastic or glass columns at different soil moisture content were similar and that the residence of these compounds in soil during several days did not affect their recovery from soil. Confirmation of residue identity was performed by gas chromatography coupled with mass spectrometry.

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OBJECTIVE: To compare mean concentrations of organochlorine in women with a new diagnosis of endometriosis and in controls. DESIGN: Case-control study. SETTING: Women attending an institutional clinic of reproductive endocrinology. PATIENT(S): Cases and controls were selected among women who underwent laparoscopy for chronic pelvic pain, infertility, or tubal fulguration between January 1994 and December 1994. Eighty-six women with endometriosis and 70 controls, matched for the indication for laparoscopy, were recruited. MAIN OUTCOME MEASURE(S): Mean organochlorine plasma concentrations of 14 polychlorinated biphenyl congeners and 11 chlorinated pesticides were compared between the cases and controls. Analysis of covariance was used to adjust means for confounding variables, and odds ratios were estimated by logistic regression. RESULT(S): Crude geometric mean concentrations did not differ significantly between cases and controls for any of the organochlorine compounds. Similarly, crude or adjusted means of the sum of polychlorinated biphenyl congeners, the sum of chlordanes, or the sum of dichlorodiphenyltrichloroethanes did not differ between the groups. There was no significant linear trend in the adjusted odds ratios for endometriosis as organochlorine concentrations increased. CONCLUSION(S): These results suggest that exposure to polychlorinated biphenyls and chlorinated pesticides during adulthood is not associated with endometriosis in the general population.

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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.

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Modern analytical methodology, especially radiotracer techniques, makes it possible to detect residues of a foreign compound in animal products at levels seemingly impossible just two decades ago. Unfortunately, the ability to detect "total radioactivity" in a substrate does not assure that the chemical nature of the residues will be elucidated or that their toxicological significance can be properly assessed. Detection without identification has created a number of problems for the residue chemist and toxicologist. Among these is the problem of classifying radioactive residues in a manner that is meaningful to other scientists and which inherently denotes certain characteristics of the residues involved. While such a system is as yet incomplete, a general classification scheme has evolved in recent years that provides a common ground for categorizing radioactive residues, be they known or unknown. The system consists basically of four categories of radioactive residues: (a) free metabolites (b) conjugate metabolites (c) bound pesticide residues and (d) natural constituents. For the most part, the terms are self-explanatory, but precise definitions remain a point of debate among scientists. This paper discusses th criteria for classifying radioactive residues as perceived by the author based upon works of residue and metabolism chemists, especially those dealing with pesticide residues. Utimately, classification is dependent on the identification of total radioactive residues, a situation which is virtually impossible with many xenobiotics. Sound scientific judgment must remain the key ingredient in determining just how far one must go in identifying radioactive residues of drugs, pesticides and other chemicals which may become a component of the human diet.

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