Analysis of biogenic volatile organic compounds in zucchini flowers: identification of scent sources.

An analytical method has been applied to determine volatile organic compounds in zucchini flowers. In a first step, the analytical method was applied to characterize the main scents emitted by whole male and female living flowers of three main commercial cultivars of zucchini (Tosca, Chapin, and Consul). In a second step, the compounds were quantified in different parts of the living flowers to identify the contribution of nectar, petals, anther, and stigma to the aroma profile of the flower. The analytical method is based on headspace solid-phase microextraction coupled on-line with GC and tandem MS detection (HS-SPME-GC-MS/MS). A reference compound is added to samples as part of the field quality control procedure to check for likely analyte losses or sample decomposition. The reference compound also acts as an internal standard for quantification purposes. Results have been statistically studied applying principal component analysis (PCA), which shows that three components explain more than 91% of the variance. PCA emphasizes the great importance of nectar as being the main source of 1,4-dimethoxybenzene and 1,2,4-trimethoxybenzene, which influence the aroma profile of flowers. The remaining components can be accounted for by emissions from petals and sexual organs (adroecium and gynoecium anthers or stigmas).

Setting up of recovery profiles: A tool to perform the compliance with recovery requirements for residue analysis.

The use of the recovery term has presented some confusion in Analytical Chemistry. Recent IUPAC recommendations propose to distinguish between two terms: recovery or recovery factor, Re, and apparent recovery, Re*. Apparent recovery includes recovery factor and a new recovery term proposed in this paper, named calibration recovery, Re(C), which depends of the type of systematic error due to the matrix effect (constant and/or proportional) and is related to the applied calibration methodology. This paper highlights the dependence of the calibration recovery on the sample analyte concentration and, for extension, of the apparent recovery, defines the recovery profile, and makes evident the need to determine a "fit for purpose" analyte concentration interval to comply with a regulated recovery requirements. An approach to estimate the calibration recovery and its associated uncertainty in relation to the above-mentioned dependence is presented. The usefulness of the proposed methodology has been shown in the quantification of a pesticide by GC-ECD for assessing dermal exposure.

Assessment of potential (inhalation and dermal) and actual exposure to acetamiprid by greenhouse applicators using liquid chromatography-tandem mass spectrometry.

New analytical methods based on liquid chromatography with electrospray tandem mass spectrometry (LC-MS/MS) have been developed and validated for assessing the exposure of greenhouse workers to acetamiprid. Both ambient (potential inhalation and dermal exposure) and internal dose (biological monitoring of urine samples) measurements were carried out. Potential inhalation exposure was assessed using Chromosorb 102 cartridges connected to air personal samplers. Potential dermal exposure was estimated by using whole body dosimetry. The measurement of actual exposure was done by analyzing the parent compound in urine samples of the applicators, after a solid-phase extraction (SPE) step. The methods showed a good accuracy (72-92%), precision (2-13%) and lower limits (few microg l(-1)). The validated approaches have been applied to assess potential and actual exposure of agricultural workers spraying acetamiprid in greenhouses. The results shown the need to wear personal protective equipment (suits) in order to reduce the absorbed dose of acetamiprid.

Screening method for pesticides in air by gas chromatography/tandem mass spectrometry.

A multiresidue method for determining more than 70 pesticides in air has been validated using a single injection with gas chromatography/tandem mass spectrometry (GC/MS/MS). The method validation considered both stages of sampling and analysis. The sampling method, based on active sampling using sorption in sorbent cartidges, was validated by generating standard atmospheres. Performance parameters of the method were evaluated, with a reduction in the limits of quantification by injecting a higher volume of sample extract, and increase of selectivity by the use of MS/MS detection mode. The method was based on solid-phase extraction, which permits a degree of automation. The best adsorbents were found to be Chromosorb 106 and Tenax TA. The retention capacity of these sampling sorbents allows up to 1440 L of air to be sampled without any breakthrough for most of the compounds. Data were generated for assessing the potential exposure of bystanders. The application of the method to the analysis of the air in urban locations near agricultural areas showed that pesticides were present in most of the samples.

Determination of fifteen priority phenolic compounds in environmental samples from Andalusia (Spain) by liquid chromatography-mass spectrometry.

This work describes the optimisation of a method to determinate fifteen phenolic compounds in waters, sediments and biota (green marine algae) by liquid chromatography coupled to mass spectrometry (LC-MS) with atmospheric pressure chemical ionisation (APCI) in the negative mode. The LC separations of the studied compounds and their MS parameters were optimised in order to improve selectivity and sensitivity. Separation was carried out with a C(18) column using methanol and 0.005% acid acetic as mobile phase in gradient mode. The molecular ion was selected for the quantitation in selective ion monitoring (SIM) mode. A solid-phase extraction (SPE) method was applied in order to preconcentrate the target analytes from water samples. However, extraction of the compounds from sediment and biota samples was carried out by liquid-solid extraction with methanol/water after studying the influence of other organic solvents. In addition, a clean-up step by SPE with HLB Oasis cartridges was necessary for sediments and biota. The proposed analytical methodology was validated in the target environmental matrices by the analysis of spiked blank matrix samples. Detection limits were 10-50 ng L(-1) for water, 1-5 microg kg(-1) for sediments and 2.5-5 microg kg(-1) for biota samples. Good recoveries and precision values were obtained for all matrices. This methodology has been successfully applied to the analysis of incurred water, sediment and biota samples from Andalusia (Spain).

Matrix-effects of vegetable commodities in electron-capture detection applied to pesticide multiresidue analysis.

The influence of the sample matrix in the analysis of pesticides in vegetable samples has been studied in order to determine if the matrix content introduces a systematic or proportional (or both) bias in the measurements. Experiments have been carried out during a 4-month period, in which calibration curves, prepared in solvent and in vegetable matrix, were prepared and analysed. A statistical treatment has been applied in order to: (i) check the stability of such calibrations during the period studied; (ii) compare both solvent and matrix-matched calibrations; and (iii) obtain a correction function. Applying the correction function to the results obtained with a solvent calibration it is possible to make a prediction of the values obtained applying a matrix-matched calibration. The performance of the correction function has been validated with recovery data. Finally the uncertainty derived from the use of each calibration plot and the correction function has been calculated.

Estimation and correction of matrix effects in gas chromatographic pesticide multiresidue analytical methods with a nitrogen-phosphorus detector.

The assessment of matrix effects in the quantification of organophosphorus pesticides in fruit and vegetables by GC-NPD, were studied applying ANCOVA. Calibration curves prepared in solvent were compared with calibration curves prepared in a blank matrix extract for eight different commodities, establishing whether the matrix induces systematic or proportional errors in the quantification of the pesticides. In such cases correction functions were obtained and validated by quantifying spiked samples using solvent calibrations and applying the correction functions to the data obtained. The results were compared with those obtained by quantification using matrix-matching calibrations and with those from 100% recovery experiments. It was found that the matrix effects can be avoided using the correction functions. Finally the contribution of the correction functions to the uncertainty of the results was estimated as well as their stability during a four month period.

Residues of methamidofos, malathion, and methiocarb in greenhouse crops.

The diminution of methamidofos, malathion, and methiocarb in different crops grown in greenhouses has been studied, including the presence of metabolites such as malaoxon, methiocarb sulfoxide, and methiocarb sulfone. The analytical method is based on dichloromethane extraction and GC-PFPD analysis. It has been validated establishing performance parameters such as recovery rates, precision, linear ranges, and limits of detection and quantification, which are low enough for ensuring that their corresponding MLRs can be adequately quantified. Samples of treated cucumbers and peppers grown in greenhouses were collected and analyzed during a 15-day period for obtaining the diminution rates of methamidofos and malathion. The behavior of methiocarb in treated green beans and tomatoes has been studied using analysis of variance (ANOVA) as the statistical tool, for establishing the influence of crop, season, application dose, and greenhouse design.

Monitoring of 6-chloronicotinic acid in human urine by gas chromatography-tandem mass spectrometry as indicator of exposure to the pesticide imidacloprid.

A new analytical method for determining 6-chloronicotinic acid (6-ClNA) in human urine is proposed. 6-ClNA is the main metabolite in warm-blooded animals after exposure to the insecticide imidachloprid. 6-ClNA was extracted from human urine using solid phase extraction (SPE) with laboratory-made cartridges of Amberlite XAD-4. A clean-up step and a derivatization process were carried out prior to gas chromatography-tandem mass spectrometric (GC-MS-MS) determination. A study on the influence of pH in the extraction process revealed that it affects the analyte extraction efficiency. A working pH zone was defined between 0.8 and 2.8. Calibration curves were studied in the concentration range of 0.5-100 ng mL(-1) and showed good linearity. Limits of detection and determination of the method were 16 and 56 pg mL(-1) respectively. The mean recovery at 10 and 100 ng mL(-1) was between 97.2 and 102.1% and the repeatability was lower than 5.4% in all cases. The analysis of urine samples of five agricultural workers from Almería (Spain) did not detect the metabolite.

Gas chromatographic method for assessing the dermal exposure of greenhouse applicators to dimethoate and malathion.

An analytical method is developed to determine potential and actual dermal exposure to dimethoate and malathion for agricultural workers using whole body dosimetry. The methodology described includes three different aspects: the validation of the analytical method incorporating a matrix effect for establishing performance parameters such as recovery rates (between 92% and 103% for both pesticides), limits of detection and quantitation, and precision of measurements (RSD < 10%); a field sampling strategy developing a procedure for collecting samples and carrying out field spikes and field blanks in order to ensure the stability of samples during transport, storage, and analysis; and finally, a quality control procedure for ensuring that data are under statistical control. The method is applied to evaluate the potential and actual dermal exposure as well as its distribution for a pesticide applicator and the applicator's assistant after a greenhouse application. Operator exposure levels of approximately 68 mL/h, and 25 mL/h in the case of the assistant, are found. The body areas most exposed are the lower body and hands.

Evaluation of endosulfan residues in vegetables grown in greenhouses.

The reduction in residue levels of endosulfan with time after treatment of tomatoes, green beans, peppers and cucumbers grown in different types of commercial greenhouses (flat- and asymmetric-roof greenhouses) in Almería (Spain) was investigated. A study of the major and minor degradation products of endosulfan in peppers and cucumbers (endosulfan-sulfate, -ether and -lactone) was carried out using gas chromatography-tandem mass spectrometry (GC-MS/MS). To establish the influence of environmental conditions on the degradation of endosulfan, several field trials have been carried out in which crops were sprayed at different rates (full, half- and quarter- of those rates recommended) during two seasons (spring and winter). For statistical purposes, the disappearance of endosulfan with time was considered to follow a pseudo-first-order reaction. Analysis of variance (ANOVA) has been applied to the results obtained. Half-lives of residue disappearance were 4.03-4.68 days in green beans, 4.03-4.20 days in tomatoes, 8.22 days in peppers and 7.97 days in cucumbers. Half-lives in spring were shorter than in the winter season. The application rate and the type of greenhouse did not influence the half-lives.

Gas chromatographic-tandem mass spectrometric analytical method for the study of inhalation, potential dermal and actual exposure of agricultural workers to the pesticide malathion.

New analytical gas chromatographic-tandem mass spectrometric approaches have been developed for assessing both potential and actual exposure of agricultural workers to malathion. The metabolites alpha- and beta-malathion monocarboxylic acids have been determined after a derivatisation process in order to obtain their hexafluoroisopropyl esters. Whole body dosimetry was used for potential dermal exposure assessment. Potential exposure by inhalation was estimated using personal air samplers and polyurethane foam plugs as sorbents. The intern dose measurements were carried out by analysing samples of urine after solid-phase extraction with C18. The recoveries of the analytes of the three matrices were between 90 and 102%. Quantification limits were lower than 0.24 ng L(-1). The proposed methods have been applied to evaluate potential and actual exposure of applicators spraying malathion in greenhouses.

Determination of imidacloprid and its metabolite 6-chloronicotinic acid in greenhouse air by high-performance liquid chromatography with diode-array detection.

A method is described for analysing and sampling imidacloprid and its metabolite 6-chloronicotinic acid in greenhouse air by high-performance liquid chromatography (HPLC) with diode-array detection (DAD). The trapping efficiency of two solid sorbents, Amberlite XAD-2 and Amberlite XAD-4 and the use of different desorption procedures have been tested. To validate the methodology, standard atmospheres containing known concentrations of these pesticides and with different relative humidities were generated. No breakthrough was observed in the range of concentrations studied. Dissipation of analytes was investigated in a 24 h period after application by using personal samplers in a field experiment.

Levels of metamidophos in air and vegetables after greenhouse applications by gas chromatography.

The diminution of metamidophos residue levels with time in vegetables an greenhouse air was investigated after treatment of tomatoes and green beans. A gas chromatographic method using dichloromethane as an extraction solvent has been developed to analyse metamidophos in vegetables, with obtained recoveries higher than 89%. The reliability of several sorbents for air sampling was tested using standard atmospheres resulting in recoveries higher than 90% from PUF, XAD-2, XAD-4 and Supelpak using Soxhlet extraction with acetone. The dissipation of metamidophos in greenhouse air was studied 52 h after application. Finally the effect of crop, type of greenhouse, season and dose applied on the dissipation kinetic of metamidophos in vegetables, was statisTically studied by analysis of variance resulting in crop and season being the most significant factors.

Analyses of chlorothalonil and dichlofluanid in greenhouse air.

A method to sample and analyze chlorothalonil and dichlofluanid in greenhouse air was evaluated. Analysis was performed by gas chromatography with electron capture detection and gas chromatography-mass spectrometry. Solid sorbents such as Chromosorb 102, Porapak R, Supelpak-2, Amberlite XAD-2, Amberlite XAD-4, and polyurethane foam were studied. The use of Soxhlet extraction and solvent desorption with sonication to desorb the pesticides from these sorbents were compared. A procedure to generate atmospheres containing known concentrations of these fungicides was established to study sorption capacity and sampling conditions. Breakthrough and storage of pesticides also were studied. Dissipation of analytes in a 24 h period after application was studied by using personal samplers in a field experiment.