Presence of parabens in children's faeces. Optimization and validation of a new analytical method based on the use of ultrasound-assisted extraction and liquid chromatography-tandem mass spectrometry.

Due to their antimicrobial properties, parabens are a family of synthetic chemical compounds widely used as preservative additives in food and cosmetics. For this reason, humans are highly exposed to them. These substances are capable of altering the proper functioning of the endocrine system and are classified as endocrine disrupting chemicals (EDCs). Traditionally, urine has been the typical matrix studied as an excretion route. However, faeces contain valuable information. In the present study, the presence of methyl-, ethyl-, isopropyl-, propyl-, isobutyl-, butyl- and phenylparaben in stool samples from children has been evaluated. A new analytical method has been optimised and validated. The method is based on the use of ultrasound-assisted extraction followed by clean-up of the extracts by dispersive solid phase extraction dSPE). Parabens were analysed by ultrahigh performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The matrix effect was evaluated and a significant effect was observed for all analytes. Therefore, calibration and validation were performed by addition of different concentrations of analytes to faecal blanks. The coefficient of determination (%R2) for calibration curves was higher than 98.9% in all cases. The limits of detection and quantification were between 0.2 and 0.4 and 0.6-1.0 ng g-1 respectively. The recovery for accuracy assessment had values between 89.0% and 112.7% with an RSD of less than 15% in all cases. The method was successfully applied to 14 samples from children volunteers, 100% of which showed contamination by at least one of the analysed compounds.

Determination of ultraviolet filters in human nails using an acid sample digestion followed by ultra-high performance liquid chromatography-mass spectrometry analysis.

Ultraviolet filters (UV-filters) are specific chemicals that absorb and reflect UVA and UVB radiation from the sun. They are regularly used in sunscreens and in other personal care products (PCPs), and in products like plastics, adhesives, toys, or furniture finishes. This work develops and validates a new method to determine concentrations of UV-filters (BP-1, BP-2, BP-3, BP-6, BP-8, 4-OH-BP, THB, AVB) in human nail samples. Nails are easily available and are considered to be suitable indicators of cumulative and continued exposure to harmful chemicals. The treatment of nail samples includes microwave assisted digestion/extraction (MAE) in a methanolic solution of o-phosphoric acid (0.05 mol L-1) followed by analyte determination using ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS/MS) in multiple reaction monitoring mode. The analytes were separated in less than 10 min. The digestion procedure was optimized using multivariate techniques. Matrix-matched calibration with a pig hoof matrix was used for validating the method. A study of accuracy with spiked blank samples was also conducted. The calculated detection limits varied between 0.2 and 1.5 ng g-1, and quantification limits between 1.0 and 5.0 ng g-1. The trueness of the method was an estimation of the recovery, which was between 90.2% and 112.2%; with an estimated precision (relative standard deviation, % RSD) lower than 12.3% for all UV-filters. Nail samples were obtained from 22 volunteers (male and female). The results showed that BP-1 and BP-3 mainly bioaccumulate in human nails.

Determination of endocrine disrupting chemicals in human nails using an alkaline digestion prior to ultra-high performance liquid chromatography-tandem mass spectrometry.

Rapid industrialization has resulted in a progressive increase in human exposure to hazardous chemicals. The present work develops and validates a new method to determinate 18 endocrine disrupting chemicals (EDCs) in human nail samples. In contrast to other common biological samples, nail sampling is non-invasive and since they take several months to grow out, they are well suited for measuring and reflecting the cumulative exposure to harmful substances in the long term. A digestion of samples with a 0.04 M solution of sodium hydroxide is carried out followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), working in multiple-reaction-monitoring (MRM) mode. The compounds were separated in 8 min. Multivariate optimization strategies were used for the optimization of the parameters that affects the digestion procedure. The validation was developed using a matrix-matched calibration and a recovery assay with spiked samples. The limits of detection and quantification ranged from 0.3 to 1.2 ng g-1 and from 1 to 5 ng g-1, respectively. Recovery rates for spiked samples were between 88% and 113% and the relative standard deviation (% RSD) was lower than 12.7% for all studied EDCs. The method was applied for the analysis of these compounds in human nail samples from volunteers. All samples tested positive for several of the analyzed EDCs.

Determination of quinolone residues in raw cow milk. Application of polar stir-bars and ultra-high performance liquid chromatography-tandem mass spectrometry.

Seventeen quinolone antibiotics were determined in cows' milk. A method of high sensitivity, selectivity and accuracy was developed. Accuracy (trueness and precision), linearity, sensitivity, selectivity, decision limit and detection capability were established following the recommendations of the Commission Decision 2002/657/EC and the Food and Drug Administration (FDA) guideline. The use of polar stir-bar sorptive extraction (SBSE) prior to UHPLC-MS/MS analysis is proposed. The variables that affect SBSE were optimised using multivariate optimisation strategies. The ionic strength, the extraction time and the sample volume were studied. pH and stir-bar coating (polydimethylsiloxane, PDMS, and polyethyleneglycol modified silicone, PEG) were studied. PEG showed the best extraction yield at pH 6. For validation, a matrix-matched calibration and a recovery assay were carried out. Limits of quantification from 0.5 µg kg-1 for nalidixic acid, flumequine and piromidic acid, to 4.0 µg kg-1 for sarafloxacin were calculated. The precision (%, RSD) was lower than 15% for all antibiotics. Recoveries in fortified samples were between 88 and 114%.

Development of a New Microextraction Fiber Combined to On-Line Sample Stacking Capillary Electrophoresis UV Detection for Acidic Drugs Determination in Real Water Samples.

A new analytical method coupling a (off-line) solid-phase microextraction with an on-line capillary electrophoresis (CE) sample enrichment technique was developed for the analysis of ketoprofen, naproxen and clofibric acid from water samples, which are known as contaminants of emerging concern in aquatic environments. New solid-phase microextraction fibers based on physical coupling of chromatographic supports onto epoxy glue coated needle were studied for the off-line preconcentration of these micropollutants. Identification and quantification of such acidic drugs were done by capillary zone electrophoresis (CZE) using ultraviolet diode array detection (DAD). Further enhancement of concentration sensitivity detection was achieved by on-line CE "acetonitrile stacking" preconcentration technique. Among the eight chromatographic supports investigated, Porapak Q sorbent showed higher extraction and preconcentration capacities. The screening of parameters that influence the microextraction process was carried out using a two-level fractional factorial. Optimization of the most relevant parameters was then done through a surface response three-factor Box-Behnken design. The limits of detection and limits of quantification for the three drugs ranged between 0.96 and 1.27 µg∙L-1 and 2.91 and 3.86 µg∙L-1, respectively. Recovery yields of approximately 95 to 104% were measured. The developed method is simple, precise, accurate, and allows quantification of residues of these micropollutants in Genil River water samples using inexpensive fibers.

Polar stir bars for isolation and preconcentration of perfluoroalkyl substances from human milk samples prior to UHPLC-MS/MS analysis.

BACKGROUND: A new method for the determination of four perfluoroalkyl carboxylic acids (from C5 to C8) and perfluorooctane sulfonate in human milk samples using stir-bar sorptive extraction-ultra-HPLC-MS/MS has been accurately optimized and validated. METHODOLOGY: Polydimethylsiloxane and polyethyleneglycol modified silicone materials were evaluated. DISCUSSION: Overall, polyethyleneglycol led to a better sensitivity. After optimizing experimental variables, the method was validated reaching detection limits in the range of 0.05-0.20 ng ml(-1); recovery rates from 81 to 105% and relative standard deviations fewer than 13% in all cases. The method was applied to milk samples from five randomly selected women. All samples were positive for at least one of the target compounds with concentrations ranging between 0.8 and 6.6 ng ml(-1), being the most abundant perfluorooctane sulfonate.

Multiclass method for the determination of quinolones and ß-lactams, in raw cow milk using dispersive liquid-liquid microextraction and ultra high performance liquid chromatography-tandem mass spectrometry.

An analytical method based on a sample treatment by dispersive liquid-liquid microextraction (DLLME) followed by ultra high performance liquid chromatography-tandem mass spectrometry analysis (UHPLC-MS/MS) for the determination of 17 quinolones and 14 ß-lactams (penicillins and cephalosporins) in raw cow milk, was validated according to the European Commission guidelines as cited in the Decision 2002/657/EC. The extraction efficiency of the DLLME depends on several parameters such as the nature and volumes of extractant and dispersive solvents, pH, concentration of salt, shaking time and time of centrifugation. These variables were accurately optimized using multivariate optimization strategies. A Plackett-Burman design to select the most influential parameters and a Doehlert design to obtain the optimum conditions have been applied. Two different pH values were used for the extraction of compounds (pH 3 for acidic quinolones and ß-lactams and pH 8 for amphoteric quinolones). The method was validated using matrix-matched standard calibration followed by a recovery assay with spiked samples. The limits of quantification found ranged from 0.3 ng g(-1) for amoxicillin to 6.6 ng g(-1) for ciprofloxacin, and the precision was lower than 15% in all cases as is required by the European Regulation. The decision limits (CCα) ranged between 4.1 and 104.8 ng g(-1), while detection capabilities (CCß) from 4.2 to 109.7 ng g(-1). These values were very close to the corresponding maximum residue limits (MLRs) for the studied antibiotics. Recoveries between 72 and 110% were also obtained. Finally, in order to evaluate the applicability of the method, 28 raw cow milk samples were analysed and it was observed that 28% of the samples were positive. However, only 11% were considered non-compliant with the current EU legislation (Commission Regulation 37/2010), due to some milk samples corresponded to treated cows with these antibiotics.

Stir-membrane solid-liquid-liquid microextraction for the determination of parabens in human breast milk samples by ultra high performance liquid chromatography-tandem mass spectrometry.

In this article, stir-membrane solid-liquid-liquid microextraction (SM-SLLME) is tailored for the analysis of solid matrices and it has been evaluated for the determination of parabens in l breast milk samples. A three-phase microextraction mode was used for the extraction of the target compounds taking advantage of their acid-base properties. The unit allows the simultaneous extraction of the target compounds from the solid sample to an organic media and the subsequent transference of the analytes to an aqueous acceptor phase. The method includes the identification and quantification of the analytes by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). All the variables involved in the extraction procedure have been accurately studied and optimized. The analytes were detected and quantified using a triple quadrupole mass spectrometer (QqQ). The selection of two specific fragmentation transitions for each compound allowed simultaneous quantification and identification. The method has been analytically characterized on the basis of its linearity, sensitivity and precision. Limits of detection ranged from 0.1 to 0.2ngmL(-1) with precision better than 8%, (expressed as relative standard deviation). Relative recoveries were in the range from 91 to 106% which demonstrated the applicability of the stir-membrane solid-liquid-liquid microextraction for the proposed analytical problem. Moreover, the method has been satisfactorily applied for the determination of parabens in lyophilized breast milk samples from 10 randomly selected individuals.

Sorption and desorption of alcohol sulfate surfactants in an agricultural soil.

Alcohol sulfates are one of the most important types of commercial anionic surfactants and may pose serious environmental problems. The present study examines the sorption behavior of alcohol sulfates in an agricultural soil using a batch reactor and column experiments. Kinetics and equilibrium isotherms of the sorption and desorption processes of the following alcohol sulfate homologues have been determined: AS-C12, AS-C14, AS-C16 , and AS-C18. Sorption and desorption occurred rapidly, and equilibrium was achieved in approximately 1 h. The sorbed mass percentages were 35.1% AS-C12 , 67.2% AS-C14 , and 100% for both AS-C16 and AS-C18. A pseudo-first-order kinetic model provided an adequate fit of data. Sorption and desorption equilibrium data were fitted into 1) a linear model, with r(2) values in the ranges 0.712 to 0.988 and 0.736 to 0.983, respectively, and 2) a Freundlich model, with r(2) values in the ranges 0.956 to 0.991 and 0.891 to 0.981, respectively. Continuous-flow experiments in soil columns were carried out to obtain the breakthrough curves for each compound. The present study provides basic theoretical concepts and key parameters for developing mathematical models that simulate the migration of alcohol sulfate into agricultural soils.

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments.

The study describes the environmental monitoring of anionic surfactants-alcohol sulfates (AS) and alcohol ethoxysulfates (AES)-in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography-tandem mass spectrometry analysis (LC-MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg(-1) for AS, from 3.04 to 10.68 mg kg(-1) for AES-C12Ex and from 3.83 to 11.56 mg kg(-1) for AES-C14Ex.

Environmental monitoring study of linear alkylbenzene sulfonates and insoluble soap in Spanish sewage sludge samples.

In this work we present a monitoring study of linear alkylbenzene sulfonates (LAS) and insoluble soap performed on Spanish sewage sludge samples. This work focuses on finding statistical relations between LAS concentrations and insoluble soap in sewage sludge samples and variables related to wastewater treatment plants such as water hardness, population and treatment type. It is worth to mention that 38 samples, collected from different Spanish regions, were studied. The statistical tool we used was Principal Component Analysis (PC), in order to reduce the number of response variables. The analysis of variance (ANOVA) test and a non-parametric test such as the Kruskal-Wallis test were also studied through the estimation of the p-value (probability of obtaining a test statistic at least as extreme as the one that was actually observed, assuming that the null hypothesis is true) in order to study possible relations between the concentration of both analytes and the rest of variables. We also compared LAS and insoluble soap behaviors. In addition, the results obtained for LAS (mean value) were compared with the limit value proposed by the future Directive entitled "Working Document on Sludge". According to the results, the mean obtained for soap and LAS was 26.49 g kg(-1) and 6.15 g kg(-1) respectively. It is worth noting that LAS mean was significantly higher than the limit value (2.6 g kg(-1)). In addition, LAS and soap concentrations depend largely on water hardness. However, only LAS concentration depends on treatment type.

Matrix effect study in the determination of linear alkylbenzene sulfonates in sewage sludge samples.

We propose a study of the matrix effect in the determination of linear alkylbenzene sulfonates (LAS) in sewage sludge samples. First, a rapid, selective and sensitive method is proposed. The method involves two stages: the extraction of the compound from the samples and analysis by liquid chromatography with fluorescence detection (LC-FLD). Three different techniques of extraction (microwave-assisted extraction, Soxhlet, and ultrasounds) were compared, and microwave-assisted extraction was selected as the best suited for our purpose. Microwave-assisted extraction allows reducing the extraction time (25 min compared with 12 h for conventional Soxhlet extraction) and solvent waste (25 ml of methanol compared with 200 ml for Soxhlet or more than 50 ml for the ultrasonic procedure). Absence of matrix effect was evaluated with two standards (2ØC(8:0) and 2ØC(16:0) ) that are not commercial; therefore, neither of them was detected in sewage sludge samples and they showed similar environmental behavior (adsorption and precipitation) to LAS (C(11:0) -C(13.0) ), which allow us to evaluate the matrix effect. Validation was carried out by a recovery assay, and the method was applied to samples from different sources; therefore, they had different compositions.

Determination of insoluble soap in agricultural soil and sewage sludge samples by liquid chromatography with ultraviolet detection.

We have developed a new analytical procedure for determining insoluble Ca and Mg fatty acid salts (soaps) in agricultural soil and sewage sludge samples. The number of analytical methodologies that focus in the determination of insoluble soap salts in different environmental compartments is very limited. In this work, we propose a methodology that involves a sample clean-up step with petroleum ether to remove soluble salts and a conversion of Ca and Mg insoluble salts into soluble potassium salts using tripotassium ethylenediaminetetraacetate salt and potassium carbonate, followed by the extraction of analytes from the samples using microwave-assisted extraction with methanol. An improved esterification procedure using 2,4-dibromoacetophenone before the liquid chromatography with ultraviolet detection analysis also has been developed. The absence of matrix effect was demonstrated with two fatty acid Ca salts that are not commercial and are never detected in natural samples (C13:0 and C17:0). Therefore, it was possible to evaluate the matrix effect because both standards have similar environmental behavior (adsorption and precipitation) to commercial soaps (C10:0) to C18:0). We also studied the effect of the different variables on the clean-up, the conversion of Ca soap, and the extraction and derivatization procedures. The quantification limits found ranged from 0.4 to 0.8 mg/kg. The proposed method was satisfactorily applied for the development of a study on soap behavior in agricultural soil and sewage sludge samples.

Mobility and fate of carbetamide in an agricultural soil.

The objective of this work is to gain a better understanding of the fate of carbetamide, as a representative herbicide, after its soil application. To reach this goal, batch and column laboratory experiments were performed and a transport model was proposed consistent with these results. Then field-scale experiments were carried out for two years and the results compared with those that would be obtained from the transport model, once the degradation terms were introduced. All this is done for four different scenarios: first, considering that the soil is under its natural condition; second, the soil is amended with organic carbon by the addition of stabilized sewage sludge; third, considering that the percolating aqueous phase contains a significant quantity of surfactant [Linear Alkyl Benzene Sulfonate, (LAS)]; and fourth, the scenario in which the sewage sludge and the surfactant are present simultaneously. The Freundlich model yields a good fit to the data of the sorption isotherms obtained from batch equilibrium experiments, but the isotherms are close to linear. The batch sorption/desorption kinetic data together with the column and field results indicate that the retention kinetics are quite fast and local equilibrium can be assumed for the description of the sorption phenomenon. Results also prove that carbetamide is moderately retained in the original soil with a mean value of the partition coefficient of carbetamide about 0.46 (L kg(-1)). When the soil is amended with sewage sludge, this coefficient is somewhat lower, about 0.40 (L kg(-1)). A further decrease is observed 0.32 L kg(-1)) when the surfactant (LAS) at critical micelle concentration (CMC) is used. The two-region model yields a good reproduction of the results of carbetamide mobility in the soil, both at the laboratory scale and at the field scale.

Simultaneous determination of quinolone antibacterials in bovine milk by liquid chromatography-mass spectrometry.

A new liquid chromatography-mass spectrometry (LC-MS) method has been developed and validated for the simultaneous determination of eight quinolone antibacterials for veterinary use in processed bovine milk samples. The quinolones studied included marbofloxacin, ciprofloxacin, danofloxacin, enrofloxacin, sarafloxacin, difloxacin, oxolinic acid and flumequine. Also, a new sample-treatment procedure was used for extraction and preconcentration of these compounds. It involved defatting by centrifugation, protein precipitation by adding a mixture of glacial acetic acid-acetonitrile and removing acetonitrile with dichloromethane; finally, the acidified aqueous layer was evaporated to dryness in a speed vac system, resuspended in the mobile phase and filtered prior to LC injection. The mobile phase was composed of a formic acid aqueous solution 0.1% (v/v) and acetonitrile, with an initial composition of water-acetonitrile 95: 5 (v/v) and using linear gradient elution. Norfloxacin was used as internal standard. The limits of quantification found (2-7 ng g(-1)) were in all cases lower than the maximum residue limits tolerated by the European Union for these compounds in milk.

Determination of sulfophenyl carboxylic acids in agricultural groundwater samples by CE with ultraviolet absorption detection.

An analytical method for the determination of six sulfophenyl carboxylic acids, namely (p-sulfophenyl)acetic, 2-(p-sulfophenyl)propionic, 2-(p-sulfophenyl)butyric, 3-(p-sulfophenyl)butyric, 4-(p-sulfophenyl)butyric, and 5-(p-sulfophenyl)valerianic acid, in agricultural irrigation water samples was developed. It involves an SPE procedure, an on-line preconcentration normal stacking mode and subsequent separation and determination using CE with UV detection (CE-UV). p-Sulfobenzoic acid was used as internal standard. The compounds were separated with an uncoated capillary and a 25 mM ammonium acetate/acetic acid buffer solution (pH 5.5) with 2-propanol (30% v/v) and 0.75 mM CTAB. Analyses were run at -25 kV, 25 degrees C, and 100 s of hydrodynamic injection with UV detection at 225 nm. Quantification limits found ranged between 4 and 6 ng/mL. The proposed method was validated using a recovery assay. It was satisfactorily used for the determination of these compounds in groundwater samples to track down the biodegradation of linear alkylbenzene sulfonates in an agricultural soil from the fertile plain of Granada (Spain).

Simultaneous identification of natural dyes in the collection of drawings and maps from The Royal Chancellery Archives in Granada (Spain) by CE.

A simple and rapid capillary electrophoretic method with UV detection (CE-UV) has been developed for the identification of five natural dyes namely, carmine, indigo, saffron, gamboge and Rubia tinctoria root. The separation was performed in a fused-silica capillary of 64.5 cm length and 50 microm id. The running buffer was 40 mM sodium tetraborate buffer solution (pH 9.25). The applied potential was 30 kV, the temperature was 25 degrees C and detections were performed at 196, 232, 252, 300 and 356 nm. The injections were under pressure of 50 mbar during 13 s. The method was applied to the identification of carminic acid, gambogic acid, crocetin, indigotin, alizarin and purpurin in the collection of drawings and maps at the Royal Chancellery Archives in Granada (Spain). The method was validated by using HPLC as a reference method.

Sampling and identification of natural dyes in historical maps and drawings by liquid chromatography with diode-array detection.

A simple and rapid liquid chromatographic with diode-array UV-vis spectrophotometric detection (HPLC-DAD) method for identification of natural dyes has been developed. Chromatographic retention of carminic acid, indigotin, crocetin, gambogic acid, alizarin and purpurin has been studied. The mobile phase consisted of 40 mM SDS-10 mM phosphate buffer solution (pH 2.3)-0.1% TFA (eluent A) and acetonitrile (eluent B) using a programmed gradient (5% B to 95% B). Analyses were carried out on a Phenomenex, Luna 5u NH2 100(a) column (250 mm x 4.60 mm i.d., 5 microm particle) and the operating conditions were: 0.6 ml min(-1) flow rate, 20 microl volume injection and 35 degrees C column temperature. Extracts of samples of natural dyes taken from historical maps belonging to The Royal Chancellery Archives in Granada were successfully analyzed using the proposed method including a new technique for sampling.

Sensitive gas chromatographic-mass spectrometric method for the determination of phthalate esters, alkylphenols, bisphenol A and their chlorinated derivatives in wastewater samples.

Phthalate esters, alkylphenols, bisphenol A and their chlorinated derivatives are the suspected endocrine disrupters or mutagens. These compounds, commonly called endocrine disrupter chemicals (EDCs), are widely used as plastic additives, lacquers, resins, or surfactants and can be usually found in environmental samples, namely wastewaters. An accurate and reproducible gas chromatographic-mass spectrometric (GC-MS) method is proposed to measure these compounds in wastewater samples of Granada city (Spain). A solid-phase extraction with LiChrolut RP-18 cartridges was carried out and the elution was performed with a diethyl ether/methanol mixture. After isolation, solvent was removed and a silylation step was carried out using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA). Phthalate esters and silylated compounds were identified and quantified by GC-MS using a ZB-5 MS column. Bisphenol F was used as a surrogate. Quantification limits found were between 20 ng L(-1) for 4-nonylphenol and 400 ng L(-1) for benzylbutyl phthalate while inter and intra-day variability was under 5% in all cases. Recoveries for spiked samples were over 95% and under 105%. The method was validated using standard addition calibration and recovery assays.

Determination of pyrimethanil and kresoxim-methyl in soils by headspace solid-phase microextraction and gas chromatography-mass spectrometry.

A method using headspace solid-phase microextraction (HS-SPME) then gas chromatography-mass spectrometry with selected ion monitoring (GC-MS, SIM) has been developed for determination of trace amounts of the fungicides pyrimethanil and kresoxim-methyl in soil and humic materials. Both fungicides were extracted on to a fused-silica fibre coated with 85 microm polyacrylate (PA). Response-surface methodology was used to optimise the experimental conditions. For soil samples the linear dynamic range of application was 0.004-1.000 microg g(-1) for pyrimethanil and 0.013-1.000 microg g(-1) for kresoxim-methyl. The detection limits were 0.001 microg g(-1) and 0.004 microg g(-1) for pyrimethanil and kresoxim-methyl, respectively. HP-SPME-GC-MS analysis was highly reproducible-relative standard deviations (RSD) were between 6.7 and 12.2%. The method was validated by analysis of spiked matrix samples and used to investigate the presence of pyrimethanil and kresoxim-methyl above the detection limits in soil and humic materials.