Determination of flubendazole and its metabolites in eggs and poultry muscle with liquid chromatography-tandem mass spectrometry

The optimization of a quantitative and sensitive LC-MS/MS method to determine flubendazole and its hydrolyzed and reduced metabolites in eggs and poultry muscle is described. The benzimidazole components were extracted from the two matrices with ethyl acetate after the sample mixtures had been made alkaline. The HPLC separation was performed on an RP C-18 column with gradient elution, using ammonium acetate and acetonitrile as mobile phase. The analytes were detected after atmospheric pressure electrospray ionization on a tandem quadrupole mass spectrometer in MS/MS mode. The components were measured by the MS/MS transition of the molecular ion to the most abundant daughter ion. The overall extraction recovery values for flubendazole, the hydrolyzed metabolite, and the reduced metabolite in eggs (fortification levels of 200, 400, and 800 microg kg(-1)) and muscle (fortification levels of 25, 50, and 100 microg kg(-1)) were, respectively, 77, 78, and 80% and 92, 95, and 90%. The trueness (fortification levels of 400 and 50 microg kg(-1), respectively, for eggs and muscle), expressed as a percentage of the added values for these analytes, was, respectively, 89, 100, and 86 and 110, 110, and 98%. The proposed MS detection method operating in the MS/MS mode is very selective and very sensitive. The limits of detection for flubendazole and its hydrolyzed and reduced metabolites in egg and muscle were, respectively, 0.19, 0.29, and 1.14 microg kg(-1) and 0.14, 0.75, and 0.31 microg kg(-1). The limits of quantification were, respectively, 1, 1, and 2 microg kg(-1) and 1, 1, and 1 microg kg(-1). The discussed method was applied to a pharmacokinetic study with turkeys. Residue concentrations in breast and thigh muscle of turkeys orally treated with flubendazole were quantified. Medicated feed containing 19.9 and 29.6 mg kg(-1) flubendazole was provided to the turkeys for seven consecutive days. For the trial with the recommended dose of 19.9 mg kg(-1), one day after the end of the treatment, the mean sum of the flubendazole plus hydrolyzed metabolite residue values in thigh and breast muscle declined to below the maximum residue limit (50 microg kg(-1)) and were, respectively, 36.6 and 54.1 microg kg(-1). The corresponding values with the higher dose of 29.6 mg kg(-1) were, respectively, 101.7 and 119.7 microg kg(-1).     

Liquid chromatographic determination of multiresidue fluorescent derivatives of ionophore compounds, monensin, salinomycin, narasin, and lasalocid, in beef liver tissue

A liquid chromatographic (LC) method with fluorometric detection was developed to quantitatively determine residue levels of monensin, salinomycin, narasin, and lasalocid in beef liver tissue. The ionophores are extracted from the tissue, purified by both alumina and Sephadex LH-20 column chromatography, and then derivatized. Lasalocid was directly esterified with 9-anthryldiazomethane (ADAM), but monensin, salinomycin, and narasin were first acetylated with acetic anhydride and then esterified with ADAM. The ADAM derivatives were purified on a silica gel column and separated by LC using an RP C-8 5 micron column. A fluorescence detector set at 365 nm (excitation) and 418 nm (emission) was used to monitor the column effluent. The detection limits were 0.15 ppm, and the calibration curves were linear between 0.5 and 5.0 ppm for all 4 ionophores. Mean recoveries were 57, 70, 75, and 90% for lasalocid (5 ppm), monensin (2.5 ppm), salinomycin (2.5 ppm), and narasin (2.5 ppm), respectively. The ionophores were also separated and semiquantitated by using bioautography and thin layer chromatography with a vanillin spray.     

MALDI-TOF MS quantification of coccidiostats in poultry feeds

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is a relatively new technique that is having a great impact on analyses. This study is the first to demonstrate the use of linear MALDI-TOF MS to identify and quantify coccidiostats in poultry feeds. 2,5-Dihydroxybenzoic acid (DHB) was found to be the best matrix. In MALDI-TOF MS, coccidiostats form predominantly [M + Na](+) ions, with additional small amounts of [M + K](+) and [M - H + 2Na](+) ions, and no obvious fragment ions. Salinomycin and narasin were unstable in the concentrated DHB matrix solution but were stable when dried on the MALDI-TOF MS probe. A simple fast Sep-pak C18 cartridge purification procedure was developed for the MALDI-TOF MS quantification of coccidiostats in poultry feeds. The MALDI-TOF MS limit of detection for lasalocid, monensin, salinomycin, and narasin standards was 251, 22, 24, and 24 fmol, respectively. The method detection limit for salinomycin and narasin in poultry feeds was 2.4 microgram/g.     

Aflatoxins and ochratoxin A in red paprika for retail sale in Spain: occurrence and evaluation of a simultaneous analytical method

Aflatoxins are the only mycotoxins with legal limits for spices in the European Union. A further limit for ochratoxin A is expected to be adopted soon. Thus, rapid simultaneous methods for quantifying the five mycotoxins are sought. Liquid extraction, immunoaffinity column cleanup, and HPLC-FD with a wavelength program were optimized for the analysis of the five mycotoxins in paprika, a complex fatty matrix. The limits of detection ranged from 0.3 to 0.6 microg/kg. Repeatability (RSDr) ranged from 7.9 to 13.4%, and recoveries were between 61.4 and 77.8%, in both cases at the lower spike level. Aflatoxins, when found, were far below the two legal limits of 5 microg/kg for aflatoxin B 1 and 10 microg/kg for total aflatoxins. Ochratoxin A was more frequently found, with a mean of 11.8 microg/kg, and in a more varied range (SD = 18.9 microg/kg). When an automation of the precolumn derivatization step was attempted, the procedure proved to be unfeasible, but experience derived from this trial and from the general employment of this reaction enables some comments on the possibilities and limitations of this procedure and on research for an alternative one to be made.     

Occurrence of ochratoxin A in cocoa products and chocolate

In this work, the occurrence of ochratoxin A (OTA) in 170 samples of cocoa products of different geographical origins was studied. An immunoaffinity column with HPLC separation was developed to quantify low levels of OTA in cocoa bean, cocoa cake, cocoa mass, cocoa nib, cocoa powder, cocoa shell, cocoa butter, chocolate, and chocolate cream with >80% recoveries. The method was validated by performing replicate analyses of uncontaminated cocoa material spiked at three different levels of OTA (1, 2, and 5 microg/kg). The data obtained were related on the acceptable safe daily exposure for OTA. The highest levels of OTA were detected in roasted cocoa shell and cocoa cake (0.1-23.1 microg/kg) and only at minor levels in the other cocoa products. Twenty-six cocoa and chocolate samples were free from detectable OTA (<0.10 microg/kg). In roasted cocoa powder 38.7% of the samples analyzed contained OTA at levels ranging from 0.1 to 2 microg/kg, and 54.8% was contaminated at >2 microg/kg (and 12 samples at >3 microg/kg). Ochratoxin A was detected in cocoa bean at levels from 0.1 to 3.5 microg/kg, the mean concentration being 0.45 microg/kg; only one sample exceeded 2 microg/kg (4.7%). In contrast, 51.2% of cocoa cake samples contained OTA at levels > or =2 microg/kg, among which 16 exceeded 5 microg/kg (range of 5-9 microg/kg). These results indicate that roasted cocoa powder is not a major source of OTA in the diet.     

High-speed liquid chromatographic determination of monensin, narasin, and salinomycin in feeds, using post-column derivatization

A high-speed liquid chromatographic (LC) method using post-column derivatization is described for the determination of monensin, narasin, and salinomycin in a variety of animal feeds. The ionophores are extracted with hexane-ethyl acetate (90 + 10). A portion of the sample is evaporated, diluted to a known volume, and analyzed using a 6 cm 3 microns C18 column and an absorbance detector after post-column reaction with vanillin. The method has been applied to poultry and swine feeds with levels of 3-100 ppm added antibiotic. A comparison was also carried out with medicated poultry feed and beef feed lot supplement samples previously analyzed by 2 separate bioassay methods for monensin and salinomycin, respectively. Recoveries for the LC method ranged from 92.1 to 103% with an average recovery of 98.1% and a coefficient of variation of 3.65%.     

Determination of low levels of perchlorate in lettuce and spinach using ion chromatography-electrospray ionization mass spectrometry (IC-ESI-MS)

A sample preparation method was developed to quantify environmentally relevant (low micrograms per liter) concentrations of perchlorate (ClO4(-)) in leafy vegetables using IC-ESI-MS. Lettuce and spinach were macerated, centrifuged, and filtered, and the aqueous extracts were rendered water-clear using a one-step solid-phase extraction method. Total time for extraction and sample preparation was 6 h. Ion suppression was demonstrated and was likely due to unknown organics still present in the extract solution after cleanup. However, this interference was readily eliminated using a Cl(18)O4(-) internal standard at 1 microg/L in all standards and samples. Hydroponically grown perchlorate-free butterhead lettuce was spiked to either 10.3 or 37.7 microg/kg of fresh weight (FW), and recoveries were between 91 and 98% and between 93 and 101%, respectively. Five types of lettuce and spinach from a local grocery store were then analyzed; they contained from 0.6 to 6.4 microg/kg of FW. Spike recoveries using the store-bought samples ranged from 89 to 100%. The method detection limit for perchlorate in plant extracts is 40 ng/L, and the corresponding minimum reporting limit is 200 ng/L or 0.8 microg/kg of FW.     

Matrix solid-phase dispersion extraction and gas chromatographic determination of chloramphenicol in muscle tissue

A method based on matrix solid-phase dispersion (MSPD) was developed for the gas chromatographic (GC) determination of chloramphenicol (CAP) residues in animal muscle tissue. Muscle tissue was blended with octadecylsilyl-derivatized silica (C(18)). A column made from the C(18)/muscle tissue matrix was washed with n-hexane and acetonitrile/water (5 + 95), after which CAP was eluted with acetonitrile/water (50 + 50) and partitioned into ethyl acetate. The final extract was evaporated, and a trimethylsilyl derivative of CAP was prepared with Sylon HTP and detected by GC with an electron capture detector (ECD) and a mass spectrometer. For quantitation, the internal standard used was the meta isomer of CAP (m-CAP) for GC-ECD. Muscle tissue samples were fortified at three concentration levels. At 5, 10, and 15 microg/kg levels the respective mean recoveries were 93, 96, and 98%, and the repeatabilities were 13, 11, and 3%. The detection and quantitation limits with ECD were 1.6 and 4.0 microg/kg, respectively. No statistically significant difference was observed in the efficiency of CAP extraction from muscle tissue of various animals (bovine, porcine, and poultry) by the MSPD technique.     

Determination of sulfonylurea herbicides in water and food samples using sol-gel glass-based immunoaffinity extraction and liquid chromatography-ultraviolet/diode array detection or liquid chromatography-tandem mass spectrometry

Immunoaffinity supports (IAS) were prepared using broad specific polyclonal anti-sulfonylurea (SU) antibodies immobilized in sol-gel glass. Two different kinds of supports were applied, crushed sol-gel monoliths and sol-gel-coated highly porous silica particles. Both were used for the quantitative enrichment of SUs in natural water and food samples followed by high-performance liquid chromatography-ultraviolet/diode array detection (HPLC-UV/DAD) and tandem mass spectrometry (LC-MS/MS), respectively. Loading, washing, and elution conditions of IAS were optimized. The capacity of supports was determined for 30 SUs and compared with the cross-reactivity pattern of the direct competitive enzyme-linked immunosorbent assay. The capacities correlated well with the affinity to individual SU compounds. Even analytes to which the polyclonal antibodies showed only a lower cross-reactivity could be enriched to a certain degree, if a sufficient capacity of IAS was provided. The IAS could be reused at least 10 times without a loss of effectiveness. Recovery of 16 selected SUs extracted from spiked water and food samples was dependent on the affinity of both immobilized antibodies to single compounds and matrix interferences. In water, 13 SUs showed recoveries higher than 80% when immunoaffinity extraction was used in combination with LC-UV/DAD. On the basis of the enrichment of 200 mL of aqueous sample, corresponding limit of detection (LOD) values ranged between 20 and 100 ng/L. The recoveries of 10 SUs, which were extracted from 10 g of potato spiked at a 10 microg/kg level, were higher than 75%. For grain samples, recoveries were at the same order for at least five SU herbicides. The LOD of LC-MS/MS measurements was about 1 order of magnitude higher, i.e., gave LODs between 1.1 and 6.9 microg/kg of food sample, depending on the compound and extraction procedure. These LODs provide evidence that the main advantage of the prepared IAS is their high selectivity for group specific recognition of SUs as compared to other nonspecific solid phase extraction materials.     

Development of a solid-phase extraction method for phenoxy acids and bentazone in water and comparison to a liquid-liquid extraction method

A rapid solid-phase extraction (SPE) method was developed for the determination of bentazone and the phenoxy acids 2,4-D, dichlorprop, MCPA, and mecoprop in Norwegian environmental water samples. Cartridges with a high-capacity cross-linked polystyrene-based polymer were used for off-line preconcentration. The effects of elution solvent, elution volume, sample volume, sorbent mass, pH, and flow rate on the recoveries of the pesticides were investigated using HPLC. Average recovery of >90% was achieved with 500 mg sorbents using 2 mL of methanol with 5% NH3 as elution solvent. The recoveries were independent of sample pH in the tested range of pH 1-7. Using a sample volume of 200 mL, the limits of determination for the phenoxy acids and bentazone are 0.02 microg/L. Sample volumes up to 2000 mL at a flow rate of 60 mL/min could be handled without any loss of analytes, which makes it possible to lower the limits of determination. The SPE method was compared to a routinely used liquid-liquid extraction method. Three different water matrices spiked at 1.0 and 0.05 microg/L were extracted, and the quantification was performed by GC-MS. Both methods permitted the determination of phenoxy acids and bentazone in distilled water, creek water, and well water down to a level of 0.05 microg/L with recoveries >80% for 200 mL samples. Important advantages of the SPE method compared to the liquid-liquid extraction method were the short extraction times, lack of emulsions, use of disposable equipment, and reduced consumption of organic solvents.     

Determination of bentazone, dichlorprop, and MCPA in different soils by sodium hydroxide extraction in combination with solid-phase preconcentration

A method for the extraction of bentazone, dichlorprop, and MCPA in three selected Norwegian soils of different textures is described. Initially three different extraction methods were tested on one soil type. All methods gave recoveries >80% for the pesticide mixture, but extraction with sodium hydroxide in combination with solid-phase preconcentration was used for further recovery tests with soils of different properties spiked at four herbicide concentration levels (0.001-10 microg/g of wet soil). The method was rapid and easy and required a minimum of organic solvents. The recoveries were in the range of 82-109, 80-123, and 45-91% for the soils containing 1.4 (Hole), 2.5 (Kroer), and 37.8% (Froland) organic carbon, respectively. Limits of quantification using GC-MS were 0.0003 microg/g of wet soil for bentazone and 0.0001 microg/g of wet soil for both dichlorprop and MCPA.     

Determination of metaldehyde in suspected cases of animal poisoning using gas chromatography-ion trap mass spectrometry.

A method was developed to detect the molluscicide metaldehyde in samples of stomach contents for forensic toxicology investigations. Gas chromatography-ion trap mass spectrometry in full-scan mode was used to identify and quantify metaldehyde. The limit of detection based on mass chromatograms for the m/z 89 ion was 3 microg/g. Mean recoveries from six different spiked samples were 74% at 25 microg/g and 94% at 500 microg/g. The relative standard deviation of six replicate determinations of a sample containing 632 microg/g metaldehyde was 7.3%.     

Determination of florfenicol amine residues in animal edible tissues by an indirect competitive ELISA

Florfenicol (FF) is a broad-spectrum antibiotic used increasingly in aquaculture, livestock, and poultry to treat diseases. To avoid using labor-intensive instrumental methods to detect residues of FF in food and food products, a simple and convenient indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) method for florfenicol's major metabolite, florfenicol amine (FFA), was developed using a polyclonal antibody prepared in this study. FFA was covalently attached to carrier protein as immunogen by using the glutaraldehyde method. The antibodies obtained were characterized by an ELISA method and showed excellent specificity and sensitivity with the 50% inhibition values (IC 50) of 3.34 microg/L for FFA in PBS buffer. In the ELISA, sample extractions were performed by ethyl acetate/ammonium hydroxide (90 + 10, v/v) following combined acid hydrolysis of FF and its known metabolites. The limits of detection (LOD) calculated from the analysis of 20 known negative swine muscle, chicken muscle, and fish samples were 3.08, 3.3, and 3.86 microg/kg (mean + 3 SD), respectively. Recoveries of FFA fortified at the levels of 5, 50, 100, and 300 microg/kg ranged from 64.6 to 124.7%, with coefficients of variation of 11.3-25.8% over the range of FFA concentrations studied. Validation of the ELISA method with FFA-fortified swine muscle at the levels of 10, 50, 100, and 200 microg/kg was carried out using GC, resulting in a similar correlation in swine muscle ( r = 0.97). The results suggest that this ELISA is a specific, accurate, and sensitive method, which is suitable for use as a screening method to detect residues of FFA in animal edible tissues.     

Parameters affecting extraction of selected fungicides from vineyard soils

This paper describes a sensitive method for the simultaneous quantification of eight commonly used grapevine fungicides in vineyard soils: cyprodinil, fludioxonil, metalaxyl, penconazole, pyrimethanil, procymidone, tebuconazole, and vinclozolin. The fungicides are extracted from the soil sample by sonication with water followed by shaking with ethyl acetate and are quantified by gas chromatography with mass spectrometry. Average extraction efficiencies in a sample of seven spiked, previously fungicide-free soils were > or =79% for all of the analytes, method precisions were > or =17%, and quantification limits were < or =50 microg/kg. However, because recoveries varied considerably from soil to soil, there is a need to control for soil matrix differences (mainly soil pH and exchangeable calcium content); as a consequence, soil fungicide contents must be quantified by the standard additions method. When the method was applied in this way to soil samples from vineyards belonging to the specified wine-growing region of Rias Baixas (Galicia, northwestern Spain) taken at the beginning of October (1 month after the crop's final treatment), levels of fludioxonil as high as 991 microg/kg were found, but at the start of the season (9 months after the previous crop's final treatment) only fludioxonil was detected at levels higher than its limit of quantification (45 and 52 microg/kg).     

Liquid chromatographic determination of natural and synthetic colorants in lyophilized foods using an automatic solid-phase extraction system

Five synthetic and five natural colorants were determined in lyophilized dairy products and fatty foods using an automatic method based on lixiviation and a solid-phase extraction process that includes cotton and RP-C(18) columns for the sequential retention of synthetic colorants and natural colorants, respectively. The lyophilization of the sample coupled with the separation procedure provides clean extracts despite the complexity of the matrices studied. In addition, the lyophilization process preserves the sample for at least 2 months without changes in the concentrations of the colorants. Identification and determination of synthetic and natural colorants were carried out using a liquid chromatograph equipped with a diode array detector. The detection limits achieved for all of the colorants (0.03-75 microg/g of lyophilized sample) allowed their determination within the limits established by the European Union, with good precision (approximately 4.5%). In addition, colorants spiked to different foods provided average recoveries (spiked at three concentration levels in four types of dairy samples and in three types of fatty foods) near 94 +/- 4%.     

Chloramphenicol extraction from honey, milk, and eggs using polymer monolith microextraction followed by liquid chromatography-mass spectrometry determination

A rapid confirmatory method for monitoring chloramphenicol (CAP) residues in honey, whole milk, and eggs is presented. This method is based on the polymer monolith microextraction (PMME) technique and high-performance liquid chromatography (HPLC)-electrospray ionization mass spectrometry (MS). A poly(methacrylic acid-ethylene glycol dimethacrylate) monolithic capillary column was selected as the extraction medium. To obtain optimum extraction efficiency, several parameters related to PMME were investigated. After dissolution in 20 mM phosphate solution at pH 4.0 and centrifugation, honey, eggs, or milk samples were directly passed through the extraction tube. The LC-MS instrument was equipped with an electrospray ion source and a single quadrupole. The eluates were analyzed by LC-MS in the negative-ion mode and by monitoring a pair of isotopic ions for the target compound. The in-source collision-induced dissociation process produced confirmatory ions. The recoveries of CAP from real samples spiked at 0.1-10 ng/g (honey), 0.2-10 ng/mL (milk), and 0.2-10 ng/g (egg) were in the range of 85-102%, with relative standard deviations ranging between 2.1% and 8.9%. The limits of detection (S/N = 3) were 0.02 ng/g, 0.04 ng/mL, and 0.04 ng/g in honey, milk, and eggs, respectively. The proposed method was proved to be robust in monitoring CAP residue in honey, milk, and eggs.     

Determination of triazine and chloroacetanilide herbicides in soils by microwave-assisted extraction (MAE) coupled to gas chromatographic analysis with either GC-NPD or GC-MS

A simple and rapid method based on microwave-assisted extraction (MAE) coupled to gas chromatographic analysis was developed for the analysis of triazine (atrazine, cyanazine, metribuzine, simazine and deethylatrazine, and deisopropylatrazine) and chloroacetanilide (acetochlor, alachlor, and metolachlor) herbicide residues in soils. Soil samples are processed by MAE for 5 min at 80 degrees C in the presence of acetonitrile (20 mL/sample). Mean recovery values of most solutes are >80% in the 10 to 500 microg/kg fortification range with respective RSDs (relative standard deviations) < 20%. The limits of quantification (LOQ) and limits of detection (LOD) are 10 and 1 to 5 microg/kg, respectively. The method was validated with two types of soils containing 1.5 and 3.0% organic matter content, respectively; no statistically significant differences were found between solute recovery values from the two types of soils. The solute mean recovery values from freshly spiked (24 h aging) and spiked samples stored refrigerated for one week before processed were also not statistically different. Residue levels determined in field weathered soils were higher when soils were processed by MAE than with a comparison method based on flask-shaking of soil suspensions overnight. Extracts were analyzed by a gas chromatographic system equipped either with a thermionic (GC-NPD) or a mass spectrometric detector (GC-MS).     

Acid-induced phase separation of anionic surfactants for the extraction of 1,4-dichlorobenzene from honey prior to liquid chromatography

The acid-induced liquid-liquid phase separation of anionic surfactants in aqueous solutions and its applicability to cloud point extraction methodology were applied as a tool for the extraction of 1,4-dichlorobenzene (p-DCB) from aqueous samples. p-DCB is extracted into the micelles of sodium dodecane sulfonate (SDSA) in a 4.2 M HCl solution. The micellar phase is separated from the bulk aqueous solution after centrifugation and collected from the surface of the suspension. The micellar extracts are injected into a high-performance liquid chromatographic apparatus and quantified at 225 nm with a reference wavelength of 280 nm. Following the proposed methodology, a preconcentration factor of ca. 160 is achieved (starting from 50 mL solutions) allowing for detection limits at the low microg/L level. Application to honey samples produced detection limits of 2.5 microg/kg with quantification limits of 7.5 microg/kg, while the recoveries of the method ranged from 85% at high concentrations to 95% at lower concentrations of p-DCB. The combined uncertainty of the entire analytical procedure was 4.5% at the concentration level of 30 microg/kg allowing for reliable and reproducible results for the determination of p-DCB at the concentration levels considered as thresholds for EU and U.S. legislation (10 microg/kg).     

Molecularly imprinted polymer online solid-phase extraction coupled with high-performance liquid chromatography-UV for the determination of three sulfonamides in pork and chicken

A selective imprinted amino-functionalized silica gel sorbent was prepared by combining a surface molecular imprinting technique with a sol-gel process for online solid-phase extraction-HPLC determination of three trace sulfonamides in pork and chicken muscle. The imprinted functionalized silica gel sorbent exhibited selectivity and fast kinetics for the adsorption and desorption of sulfonamides. With a sample loading flow rate of 4 mL min (-1) for 12.5 min, enhancement factors and detection limits for three sulfonamides ( S/ N = 3) were achieved. The precision (RSD) for nine replicate online sorbent extractions of 5 microg L (-1) sulfonamides was less than 4.5%. The sorbent also offered good linearity ( r (2) > 0.99) for online solid-phase extraction of trace levels of sulfonamides. The method was applied to the determination of sulfonamides in pork and chicken muscle samples. The prepared polymer sorbent shows promise for online solid-phase extraction for HPLC determination of trace levels of sulfonamides in pork and chicken samples.     

Analysis of chlorothalonil and three degradates in sediment and soil

A method has been developed for the simultaneous extraction of chlorothalonil and three of its degradates (4-hydroxy-2,5,6-trichloroisophthalonitrile, 1-carbamoyl-3-cyano-4-hydroxy-2,5,6-trichlorobenzene, and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene) from soils and sediments; the compounds were extracted using sonication with acetone and isolation of the parent compound and matrix interferences from the degradates by solid phase extraction (SPE). The chlorothalonil fraction underwent further coextracted matrix interference removal with Florisil. The degradates were derivatized with N, O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) and chlorotrimethylsilane (TMCS). All compounds were analyzed by gas chromatography-mass spectrometry (GC-MS). Recoveries on a spiked (20 and 200 microg kg (-1)) sediment ranged from 80% to 91% with calculated limits of detection of 1-5 microg kg (-1) dry weight sediment. An additional 20 sediment samples were collected in watersheds from the Southeastern United States where chlorothalonil is used widely on peanuts and other crops. None of the target compounds were detected. Laboratory fortified recoveries of chlorothalonil and its degradates in these environmental sediment samples ranged from 75% to 89%.