A simple, fast, and inexpensive method for the determination of pesticide residues in fruits and vegetables is introduced. The procedure involves initial single-phase extraction of 10 g sample with 10 mL acetonitrile, followed by liquid–liquid partitioning formed by addition of 4 g anhydrous MgSO4 plus 1 g NaCl. Removal of residual water and cleanup are performed simultaneously by using a rapid procedure called dispersive solid-phase extraction (dispersive-SPE), in which 150 mg anhydrous MgSO4 and 25 mg primary secondary amine (PSA) sorbent are simply mixed with 1 mL acetonitrile extract. The dispersive-SPE with PSA effectively removes many polar matrix components, such as organic acids, certain polar pigments, and sugars, to some extent from the food extracts. Gas chromatography/mass spectrometry (GC/MS) is then used for quantitative and confirmatory analysis of GC-amenable pesticides. Recoveries between 85 and 101% (mostly >95%) and repeatabilities typically <5% have been achieved for a wide range of fortified pesticides, including very polar and basic compounds such as methamidophos, acephate, omethoate, imazalil, and thiabendazole. Using this method, a single chemist can prepare a batch of 6 previously chopped samples in <30 min with approximately $1 (U.S.) of materials per sample.

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A collaborative study was conducted to determine multiple pesticide residues in fruits and vegetables using a quick, simple, inexpensive, and effective sample preparation method followed by concurrent analysis with gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). For short, the method is known as QuEChERS, which stands for quick, easy, cheap, effective, rugged, and safe. Twenty representative pesticides were fortified in 3 matrixes (grapes, lettuces, and oranges) at 3 duplicate levels unknown to the collaborators ranging from 10 to 1000 ng/g. Additionally, 8 incurred pesticide residues were determined. Thirteen laboratories from 7 countries provided results in the study, and a variety of different instruments were used by collaborators. The QuEChERS procedure simply entails 3 main steps: (1) a 15 g homogenized sample is weighed into a 50 mL centrifuge tube to which 15 mL acetonitrile containing 1 HOAc is added along with 6 g MgSO4 and 1.5 g NaOAc, and the tube is shaken and centrifuged; (2) a portion of the extract is mixed with 3 + 1 (w/w) MgSO4primary secondary amine sorbent (200 mg/mL extract) and centrifuged; and (3) the final extract is analyzed by GC/MS and LC/MS/MS. To detect residues <10 ng/g in GC/MS, large-volume injection of 8 L is typically needed, or the extract can be concentrated to 4 g/mL in toluene, in which case 2 L splitless injection is used. In the study, the averaged results for data from 713 laboratories (not using internal standardization) for the 18 blind duplicates at the 9 spiking levels in the 3 matrixes are as follows [%recovery and reproducibility relative standard deviation (RSDR, %)]: atrazine, 92 (18); azoxystrobin, 93 (15); bifenthrin, 90 (16); carbaryl, 96 (20); chlorothalonil, 70 (34); chlorpyrifos, 89 (25); cyprodinil, 89 (19); o, p-DDD, 89 (18); dichlorvos, 82 (21); endosulfan sulfate, 80 (27); imazalil, 77 (33); imidacloprid, 96 (16); linuron, 89 (19);methamidophos, 87 (17); methomyl, 96 (17); procymidone, 91 (20); pymetrozine, 69 (19); tebuconazole, 89 (15); tolylfluanid (in grapes and oranges), 68 (33); and trifluralin, 85 (20). For incurred pesticides, kresoxim-methyl (9.2 3.2 ng/g) and cyprodinil (112 18) were found in the grapes; permethrins (112 41), -cyhalothrin (58 11), and imidacloprid (12 2) were determined in the lettuces; and ethion (198 36), thiabendazole (53 8), and imazalil (13 4) were determined in the oranges. Chlorpyrifosmethyl (200 ng/g) was used as a quality control standard added during sample homogenization and yielded 86% recovery and 19% RSDR. Intralaboratory repeatabilities for the method averaged 9.8% RSD for all analytes. The results demonstrate that the method is fit-for- purpose to monitor many pesticide residues in fruits and vegetables, and the Study Director recommends that it be adopted Official First Action.

A modification that entails the use of buffering during extraction was made to further improve results for certain problematic pesticides (e.g., folpet, dichlofluanid, chlorothalonil, and pymetrozine) in a simple, fast, and inexpensive method for the determination of pesticides in produce. The method, known as the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for pesticide residues in foods, now involves the extraction of the sample with acetonitrile (MeCN) containing 1% acetic acid (HAc) and simultaneous liquid–liquid partitioning formed by adding anhydrous MgSO4 plus sodium acetate (NaAc). The extraction method is carried out by shaking a centrifuge tube which contains 1 mL of 1% HAc in MeCN plus 0.4 g anhydrous MgSO4 and 0.1 g anhydrous NaAc per g sample. The tube is then centrifuged, and a portion of the extract is transferred to a tube containing 50 mg primary secondary amine sorbent plus 150 mg anhydrous MgSO4/mL of extract. After a mixing and centrifugation step, the extract is transferred to autosampler vials for concurrent analysis by gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry. Independent of the original sample pH, the use of buffering during the extraction yields pH <4 in the MeCN extract and >5 in the water phase, which increases recoveries of both acid- and base-sensitive pesticides. The method was evaluated for 32 diverse pesticides in different matrixes, and typical percent recoveries were 95 ± 10, even for some problematic pesticides. Optional solvent exchange to toluene prior to GC/MS analysis was also evaluated, showing equally good results with the benefit of lower detection limits, but at the cost of more time, material, labor, and expense.

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Two rapid methods of sample preparation and analysis of fatty foods (e.g., milk, eggs, and avocado) were evaluated and compared for 32 pesticide residues representing a wide range of physicochemical properties. One method, dubbed the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for pesticide residue analysis, entailed extraction of 15 g sample with 15 mL acetonitrile (MeCN) containing 1% acetic acid followed by addition of 6 g anhydrous magnesium sulfate and 1.5 g sodium acetate. After centrifugation, 1 mL of the buffered MeCN extract underwent a cleanup step (in a technique known as dispersive solid-phase extraction) using 50 mg each of C18 and primary secondary amine sorbents plus 150 mg MgSO4. The second method incorporated a form of matrix solid-phase dispersion (MSPD), in which 0.5 g sample plus 2 g C18 and 2 g anhydrous sodium sulfate was mixed in a mortar and pestle and added above a 2 g Florisil column on a vacuum manifold. Then, 5 × 2 mL MeCN was used to elute the pesticide analytes from the sample into a collection tube, and the extract was concentrated to 0.5 mL by evaporation. Extracts in both methods were analyzed concurrently by gas chromatography/mass spectrometry and liquid chromatography/tandem mass spectrometry. The recoveries of semi-polar and polar pesticides were typically 100% in both methods (except that basic pesticides, such as thiabendazole and imazalil, were not recovered in the MSPD method), but recovery of nonpolar pesticides decreased as fat content of the sample increased. This trend was more pronounced in the QuEChERS method, in which case the most lipophilic analyte tested, hexachlorobenzene, gave 27 ± 1% recovery (n = 6) in avocado (15% fat) with a <10 ng/g limit of quantitation.

Validation experiments were conducted of a simple, fast, and inexpensive method for the determination of 229 pesticides fortified at 10–100 ng/g in lettuce and orange matrixes. The method is known as the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for pesticide residues in foods. The procedure involved the extraction of a 15 g sample with 15 mL acetonitrile, followed by a liquid–liquid partitioning step performed by adding 6 g anhydrous MgSO4 plus 1.5 g NaCl. After centrifugation, the extract was decanted into a tube containing 300 mg primary secondary amine (PSA) sorbent plus 1.8 g anhydrous MgSO4, which constituted a cleanup procedure called dispersive solid-phase extraction (dispersive SPE). After a second shaking and centrifugation step, the acetonitrile extract was transferred to autosampler vials for concurrent analysis by gas chromatography/mass spectrometry with an ion trap instrument and liquid chromatography/tandem mass spectrometry with a triple quadrupole instrument using electrospray ionization. Each analytical method was designed to analyze 144 pesticides, with 59 targeted by both instruments. Recoveries for all but 11 of the analytes in at least one of the matrixes were between 70–120% (90–110% for 206 pesticides), and repeatabilities typically <10% were achieved for a wide range of fortified pesticides, including methamidophos, spinosad, imidacloprid, and imazalil. Dispersive SPE with PSA retained carboxylic acids (e.g., daminozide), and <50% recoveries were obtained for asulam, pyridate, dicofol, thiram, and chlorothalonil. Many actual samples and proficiency test samples were analyzed by the method, and the results compared favorably with those from traditional methods.

Analytical methods for contaminant monitoring are generally targeted; i.e., they measure defined lists of compounds. Routine monitoring projects using targeted methods are not usually designed to screen for unrecognized or novel contaminants and therefore miss compounds within the region or population of study that cause, or have the potential to cause, adverse biological impacts. We describe a nontargeted analytical method utilizing direct sample introduction coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry. To test the capabilities of this instrumental method within the context of marine contaminant surveys, we characterized a broad array of nonpolar, persistent, and bioaccumulative contaminants in Atlantic common dolphin ( Delphinus delphis ) blubber, including compounds that are not typically monitored. Compound identifications were made by searching a standard reference database, by contemporaneously analyzing mass spectra from reference standards, and by de novo interpretation. We identified a total of 271 compounds belonging to 24 classes; all compounds but 1 were halogenated. Anthropogenic contaminants and halogenated natural products were concurrently detected. A total of 86 compounds were anthropogenic contaminants that are not routinely targeted in environmental surveys, and 54 compounds were halogenated natural products. A total of 112 spectra were identified de novo, demonstrating that exclusive reliance on commercially available reference standards and mass spectral libraries may miss a significant fraction of identifiable compounds. We also cataloged 27 halogenated mass spectra that were not able to be identified. Due to the volume and complexity of the identification data, we developed custom software to organize and provide shared access to the identified mass spectra and related information. The nontargeted analytical method and data reporting system, in combination with the analysis of a high-trophic-level sentinel species, demonstrates a framework for creating an inventory of persistent and bioaccumulative contaminants in marine environments, with the future goal of suggesting new compounds for further investigation by targeted monitoring and risk assessment.