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Background: Residues of polar pesticides cannot be determined by QuEChERS-based multiresidue extractions because of their non-amenability to reverse-phase chromatographic separation and poor recoveries. On the other hand, single-residue methods pose limitations because of the various requirements of sample preparation and LC-MS/MS conditions. A new multiresidue method is thus warranted for rapid and simultaneous analysis of polar pesticides., Objective: The study developed a multiresidue method for the simultaneous analysis of glyphosate and its metabolite (aminomethylphosphonic acid, AMPA), glufosinate and its metabolites (3-methylphosphinicopropionic acid and N-acetyl-glufosinate), ethephon, fosetyl-aluminum and its metabolite (phosphonic acid), and trimesium in grape and pomegranate by LC-MS/MS., Method: The homogenized samples (10 g) were extracted with acidified methanol (20 mL). An aliquot of the extract was diluted with acetonitrile (1 + 1) and measured by LC-MS/MS using a Torus DEA column. The performance of a hydrophilic interaction liquid chromatography (HILIC) column and an "anionic polar pesticides" (APP) column was also evaluated., Results: The method performance on the Torus DEA column was satisfactory for all compounds (recoveries = 77-104%, repeatability-RSD, <11%) at limit of quantification (LOQ) (0.01 mg/kg), and with higher levels in grape and pomegranate. The only exception was AMPA, which had an LOQ of 0.05 mg/kg. In the APP column, AMPA could be determined with an LOQ of 0.01 mg/kg. Trimesium, which had poor retention in Torus DEA, performed better in an XBridge HILIC column (retention time = 4.2 min, LOQ = 0.01 mg/kg). The inter-laboratory validation experiment yielded comparable results with high accuracy and precision., Conclusions: The method could screen the residues of all compounds on a Torus DEA column. For AMPA and trimesium, the APP and XBridge HILIC columns provided superior method performances. Since isotopically labeled internal standards were not required, the method appeared cost-effective. Considering its compliance with the SANTE/12682/2019 validation guidelines and EU-MRLs, the method can be recommended for regulatory testing purposes., Highlights: A high-throughput residue analysis method targeting nine polar and ionic compounds in grape and pomegranate involved a single multiresidue extraction, followed by direct analysis using LC-MS/MS. A satisfactory method performance was achieved through intra- and inter-laboratory validation. The method sensitivity met the EU-MRLs and the SANTE/12682/2019 analytical quality control criteria., (© The Author(s) 2022. Published by Oxford University Press on behalf of AOAC INTERNATIONAL. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: Aflatoxin M1 (AFM1) is a carcinogenic hydroxylated metabolite commonly found in milk. It is relatively stable toward decontamination procedures posing a major health risk, and it requires an international regulatory mandate of detection at trace levels., Objective: To develop a high-throughput, reliable, and compliant method for the identification of AFM1 in milk samples using atmospheric pressure-matrix assisted laser desorption/ionization (AP-MALDI) selected reaction monitoring (SRM) quantitation., Method: The milk sample was diluted in water and cleaned with immunoaffinity chromatography (IAC), followed by analysis using AP-MALDI hyphenated with a triple quadrupole mass spectrometer for SRM., Results: A fast and reliable AP-MALDI SRM quantitative method was developed for the determination of AFM1 with analysis time of 1 min per sample. The diagnostic product ions of AFM1 at 273.1 u and 229.2 u were monitored during the SRM. The calibration curves yielded excellent linearity (R2 = 0.99) with good recoveries for quality control samples (97-106%). The ion ratios of the qualifier to quantifier displayed excellent RSD (1-7.8%) for n = 3., Conclusions: The developed method provided rapid quantification for AFM1. The fast AP-MALDI SRM method can allow analysis of AFM1 in a large number of milk samples. Given the time required for analysis, cost-effectiveness, and superior analytical performance, this method can be adopted in commercial food testing laboratories., Highlights: Aflatoxins (AF) are a major health risk. Speedy analysis of large sample sizes from food is a risk mitigation strategy but remains an unmet need. Quantitative, chromatography-free, and internal standard-free AP-MALDI SRM based analysis of AF is a high-throughput and cost-efficient alternative. Satisfactory performance was achieved for quantitative AP-MALDI SRM analysis of AFM1 in milk subsequent to a simple sample clean-up step., (© The Author(s) 2022. Published by Oxford University Press on behalf of AOAC INTERNATIONAL. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: The testing of aflatoxins (AFs) in fresh and processed foods is highly in demand to comply with trade regulations. Consequently, commercial laboratories face huge AF sample loads in food consignments. Worldwide, there is a rising interest in implementing automation to increase sample throughput in AF analysis., Objective: This study sought to evaluate the performance of an automated cleanup and HPLC analysis system for determination of regulated AFs (B1, B2, G1, G2) in rice, flattened rice, sorghum, raw and processed peanut, almond, peanut butter, and wheat-based cookies., Methods: The samples were extracted with methanol-water (80:20), diluted with Triton X-100, and subjected to automated analysis, where the cleanup step through immunoaffinity column (IAC) and HPLC-fluorescence analyses (involving postcolumn bromination-derivatization) were performed in 10 and 11 min, respectively. The method was validated in all test matrices at the LOQ and higher levels. The method performance was also evaluated against a conventional workflow where cleanup and HPLC analysis were manually performed., Results: The LOQ for peanut, sorghum, rice, and flattened rice was 0.125 ng/g, while it was 0.5 ng/g for peanut butter, almond, and wheat-based cookies. In all matrices, the recoveries at LOQ and higher levels were satisfactory. The double-cartridge exchange system completed the analysis of ∼96 injections in 18 h. Each IAC could be reused 15 times without incurring any recovery loss. The automated system provided a better precision (RSD < 9%) than the conventional workflow (RSD = 12-15%)., Conclusions: Because of its high-throughput nature, this method is recommended for routine analysis of AFs., Highlights: A high-throughput method is reported where cleanup and HPLC analysis of AFs were automatically performed. Each IAC could be used 15 times without any loss of recovery. The method performance was better than the conventional approach and complied with the analytical quality control guidelines., (© AOAC INTERNATIONAL 2021. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: For years, turmeric has been used in several cuisines worldwide because of its proven health benefits. However, as its cultivation often involves applications of polar and semi-polar pesticides, their residues might cause health hazards to consumers. The dearth of a validated LC-MS/MS method for the residue analysis of these pesticides in turmeric has warranted the present study., Objective: The aim was to develop and validate a multi-residue method for simultaneous determination of multi-class pesticides in turmeric (both rhizome and powder) by LC-MS/MS., Method: Both the rhizome and powder samples (1 kg) were soaked in water for 30 min, followed by homogenization. Each homogenate (2 g) was mixed with 10 mL water, and extracted with acetonitrile (10 mL) in the presence of acetic acid and NaCl. The extract was cleaned by using dispersive solid phase extraction (dSPE) with graphitized carbon (5 mg/mL) sorbent. The cleaned extract was measured by LC-MS/MS with a runtime of 20 min. The method was validated on 211 multi-class pesticides., Results: The method performance was satisfactory at 10 ng/g and higher levels, in compliance with the SANTE/12682/2019 guidelines. The dSPE cleanup was effective in minimizing the matrix effects. The use of matrix-matched calibrations specific for turmeric powder and rhizome corrected all recoveries within the satisfactory range of 70-120%. The precision -RSDs were <20% for all test pesticides. The Horwitz ratio and measurement uncertainty results were satisfactory as well., Conclusions: As the method was convenient, selective, accurate, and repeatable, it is recommended for regulatory and commercial testing purposes., Highlights: For the first time, this study reports a validated LC-MS/MS method for the multi-residue analysis of pesticides in turmeric. The method provided a high throughput analysis of multi-class pesticides in turmeric rhizome and powder matrices with satisfactory selectivity, sensitivity, accuracy, and precision. The method performance satisfied the requirements of the SANTE/12682/2019 guidelines, and the method sensitivity complied with the EU-MRL requirements., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background and Objectives: Turmeric is widely used as an ingredient of food and medicinal products. There exists no validated method for multi-residue analysis of pesticides in turmeric., Objective: This study was undertaken to develop a simple and robust method for the quantitative determination of multi-class pesticides in turmeric powder and rhizome by GC-MS/MS., Method: Initially, the samples were soaked in water for 30 min and homogenized to a fine paste. A portion of this paste (2 g) was extracted with acetonitrile (2 mL) and partitioned with hexane (2 mL) after adding 5 mL of 20% NaCl. The cleanup step involved dispersive solid phase extraction with graphitized carbon black (GCB, 5 mg/mL). Its performance was evaluated against primary secondary amine (PSA) and C18 sorbents. The cleaned extract was evaporated to dryness and reconstituted in ethyl acetate before GC-MS/MS analysis. The method was validated for a mixture of 208 multi-class pesticides at 10 ng/g and higher levels (i.e., 20 and 50 ng/g)., Results: The findings, which demonstrated a satisfactory recovery and precision (RSDs <20%) for all compounds at 10 ng/g and higher spiking levels, are aligned with the analytical quality control criteria of SANTE/12682/2019 guidelines. The cleanup effect of GCB was much superior to that of PSA, C18, and their combinations. The solvent exchange step with hexane was effective in removing co-extractives and minimizing matrix effects., Conclusions: This method complies with the regulatory requirements and is fit-for-purpose for pesticide residue monitoring in turmeric., Highlights: The study reports a validated GC-MS/MS method for multi-residue analysis of pesticides in turmeric for the first time. The method provided a high throughput analysis of multi-class pesticides in turmeric rhizome and powder matrices with satisfactory selectivity, sensitivity, accuracy, and precision., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: Moringa pods are known for their nutritional and health benefits. The cultivation of this crop receives frequent pesticide applications. In the absence of risk assessment data, maximum residue limits of pesticides in this crop are considered at the default level (0.01 mg/kg). However, there exists scarcely any validated method for pesticide residue analysis in this matrix., Objective: This study was undertaken to develop and validate a multiresidue method for the simultaneous analysis of multi-class pesticides in moringa pods by gas chromatography-tandem mass spectrometry (GC-MS/MS), and liquid chromatography-tandem mass spectrometry (LC-MS/MS)., Method: The homogenized sample (10 g) was extracted with acetonitrile (10 mL). The extract was cleaned by dispersive solid-phase extraction using a combination of 50 mg primary secondary amine, 5 mg graphitized carbon black, and 25 mg C18 sorbents, and was directly analyzed by LC-MS/MS. Another portion of the extract was reconstituted in ethyl acetate before GC-MS/MS analysis. The method was validated as per the SANTE/12682/2019 guidelines using GC-MS/MS (180 pesticides) and LC-MS/MS instruments (203 pesticides)., Results: The method provided a satisfactory analysis of the targeted pesticides with good calibration linearity (r2>0.99), high precision (RSD < 20%), and accuracy (recoveries, 70 to 120%). The reconstitution of the acetonitrile extract in ethyl acetate significantly reduced the matrix effects on GC-MS/MS analysis. The use of matrix-matched standards could correct all recoveries., Conclusions: The method offered a large-scale analysis of multi-class pesticides with high accuracy, and precision at 10 ng/g, and higher levels. The method performance complied with the regulatory requirements, and thus, can be implemented in routine testing purposes., Highlights: The study reports a validated method for large-scale multiresidue analysis of pesticides in moringa matrix for the first time. The method provided a high throughput analysis of multi-class pesticides with satisfactory selectivity, sensitivity, accuracy, and precision., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: Indaziflam (IND) is a herbicide that is used in palm oil plantations for broad spectrum management of weeds. Until now, no validated method has been available for residue estimation of this herbicide in palm oil products., Objective: In this study, we report a rapid method for the residue analysis of IND and its metabolites, viz., IND-carboxylic acid, diaminotriazine, and triazine indanone in a wide range of palm oil matrices using liquid chromatography-tandem mass spectrometry (LC-MS/MS)., Method: The optimized sample preparation workflows included two options: (1) acetonitrile extraction (QuEChERS workflow), followed by freezing at -80°C and (2) acetonitrile extraction, followed by cleanup through a C18 solid phase extraction (SPE) cartridge. The optimized LC runtime was 7 min. All these analytes were estimated by LC-MS/MS multiple reaction monitoring., Results: Both sample preparation methods provided similar method performance and acceptable results. The limit of quantification (LOQ) of IND, IND-carboxylic acid, and triazine indanone was 0.001 mg/kg. For diaminotriazine, the LOQ was 0.005 mg/kg. The method accuracy and precision complied with the SANTE/12682/2019 guidelines of analytical quality control., Conclusions: The potentiality of the method lies in a high throughput analysis of IND and its metabolites in a single chromatographic run with high selectivity and sensitivity. Considering its fit-for-purpose performance, the method can be implemented in regulatory testing of IND residues in a wide range of palm oil matrices that are consumed and traded worldwide., Highlights: This work has provided a validated method for simultaneous residue analysis of indaziflam and its metabolites in crude palm oil and its derived matrices with high sensitivity, selectivity, and throughput., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background and Objective: Aflatoxin (AF) contamination is one of the major regulatory concerns for animal feed. As feed is a complex analytical matrix, validated methods on AFs in feed are scanty. The available methods involve a derivatization step before AF analysis by high-performance liquid chromatography (HPLC) with fluorescence detection (FLD). The aim of this study was thus to develop and validate a simple and rapid method for direct analysis of AFs (AFB1, AFB2, AFG1, AFG2) in a range of animal feed matrices., Methods: Feed samples were extracted with 80% methanol, followed by dilution with water and immmunoaffinity column cleanup. AFs were estimated using an ultra-high performance liquid chromatography (UHPLC) instrument. Use of a large volume flow cell in FLD allowed direct analysis of all AFs with high sensitivity. The method was thoroughly validated in a range of feed matrices., Results: This sample preparation workflow minimized co-extractives, along with matrix interferences. In pigeon pea husk feed, the method provided a limit of quantification (LOQ) of 0.5 ng/g for each AF with recoveries of AF- B1, B2, G1, and G2 as 71.5, 75.6, 82.4, and 78.2%, respectively. The precision (relative standard deviation, RSD) was below 5%. A similar method performance was also recorded in other matrices, including wheat bran feed and poultry feed., Conclusions: The optimized method is suitable for regulatory testing because it is simple, robust, cost-effective, and high throughput in nature, with high sensitivity and selectivity., Highlights: Our workflow has provided a straightforward method for the analysis of AFs in a wide range of animal feed matrices with high sensitivity, selectivity, throughput, and cost-effectiveness. The method allowed a direct analysis of AFs by UHPLC-FLD without a step of derivatization., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: Pharmaceuticals and personal care products (PPCPs) are present in the environment in trace concentrations. These compounds may cause health hazards to human beings and animals. The concerns related to their existence has led to development of a number of sensitive, accurate, and robust analytical methods., Objective: This article aims to review the recently developed chromatography-MS-based methods for the analysis of PPCPs in varied aqueous matrices and also presents a brief overview of the current status of PPCPs in the Indian aquatic environment., Methods: It demonstrates existing and recent trends in sampling, sample preparation techniques, and instrumentation methods for estimation of PPCPs in water., Results: Solid-phase extraction is found to be the most commonly used sample preparation technique, and LC-tandem MS (MS/MS; with electrospray ionization) is the most extensively used instrumentation technique for the analysis of PPCPs., Conclusions: The analytical methods reviewed here provide a detailed overview of the procedures for detection and quantification of PPCPs in water. These methods are useful for monitoring these compounds in environmental matrices and facilitate risk assessment studies., Highlights: This paper reviews the analytical methods for estimation of PPCPs in aquatic environmental matrices and presents their comprehensive evaluation., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: False detection of pesticides in agricultural produce may raise serious questions regarding both consumer safety and trade. High levels of delta-hexachlorocyclohexane (δ-HCH; 11.7-22.3 mg/kg) were detected in some tobacco samples in a retention time-based GC analysis. Hence, the selection of an appropriate analytical method is an uncompromisable necessity., Objectives: This research work aimed to elucidate false detection of pesticides along with identification of coeluting tobacco matrix compounds to understand the dynamics of false detection with an increase in the number of analyzed pesticides and to screen suitable analytical methods., Methods: Initially, retention time-based GC analysis was performed for monitoring of 10 pesticide residues in tobacco leaf matrix, followed by GC-MS/selected-ion monitoring (SIM) analysis. Then, the total number of pesticides to be analyzed was increased to 47, and residue analysis was performed by involving GC-MS/SIM and multidimensional (MD) GC-MS., Results: A false-positive detection of δ-HCH due to a coeluting tobacco aroma compound, neophytadiene, during residue analysis of 10 pesticides in tobacco (Nicotiana tabacum L.) leaf was observed. This problem was resolved by employing the unique quantifier and qualifier ions in SIM mode. However, with 47 pesticides, neophytadiene completely masked the signal of δ-HCH, which resulted in an impure spectrum of δ-HCH (<30% similarity match) even after application of selective quantifier and qualifier ions. Finally, MDGC-MS analysis could resolve it by chromatographic separation of the said analyte from the coeluting matrix compound., Conclusions: The findings of this work offer the potential to minimize false reporting of target pesticides to comply with consumer safety and trade standards., Highlights: The study identifies various tobacco matrix compounds coeluting with pesticides during multiresidue analysis. Neophytadiene, a tobacco aroma compound, resulted in false-positive detection of δ-HCH. The MDGC-MS could be effectively used as a confirmatory analysis tool for reliable detection of pesticide residue in tobacco leaf matrix., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: As a powerful antioxidant and natural colorant, anthocyanins are being used increasingly as a component of food supplements and nutraceutical products. Hence, its characterization is a prerequisite for further exploration of its nutraceutical potential. UV-Vis and MS are the two important techniques, which have been largely employed for the qualitative and quantitative determination of anthocyanins. However, a comprehensive review of the applications of these techniques in literature is scarce., Objective: This paper aims to review the utilization of UV-Vis spectral data as well as mass spectral data for characterization and putative identification of anthocyanins with approaches of quantification., Methods: The techniques described in literature have been thoroughly reviewed and comparatively evaluated. The complementary approaches of UV-Vis and MS spectra have been discussed for identification and quantification of these compounds., Results: Valuable information about the chemical composition and structure of anthocyanins can be predicted from the UV-Vis spectral data, such as number and type of glycosylation as well as absence or presence of acylation, to name a few. It is also pointed out that for their structural confirmation, selectivity of mass detectors with unit and high-resolution analysis could be effective., Conclusions: The combination of LC-MS with UV-Vis spectroscopy provides complementary information on structural details of anthocyanins. In case the analytical reference standards are available, a triple quadrupole mass spectrometer provides selectivity and quantitative sensitivity in analysis. On the other hand, high-resolution MS analysis provides valuable information for tentative identification during nontarget screening of compounds when the reference standard is not available., Highlights: This paper reviews the applications of UV-Vis spectroscopy and LC-MS for qualitative and quantitative analysis of anthocyanins., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: Pesticide residues are routinely tested in spices for trade compliance. This results in a huge sample load for food testing laboratories and demands automation in sample preparation. Although there exists a method for the analysis of pesticides in fruits using an automated sample cleanup by mini-solid-phase extraction (mini-SPE) technique, no study is available to date on spices., Objective: This study aims to develop an automated sample cleanup method using mini-SPE technique in a range of spices, including chili powder, turmeric, black pepper, cumin, coriander, and cardamom., Methods: This automated sample preparation workflow involved an X-Y-Z instrument autosampler, and a set of mini-SPE cartridges comprising cleanup sorbents. Spice samples were extracted by acetonitrile, and the extract was put into an autosampler vial for automated mini-SPE cleanup before analysis by GC tandem MS. For an efficient cleanup, three different sorbent compositions were compared along with various automated workflows., Results: For the relatively simple matrixes (e.g., coriander, cumin, and cardamom), the LOQ for the target pesticides was 10 ng/g with acceptable recovery, and precision. The method provided an LOQ of 10 ng/g for around 77% of the compounds in the relatively complex matrixes (e.g., turmeric, chili powder, and black pepper). The remainder of the compounds had satisfactory recoveries at 20 ng/g and higher levels., Conclusions: Given its time effectiveness and efficient analytical performance, this method can be adopted in commercial food testing laboratories for time-bound analysis of a large volume of samples., Highlights: The study describes effectiveness of the automated mini-SPE cleanup in multiresidue analysis of pesticides in a range of spice matrixes. The method facilitates high-throughput residue analysis in compliance with the regulatory requirements of sensitivity and method performance., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

Background: Mycotoxins such as aflatoxins (AFs) and ochratoxin A (OTA) can pose severe health hazards because of their toxicity. Given a wide range of food matrices susceptible to fungal infections and possible cooccurrence of mycotoxins at different concentrations, validated multimycotoxin and multimatrix methods are strongly warranted. Objective: The aim of this research was to develop a simple and fast ultra-high performance LC (UHPLC) fluorescence detection (FLD)-based method to simultaneously determine AFs (B1, G1, B2, and G2) and OTA and, furthermore, to carry out single-laboratory validation in a range of cereals and processed product matrices. Methods: The sample preparation involved homogenization and extraction with methanol-water (80 + 20). For cleanup, an aliquot (3 mL) was diluted with phosphate-buffered saline, loaded on an immunoaffinity column (AFLAOCHRA PREP ® ), and eluted with methanol (1 mL). The cleaned extract was diluted with 0.2% acetic acid (at a 1:1 ratio) before injection into an ultra-high performance liquid chromatograph. To perform simultaneous analysis of AFs and OTA, the FLD program was developed by switching the excitation wavelength in a single chromatographic run. Results: The method provided LOQs of 0.25 and 1 ng/g for AFs and OTA, respectively, without involving any derivatization. In rice, the recoveries of AFs ranged from 84 to 106%, whereas OTA had a recovery above 72%, with the repeatability relative SDs <12% for both analytes. The method was successfully applied to a range of naturally contaminated market samples. Conclusions: The method is suitable for regulatory testing because of its significant time and cost effectiveness and sensitivity in compliance with the regulatory maximum levels. Highlights: The study achieves high-throughput analysis of AFs and OTA in raw and processed cereals using simultaneous extraction, cleanup, and UHPLC-FLD. Method sensitivity complies with the regulatory maximum levels. Single-laboratory validation results meet analytical QC requirements.

A QuEChERS technique-based sample preparation method was optimized and validated in small cardamom to monitor the residues of 154 pesticides by LC with tandem MS. The proposed multiresidue method involved soaking powdered cardamom (2 g) in water (8 mL) for 30 min, followed by extraction with acetonitrile (10 mL). Cleanup by dispersive SPE was performed using primary secondary amine (25 mg/mL), C18 (25 mg/mL), and anhydrous magnesium sulfate (150 mg/mL). The method was validated as per the SANTE/11945/2015 guidelines at 5, 10, 50, and 100 ng/g spiking levels, and most of the analytes showed recoveries between 70 and 120% (with RSDs ≤20%). The LOQ of ≤10 ng/g was achieved for almost 90% of the target pesticides. The measurement uncertainties were evaluated at 100 ng/g, and the global uncertainty values were below 22% for all the analytes.

A chromatography-free atmospheric pressure matrix-assisted laser desorption/ionization high-resolution mass spectrometry (AP-MALDI HRMS) method is described for the simultaneous and quantitative detection of triazines and triazoles in grapes. The analytes were detected reproducibly with high mass accuracy (mass error within 5 ppm) and further confirmed by collision-induced dissociation fragmentation in tandem MS. The LODs and LOQs for all the analytes were found to be in the nanogram per gram level (15-20 ng/g LOQ). Internal standard-normalized high-resolution accurate mass-extracted (HR-AM) peak intensities of the detected ions were used to generate the concentration response curves. Linearity (with R2 values around 0.99) was obtained for these curves within a concentration range of 20-200 ng/g of the individual analytes. The accuracy and precision of the method were further established using QC samples. Validation and performance comparison of the AP-MALDI HRMS method with an existing standard method using LC with triple quadrupole MS was carried out (evaluating sensitivity, accuracy, precision, and analysis time) using 20 table-grape field samples after QuEChERS extraction.

A quick, sensitive multiresidue method was developed for the analysis of 19 multiclass pharmaceuticals and personal care products (PPCPs) in surface water and sewage water. The proposed modified QuEChERS method involved the extraction of water samples (10 mL) with acetonitrile (10 mL) after the addition of 1% acetic acid, 4 g magnesium sulfate, and 0.2 g ammonium acetate, and was validated in distilled water, surface water, and sewage water with respect to linearity, LOD and LOQ, precision, and accuracy. The LOD and LOQ varied within the ranges of 0.001-0.167 and 0.002-0.25 ng/mL, respectively. Recoveries of the target compounds ranged from 73 to 125%, with precision RSD values <27%. The method provided a precise estimation of PPCPs in field samples, and acetaminophen, atenolol, metformin, sulfamethoxazole, carbamazepine, methylparaben, and triclosan were detected in concentrations ranging from 0.10 to 1.40 and 0.10 to 3.4 ng/mL in surface water and sewage water, respectively. This is an innovative application of the QuEChERS approach for estimation of PPCPs from aqueous matrixes. The method provides significantly higher output (preparation of 25-30 samples a day) compared to conventional SPE-based methods (<10 samples a day).

A sensitive and accurate LC with tandem MS (MS/MS)-based method was developed and validated for the analysis of the herbicide glyphosate, its metabolite aminomethylphosphonic acid (AMPA), and glufosinate after derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) in various plant matrixes. The method also covers direct analysis of the glufosinate metabolites 3-methylphosphinicopropionic acid (3-MPPA) and N-acetyl-glufosinate (NAG). The homogenized samples were extracted with 0.1% formic acid in water-dichloromethane (50 + 50). The aqueous layer was derivatized with FMOC-Cl, cleaned through an HLB SPE cartridge, and determined by LC-MS/MS. The sample size, extraction solvent, sample-to-solvent ratio, derivatization conditions, and cleanup procedure were thoroughly optimized, the LOQs of glyphosate, glufosinate, and AMPA were 0.5 ng/g in grape, corn (leaf and seed), and cotton (leaf, seed, and oil) and 2 ng/g in soybean and tea. The LOQs of NAG and 3-MPPA were 50 ng/g in all the test matrixes, except tea and soybean, for which the LOQ was 100 ng/g. In all cases, average recoveries were >80%. The method successfully performed the estimation of glyphosate in incurred corn and cotton leaf samples collected from supervised field trials.

Curcuminoids, the active principle of Curcuma longa L, is one of the most researched subjects worldwide for its broad-spectrum biological activities. Being traditionally known for their anticancer properties and issues related to bioavailability, the curcuminoids, including diferuloylmethane (curcumin), have gained special attention. Thus, the current study focused on the purity profiling of curcuminoids when extracted by accelerated solvent extraction, which was run with turmeric rhizome powder (20 g) at 1500 psi and at 50°C, with a static time of 10 min and with three cycles. The performance of ethanol, ethyl acetate, and acetone as extraction solvents was comparatively evaluated. Once extracted, the individual curcuminoids (curcumin, demethoxycurcumin, and bisdemethoxycurcumin) were purified by column chromatography, followed by preparative TLC, and the compounds were characterized by spectroscopic and chromatographic techniques. The HPLC method was standardized by using a gradient mobile phase of water and acetonitrile containing 0.1% formic acid. The LODs were calculated as 0.27, 0.33, and 0.42 μg/mL for curcumin, demethoxycurcumin, and bisdemethoxycurcumin, respectively. Accuracy (relative percentage error) and precision RSD values of the developed HPLC method were below 5%. The intraday accuracy ranged between -0.9 and -3.63%. The physical yield was the highest in ethanol (8.4%) extraction, followed by ethyl acetate (7.4%) and acetone (6.6%). Maximum purity was recorded in acetone (46.2%), followed by ethanol (43.4%) and ethyl acetate (38.8%), with no significant differences across the individual curcuminoids. This research will be useful for future applications related to the extraction of curcuminoids at a commercial level and to their profiling in food matrixes.

Chlorimuron-ethyl, ethyl-2-[[[[(4-methoxy-6-chloro-pyrimidin-2-yl)amino]carbonyl]amino] sulfonyl]benzoate, is used as a pre- and postemergence herbicide for the control of important broadleaved weeds in soybean and maize. Due to its phytotoxicity to rotation crops, concerns regarding chlorimuron contamination of soil and water have been raised. Although it is degraded in the agricultural environment primarily via pH- and temperature-dependent chemical hydrolysis, microbial transformation also has an important role. Fungi such as Fusarium and Alternaria are unable to survive in artificial media containing chlorimuron-ethyl at 25 mg L(-1) . However, Aspergillus niger survived in minimal broth containing chlorimuron at 2 mg mL(-1) . Aspergillus niger degraded the herbicide to harvest energy through two major routes of degradation. One route involves the cleavage of the sulfonylurea bridge, resulting in the formation of two major metabolites, namely ethyl-2-aminosulfonylbenzoate (I) and 4-methoxy-6-chloro-2-amino-pyrimidine (II). The other route is the cleavage of sulfonylamide linkage, which generates the metabolite N-(4-methoxy-6-chloropyrimidin-2-yl) urea (III). Two other metabolites, saccharin (IV) and N-methyl saccharin (V), formed from metabolite II, were also identified. A metabolic pathway for the degradation of chlorimuron-ethyl by A. niger has been proposed., (© 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.)

In collaboration with WHO, IMMUNIZATION basics analyzed 126 documents from the global grey literature to identify reasons why eligible children had incomplete or no vaccinations. The main reasons for under-vaccination were related to immunization services and to parental knowledge and attitudes. The most frequently cited factors were: access to services, health staff attitudes and practices, reliability of services, false contraindications, parents' practical knowledge of vaccination, fear of side effects, conflicting priorities and parental beliefs. Some family demographic characteristics were strong, but underlying, risk factors for under-vaccination. Studies must be well designed to capture a complete picture of the simultaneous causes of under-vaccination and to avoid biased results. Although the grey literature contains studies of varying quality, it includes many well-designed studies. Every immunization program should strive to provide quality services that are accessible, convenient, reliable, friendly, affordable and acceptable, and should solicit feedback from families and community leaders. Every program should monitor missed and under-vaccinated children and assess and address the causes. Although global reviews, such as this one, can play a useful role in identifying key questions for local study, local enquiry and follow-up remain essential.

A selective and sensitive LC-MS/MS method is presented for simultaneous determination of 12 plant growth regulators, viz., indol-3-acetic acid, indol-3-butyric acid, kinetin, zeatin, 6-benzyl aminopurine, gibberellic acid, abscisic acid, chlormequat chloride, forchlorfenuron, paclobutrazole, daminozide, and 2,4-dichlorophenoxy acetic acid, in bud sprouts and grape berries. The sample preparation method involved extraction of homogenized sample (5 g) with 40 mL methanol (80%), and final determination was by LC-MS/MS in the multiple reaction monitoring (MRM) mode with time segmentation for quantification supported by complementary analysis by quadrupole-time of flight (Q-TOF) MS with targeted high-resolution MS/MS scanning for confirmatory identification based on accurate mass measurements. The recovery of the test compounds ranged within 90-107% with precision RSD less than 5% (n = 6). The method could be successfully applied in analyzing incurred residue samples, and the strength of accurate mass analysis could be utilized in identifying the compounds in cases where the qualifier MRM ions were absent or at an S/N less than 3:1 due to low concentrations.

Five different mass spectrometers interfaced to GC or LC were evaluated for their application to targeted and nontargeted screening of pesticides in two foods, spinach and ginseng. The five MS systems were capillary GC/MS/MS, GC-high resolution time-of-flight (GC/HR-TOF)-MS, TOF-MS interfaced with a comprehensive multidimensional GC (GCxGC/TOF-MS), an MS/MS ion trap hybrid mass (qTrap) system interfaced with an ultra-performance liquid chromatograph (UPLC-qTrap), and UPLC interfaced to an orbital trap high resolution mass spectrometer (UPLC/Orbitrap HR-MS). Each MS system was tested with spinach and ginseng extracts prepared through a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure. Each matrix was fortified at 10 and 50 ng/g for spinach or 25 and 100 ng/g for ginseng with subsets of 486 pesticides, isomers, and metabolites representing most pesticide classes. HR-TOF-MS was effective in a targeted search for characteristic accurate mass ions and identified 97% of 170 pesticides in ginseng at 25 ng/g. A targeted screen of either ginseng or spinach found 94-95% of pesticides fortified for analysis at 10 ng/g with GC/MS/MS or LC/MS/MS using multiple reaction monitoring (MRM) procedures. Orbitrap-MS successfully found 89% of 177 fortified pesticides in spinach at 25 ng/g using a targeted search of accurate mass pseudomolecular ions in the positive electrospray ionization mode. A comprehensive GCxGC/TOF-MS system provided separation and identification of 342 pesticides and metabolites in a single 32 min acquisition with standards. Only 67 or 81% of the pesticides were identified in ginseng and spinach matrixes at 25 ng/g or 10 ng/g, respectively. MS/MS or qTrap-MS operated in the MRM mode produced the lowest false-negative rates, at 10 ng/g. Improvements to instrumentation, methods, and software are needed for efficient use of nontargeted screens in parallel with triple quadrupole MS.

A selective and rapid multiresidue analysis method is presented for simultaneous estimation of 12 plant growth regulators (PGRs), namely, auxins (indol-3-acetic acid, indol-3-butyric acid, and naphthyl acetic acid), cytokinins (kinetin, zeatin, and 6-benzyladenine), gibberellic acid (GA3), abscisic acid, and synthetic compounds, namely, forchlorfenuron, paclobutrazole, isoprothiolane, and 2,4-dichlorophenoxy acetic acid (2,4-D) in bud sprouts and grape berries at the development stages of 2-3 and 6-8 mm diameters, which are the critical phases when exogenous application of PGRs may be necessary to achieve desired grape quality and yield. The sample preparation method involved extraction of plant material with acidified methanol (50%) by homogenization for 2 min at 15000 rpm. The pH of the extract was enhanced up to 6 by adding ammonium acetate, followed by homogenization and centrifugation. The supernatant extract was cleaned by SPE on an Oasis HLB cartridge (200 mg, 6 cc). The final extract was measured directly by LC/MS/MS with electrospray ionization in positive mode, except for 2,4-D, GA3, and abscisic acid extracts, which required analysis in negative mode. Quantification by multiple reaction monitoring (MRM) was supported with full-scan mass spectrometric confirmation using "information-dependent acquisition" triggered with MRM to "enhanced product ionization" mode of the hybrid quadrupole-ion trap mass analyzer. The LOQ of the test analytes varied between 1 and 10 ng/g with associated recoveries of 80-120% and precision RSD <25% (n = 8). Significant matrix-induced signal suppression was recorded when the responses for pre- and postextraction spikes of analytes were compared; this could be resolved by using matrix-matched calibration standards. The method could successfully be applied in analyzing incurred residue samples and would, therefore, be useful in precisely deciding the necessity and dose of exogenous applications of PGRs on the basis of measured endogenous levels.

This paper describes single-laboratory validation of a multiresidue method for the determination of 135 pesticides, 12 dioxin-like polychlorinated biphenyls, 12 polyaromatic hydrocarbons, and bisphenol A in grapes and wine by GC/time-of-flight MS in a total run time of 48 min. The method is based on extraction with ethyl acetate in a sample-to-solvent ratio of 1:1, followed by selective dispersive SPE cleanup for grapes and wine. The GC/MS conditions were optimized for the chromatographic separation and to achieve highest S/N for all 160 target analytes, including the temperature-sensitive compounds, like captan and captafol, that are prone to degradation during analysis. An average recovery of 80-120% with RSD < 10% could be attained for all analytes except 17, for which the average recoveries were 70-80%. LOQ ranged within 10-50 ng/g, with < 25% expanded uncertainties, for 155 compounds in grapes and 151 in wine. In the incurred grape and wine samples, the residues of buprofezin, chlorpyriphos, metalaxyl, and myclobutanil were detected, with an RSD of < 5% (n = 6); the results were statistically similar to previously reported validated methods.

An analytical method is reported for residue analysis of the fungicide meptyldinocap in different fruit matrixes that involves extraction with ethyl acetate, hydrolysis of the residues with ethanolamine, and determination by LC/MS/MS. The method involves extraction of 10 g sample with 10 mL ethyl acetate; evaporation of the ethyl acetate phase to dryness, and subsequent hydrolysis of the residues to 4,6-dinitro-2-(1-methylheptyl) phenol on reaction with 1% ethanolamine. The pH of this hydrolyzed product was neutralized with formic acid and analyzed by LC/MS/MS. The hydrolysis reaction followed pseudo-first-order kinetics, and the reaction product was spectroscopically confirmed as 2-(1-methylheptyl)-4,6-dinitrophenol. The method offered > 80% recoveries at an LOQ of 10 ng/g for grape and mango, 25 ng/g for pomegranate with intralaboratory Horwitz ratio < 0.5, and measurement uncertainties < 10% at LOQ levels. Considering first-order rate kinetics, activation energy, enthalpy of activation, and entropy of activation varied as solvent > mango > grape > pomegranate. Free energy of activation at 298 K was higher than at 280 K and was similar for solvent and three matrixes at both temperatures.

A multiresidue analysis method was optimized and validated for simultaneous estimation of 21 synthetic pyrethroid pesticides and their isomers in grape matrix at 10 ng/g and higher levels. The method involves extraction of a 10 g sample with 10 mL ethyl acetate, cleanup by dispersive SPE with primary-secondary amine (25 mg) sorbent, and estimation by GC/MS/MS large volume injection (LVI) through a programmed temperature vaporizer (PTV) injector. The PTV-LVI parameters of the gas chromatograph and the multiple reaction monitoring (MRM) parameters of the ion trap mass spectrometer were optimized for each compound to achieve the highest SIN. For each analyte, the unique and most abundant MRM transition was used for quantification, along with the next most abundant MRM transition for confirmatory identification. The abundance ratio of the confirmatory to quantifier MRMs was used to ensure unambiguous residue monitoring in unknown samples within a 20% tolerance range at the 10 ng/g level. The analytes were separated on a TR-5MS capillary column within a 22 min run time. The method was selective and sensitive and ensured separation of the synthetic pyrethroids from high-boiling matrix components. The LOD and LOQ of the analytes ranged between 0.5 to 3.1 and 2.5 to 10 ng/g, respectively. Linearity of solvent and matrix-matched calibrations between 2.0 and 250 ng/g was established for each compound with r2 > 0.99. Recovery at 10, 25, and 50 ng/g levels of fortification in grapes ranged within 77-115% with associated RSD values (n = 8) up to 20%.

Single-laboratory validation results are reported for the multiresidue determination of 82 pesticides at < or = 10 ng/g levels in pomegranate, apple, and orange. Samples were extracted with ethyl acetate, and the extracts were cleaned up by dispersive solid-phase extraction with primary secondary amine sorbent. The concentrations of the pesticides were estimated within 18 min of chromatographic run time by liquid chromatography/mass spectrometry with multiple-reaction monitoring. The method was reproducible (HorRat of < 0.5 at 10 ng/g) with measurement uncertainties of < 15% for all the compounds at 10 nglg in all 3 matrixes. The limits of quantitation ranged from 2.5 to 5.0 ng/g with recoveries of 70-120% for most pesticides. Matrix-induced signal suppressions were significantly higher in orange compared with those in pomegranate and apple. The method offers a less expensive and safer alternative to the existing multiresidue analysis methods for fruits and vegetables.

Background: A large outbreak of poliomyelitis due to poliovirus type 3 (P3) occurred in India in 1999. This raised concerns about oral poliovirus vaccine (OPV) effectiveness, particularly the type 3 component, in preventing clinical disease and offered an opportunity to describe the epidemiology of a P3 outbreak., Methods: We reviewed data collected by the National Polio Surveillance Project to describe the outbreak and conducted a case-control study to determine risk factors for the development of paralytic poliomyelitis. The P3 cases with paralysis onset in 2000 were enrolled with four controls per case, matched for age and neighbourhood., Results: Of 1126 virologically confirmed poliomyelitis cases reported in 1999, 719 (64%) were due to P3. We enrolled 48 (80%) of 60 cases and 175 matched controls. Age (30.6 months, cases versus 30.4 months, controls) and vaccination status (median 5.8 OPV doses, cases versus 6.1 OPV doses, controls) were similar among cases and controls. The only significant difference between the groups was the proportion that received any injection in the last 30 days prior to paralysis onset or the corresponding reference date for controls (35.4% versus 12.3%, adjusted odds ratio [OR] = 3.9, 95% CI: 1.8-12.5)., Conclusions: Cases and controls had similar vaccination histories. The only significant risk factor for paralytic illness was having received any injection in the 30 days before onset. Our study confirms that injections administered during the poliovirus incubation period can provoke paralytic poliomyelitis. Injections in polio-endemic countries should only be indicated when other therapeutic options have failed or are not available.

As we progress toward eradication of polio, a growing proportion of cases of acute flaccid paralysis (AFP) reported are due to causes other than polio. AFP surveillance data from India for 1998-2000 were analyzed to determine the sensitivity and specificity of signs and symptoms present at initial case investigation and of residual weakness (which is used to classify AFP cases) for virologically confirmed poliomyelitis. Sensitivity was highest for age of <5 years (93%-97%) and residual weakness (74%-96%). Residual weakness was more sensitive among children aged <5 years. Cases of AFP in patients aged <5 years who have fever and asymmetrical paralysis are most likely to be confirmed as poliomyelitis. In countries with suboptimal surveillance for AFP, these results may help to prioritize investigation of AFP cases. The high sensitivity of residual weakness demonstrates the importance of 60-day follow-up examination for all patients with AFP, particularly those for whom the initial case investigation was inadequate or delayed.