Pesticide Analytical Manual Vol. I Regulatory Operations Chapter 2 General Analytical Operations and Information Chapter 3 Chapter 4 Multiclass Selective MRM ARMs Chapter 5 GLC Ch HPLC Table of contents page d 401: Method for N-Methylcarbamates Basic references 401-1 1/94 General Principles 401-1 1/94 Steps of the method 401-1 1/94 Extraction with methanol 401-3 E2 with methanol, reduced samp Liquid-Liquid Partitioning and Charcoal/Celite 401-5 1/94 Column clean DLI HPLC. Post-Column Derivatization 401-91/94 Flue Form FDA 2905a (6, 400-1
Pesticide Analytical Manual Vol. I 400–1 Transmittal No. 96-E1 (9/96) Form FDA 2905a (6/92) Table of Contents page date 401: Method for N-Methylcarbamates Basic References 401-1 1/94 General Principles 401-1 1/94 Applicability 401-1 1/94 Reference Standards 401-1 1/94 Steps of the method 401-1 1/94 Validation 401-2 1/94 E1 Extraction with methanol 401-3 1/94 E2 Extraction with methanol, reduced sample size 401-4 1/94 C1 Liquid-Liquid Partitioning and Charcoal/Celite 401-5 1/94 Column Cleanup DL1 HPLC, Post-Column Derivatization, 401-9 1/94 Fluorescence Detection Chapter 1 Regulatory Operations Chapter 2 General Analytical Operations and Information Chapter 3 Multiclass MRMs Chapter 5 GLC Chapter 4 Selective MRMs Chapter 6 HPLC
Pesticide Analytical Manual Vol page HPLC. Fluorescence detection 131/94 Confirmation 1/94 102: Method for Acids and Phenols Basic reference 40211/94 General Principles 40211/94 Applicability 40211/94 Reference standards 402-1 1/9 Steps of the method 40211/94 Validation 402-2 1/94 Extraction with solvents from acidified 40231/94 denatured products Extraction with acidified methylene chloride 027 1/94 Extraction with acidified methanol 402-9 1/94 E4 Extraction with acidified water/ methanol 402101/94 Extraction with acidified methanol 402111/94 Dissolution in methylene chloride/hexane 402131/94 Extraction with acidified methylene chloride 02-151/94 GPC Cleanup, methylation, and Florisi 402-171/94 column cleanup Cla GPC Clean 402-171/94 CIb Methylation 02211/94 Clc Florisil column cleanup 402221/94 Determination 402251/94 Confirmation 402251/94 403 Method for Phenylurea Herbicides Basic reference 403-11/94 General Principles 40311/94 Applicability 40311/94 Reference standard 40311/94 Steps of the method 403-11/94 Validation 40321/94 Extraction with Methanol 40331/94 Liquid-Liquid Partitioning and Florisil 40351/94 Column Cleanup dL3 HPLC, Post-Column Photolysis and 40371/94 Derivatization fluorescence detectio DL4 HPLC, Different mobile phase 403101/94 403-111/94 404 Method for benzimidazoles c referenc 40411/94 General Principles 4002 Form FDA 2905a(6/92]
SECTION 400 Pesticide Analytical Manual Vol. I 400–2 Transmittal No. 96-E1 (9/96) Form FDA 2905a (6/92) page date DL2 HPLC, Fluorescence Detection 401-13 1/94 Confirmation 401-13 1/94 402: Method for Acids and Phenols Basic Reference 402-1 1/94 General Principles 402-1 1/94 Applicability 402-1 1/94 Reference Standards 402-1 1/94 Steps of the method 402-1 1/94 Validation 402-2 1/94 E1 Extraction with solvents from acidified, 402-3 1/94 denatured products E2 Extraction with acidified methylene chloride 402-7 1/94 E3 Extraction with acidified methanol 402-9 1/94 E4 Extraction with acidified water/methanol 402-10 1/94 E5 Extraction with acidified methanol 402-11 1/94 E6 Dissolution in methylene chloride/hexane 402-13 1/94 E7 Extraction with acidified methylene chloride 402-15 1/94 C1 GPC Cleanup, methylation, and Florisil 402-17 1/94 column cleanup C1a GPC Cleanup 402-17 1/94 C1b Methylation 402-21 1/94 C1c Florisil column cleanup 402-22 1/94 Determination 402-25 1/94 Confirmation 402-25 1/94 403: Method for Phenylurea Herbicides Basic Reference 403-1 1/94 General Principles 403-1 1/94 Applicability 403-1 1/94 Reference Standards 403-1 1/94 Steps of the method 403-1 1/94 Validation 403-2 1/94 E1 Extraction with Methanol 403-3 1/94 C1 Liquid-Liquid Partitioning and Florisil 403-5 1/94 Column Cleanup DL3 HPLC, Post-Column Photolysis and 403-7 1/94 Derivatization, Fluorescence Detection DL4 HPLC, Different mobile phase 403-10 1/94 Confirmation 403-11 1/94 404: Method for Benzimidazoles Basic Reference 404-1 1/94 General Principles 404-1 1/94
Pesticide Analytical Manual Vol. I date 40411/94 Reference standards 4041 /94 Steps of the method 40411/94 Validation 4043 1/94 Extraction with methanol transfer to 40451/94 Extraction with methanol, removal of oil with 404-7 1/94 hexane, transfer to methylene chloride Extraction with methanol, removal of oil with 404-8 1/94 thylene chloride DL5 HPLC, Ion Pair Mobile Phase, UV and 4049 1/94 Fluorescence detector DL6 HPLC, Concentrated Ion Pair Mobile Phase, 404-12 1/9 UV and Fluorescence Detector DL7 HPLC, Ion Pair Mobile Phase, Changes in 404141/94 Confirmation 404141/94 res 101-a Method for N-Methylcarbamates 401-2 1/94 401-b Vacuum Rotary Evaporator 401-31/94 HPLC System for Determination of 401-91/94 N-Methylcarbamates 401-d HPLC Chromatogram of carbamates 401-121/94 and metabolites 402-a Method for Acids and Phenols 1/94 402-b Delivery Tube apparatus 402-3 1/9 403-a Method for Phenylureas 403-2 1/94 403b HPLC System for Determination of 403-71/94 Phenylurea Herbicides 403-c HPLC Chromatograms of carrot extract 403-101/94 403-d Chromatographic Pattern Comparison 403-111/94 404a lethod for benzimidazoles 0421/94 404-b Chromatograms of Benzimidazole Compounds 4104-12 9/96 404-C Effect of Ion Pairing Solution Concentration 404-18 1/94 on Chromatography of MBC Tables 401-a: Recovery of Chemicals Through Method 401 401-a-1 9/96 401-b: Recovery of Chemicals Through Method 401 401-b-l 9/96 402-a: Recovery of Chemicals Through Method 402 402-a-l 9/96 (El-E7 +Cl+DGl or DG% or DG4) 403a: Recovery of Chemicals Through Method 403 403-a-1 9/96 (El +Cl+ dl3 and DL4) Form FDA 2905a (6/92 400-3
Pesticide Analytical Manual Vol. I 400–3 Transmittal No. 96-E1 (9/96) Form FDA 2905a (6/92) page date Applicability 404-1 1/94 Reference Standards 404-1 1/94 Steps of the Method 404-1 1/94 Validation 404-3 1/94 E1 Extraction with methanol, transfer to 404-5 1/94 methylene chloride E2 Extraction with methanol, removal of oil with 404-7 1/94 hexane, transfer to methylene chloride E3 Extraction with methanol, removal of oil with 404-8 1/94 methylene chloride, transfer to methylene chloride DL5 HPLC, Ion Pair Mobile Phase, UV and 404-9 1/94 Fluorescence Detector DL6 HPLC, Concentrated Ion Pair Mobile Phase, 404-12 1/94 UV and Fluorescence Detector DL7 HPLC, Ion Pair Mobile Phase, Changes in 404-14 1/94 Detector Settings Confirmation 404-14 1/94 Figures 401-a Method for N-Methylcarbamates 401-2 1/94 401-b Vacuum Rotary Evaporator 401-3 1/94 401-c HPLC System for Determination of 401-9 1/94 N-Methylcarbamates 401-d HPLC Chromatogram of Carbamates 401-12 1/94 and Metabolites 402-a Method for Acids and Phenols 402-2 1/94 402-b Delivery Tube Apparatus 402-3 1/94 403-a Method for Phenylureas 403-2 1/94 403-b HPLC System for Determination of 403-7 1/94 Phenylurea Herbicides 403-c HPLC Chromatograms of Carrot Extract 403-10 1/94 403-d Chromatographic Pattern Comparison 403-11 1/94 404-a Method for Benzimidazoles 404-2 1/94 404-b Chromatograms of Benzimidazole Compounds 404-12 9/96 404-c Effect of Ion Pairing Solution Concentration 404-13 1/94 on Chromatography of MBC Tables 401-a: Recovery of Chemicals Through Method 401 401-a–1 9/96 (E1-E2 + C1 + DL1) 401-b: Recovery of Chemicals Through Method 401 401-b–1 9/96 (E1-E2 + C1 + DL2) 402-a: Recovery of Chemicals Through Method 402 402-a–1 9/96 (E1-E7 + C1 + DG1 or DG3 or DG4) 403-a: Recovery of Chemicals Through Method 403 403-a–1 9/96 (E1 + C1 + DL3 and DL4)
Pesticide Analytical Manual Vol page 404-a: Recovery of Chemicals Through Method 404 404-a-1 9/96 (E1E3+DL5) 4004 Form FDA 2905a(6/92]
SECTION 400 Pesticide Analytical Manual Vol. I 400–4 Transmittal No. 96-E1 (9/96) Form FDA 2905a (6/92) page date 404-a: Recovery of Chemicals Through Method 404 404-a–1 9/96 (E1-E3 + DL5)
Pesticide Analytical Manual Vol. I SECTION 401 401: METHOD FOR N-METHYLCARBAMATES BASIC REFERENCES Krause, RT(1979). Chromatogr. 185, 615-624 Krause, RT(1980)). Assoc. Off. Anal. Chem. 63, 1114-1124 Krause, RT.(1985)/. Assoc. Of Anal. Chem. 68, 734-741 GENERAL PRINCIPLES N-methylcarbamate insecticide residues, including carbamate metabolites, are ex- tracted with methanol. The extract is cleaned up by partitioning and column chromatography on a charcoal/Celite column. Residues are selectively determined with an HPLC system consisting of a reverse phase (RP)column, post-column hydrolysis and derivatization, and detection of the resultant derivative with a fluo- rescence detector Variations in the determinative step may be used for additional residues not of the N-methylcarbamate structure APPLICABILITY Consult Guide to PAM I for additional information pertinent to the appropriate application of multiresidue methodology Method is applicable to residues with an N-methylcarbamate structure in either nonfatty or fatty foods when determinative step includes post-column hydrolysis and derivatization. See Table 401-a, following method description, for chemicals tested through the method Method is applicable to naturally fluorescent residues when post-column hydrolysis and derivatization are not performed. See Table 401-b, following Table 401-a. Certain commodities, e.g., oranges, contain naturally fluorescent co-extractives that interfere with analysis. Limit of quantitation is 0.01 ppm carbofuran in high moisture products(fresh fruits and vegetables)and about 0. 02 ppm in dry products REFERENCE STANDARDS Dissolve reference standards of N-methylcarbamates in methanol to produce con- entrations of l ug/ mL. Store solutions in actinic glassware, and keep in refrigera- tor when not in use. Most carbamate standards stored in this manner are stable fo several months. However, methiocarb sulfone and sulfoxide degrade within hours and days, respectively, even with stated storage precautions STEPS OF THE METHOD Extraction E) Recommended use El (p. 401-3) Extraction with methanol high moisture products E2(P 401-4) Extraction with methanol, reduced low moisture products le size Cleanup(C) Cl (P 401-5) Two stage liquid-liquid pa artitioning products and charcoal/Celite column cleanup
Transmittal No. 94-1 (1/94) Form FDA 2905a (6/92) 401–1 Pesticide Analytical Manual Vol. I SECTION 401 401: METHOD FOR N-METHYLCARBAMATES BASIC REFERENCES Krause, R.T. (1979) J. Chromatogr. 185, 615-624 Krause, R.T. (1980) J. Assoc. Off. Anal. Chem. 63, 1114-1124 Krause, R.T. (1985) J. Assoc. Off. Anal. Chem. 68, 734-741 GENERAL PRINCIPLES N-methylcarbamate insecticide residues, including carbamate metabolites, are extracted with methanol. The extract is cleaned up by partitioning and column chromatography on a charcoal/Celite column. Residues are selectively determined with an HPLC system consisting of a reverse phase (RP) column, post-column hydrolysis and derivatization, and detection of the resultant derivative with a fluorescence detector. Variations in the determinative step may be used for additional residues not of the N-methylcarbamate structure. APPLICABILITY Consult Guide to PAM I for additional information pertinent to the appropriate application of multiresidue methodology. Method is applicable to residues with an N-methylcarbamate structure in either nonfatty or fatty foods when determinative step includes post-column hydrolysis and derivatization. See Table 401-a, following method description, for chemicals tested through the method. Method is applicable to naturally fluorescent residues when post-column hydrolysis and derivatization are not performed. See Table 401-b, following Table 401-a. Certain commodities, e.g., oranges, contain naturally fluorescent co-extractives that interfere with analysis. Limit of quantitation is 0.01 ppm carbofuran in high moisture products (fresh fruits and vegetables) and about 0.02 ppm in dry products. REFERENCE STANDARDS Dissolve reference standards of N-methylcarbamates in methanol to produce concentrations of 1 µg/mL. Store solutions in actinic glassware, and keep in refrigerator when not in use. Most carbamate standards stored in this manner are stable for several months. However, methiocarb sulfone and sulfoxide degrade within hours and days, respectively, even with stated storage precautions. STEPS OF THE METHOD Extraction (E) Recommended Use E1 (p. 401-3) Extraction with methanol high moisture products E2 (p. 401-4) Extraction with methanol, reduced low moisture products sample size Cleanup (C) C1 (p. 401-5) Two stage liquid-liquid partitioning all products and charcoal/Celite column cleanup