《美国FDA农残分析手册》（第一卷英文版）VOLUME Multiresidue methods.pdf_大学文库

Pesticide Analytical Manual Vol. I INTRODUCTION PESTICIDE ANALYTICAL MANUAL INTRODUCTION The Food and Drug Administration(FDA) is responsible under the Federal Food Drug, and Cosmetic Act for enforcing tolerances established by the environmental Protection Agency(EPA) for amounts of pesticide residues that may legally re- main on food(including animal feed). In meeting this responsibility, FDA collects and analyzes food from commercial channels of trade for determining compliance with EPA tolerances. The residue data gathered under this regulatory monitoring program are also used for evaluating the extent and significance of pesticide residues in the food supply The Pesticide Analytical Manual(PAM) is published by FDA as a repository of the analytical methods used in FDA laboratories to examine food for pesticide resi- dues for regulatory purposes. The manual is organized according to the scope of the analytical methods Volume i contains multiresidue methods (MRMs) that are used by FDa on a routine basis, because of their efficiency and broad applicability especially for analyzing foods of unknown pesticide treatment his- Volume ii contains methods designed for the analysis of commodities for resi- dues of only a single compound (although some methods are ca- pable of determining several related compounds). These methods are most often used when the likely residue is known to the chemist and/or when the residue of interest cannot be determined by com- mon mrms PAM is designed to be used by analysts experienced in trace residue analysis. All of the techniques employed are subject to potential interferences from reagents apparatus, containers, contaminated air supply, and handling by personnel. The experienced analyst is alert for these possibilities and recognizes the need to con- firm results by other techniques that measure different chemical or physical prop erties of the analyte Expe particular application by a trial of the method that includes examination of re- editors invite analysts to report results of their experiences with PAM methode agent and sample blanks and measurement of the recovery of added analyte. the Revisions Starting with transmittal 96-1(9/96), revisions of PAM I have been issued in two ways (1) changes in most manual sections will be distributed as hard(paper)copies, with symbols or marking lines that have been changed, and(2)updates to the tables 140CFR180.101(c) Form FDA 2905a(6/92)

Transmittal No. 98-1 (10/97) Form FDA 2905a (6/92) v Pesticide Analytical Manual Vol. I PESTICIDE ANALYTICAL MANUAL INTRODUCTION The Food and Drug Administration (FDA) is responsible under the Federal Food, Drug, and Cosmetic Act for enforcing tolerances established by the Environmental Protection Agency (EPA) for amounts of pesticide residues that may legally remain on food (including animal feed). In meeting this responsibility, FDA collects and analyzes food from commercial channels of trade for determining compliance with EPA tolerances. The residue data gathered under this regulatory monitoring program are also used for evaluating the extent and significance of pesticide residues in the food supply. The Pesticide Analytical Manual (PAM) is published by FDA as a repository of the analytical methods used in FDA laboratories to examine food for pesticide residues for regulatory purposes.1 The manual is organized according to the scope of the analytical methods: Volume␣ I contains multiresidue methods (MRMs) that are used by FDA on a routine basis, because of their efficiency and broad applicability, especially for analyzing foods of unknown pesticide treatment history. Volume II contains methods designed for the analysis of commodities for residues of only a single compound (although some methods are capable of determining several related compounds). These methods are most often used when the likely residue is known to the chemist and/or when the residue of interest cannot be determined by common MRMs. PAM is designed to be used by analysts experienced in trace residue analysis. All of the techniques employed are subject to potential interferences from reagents, apparatus, containers, contaminated air supply, and handling by personnel. The experienced analyst is alert for these possibilities and recognizes the need to confirm results by other techniques that measure different chemical or physical properties of the analyte. Experienced residue analysts are aware that no report of validation in another laboratory can substitute for verification that the method does indeed work in the analyst’s own laboratory. The analyst should verify method performance in each particular application by a trial of the method that includes examination of reagent and sample blanks and measurement of the recovery of added analyte. The editors invite analysts to report results of their experiences with PAM methods. Revisions Starting with transmittal 96-1 (9/96), revisions of PAM I have been issued in two ways: (1) changes in most manual sections will be distributed as hard (paper) copies, with symbols or marking lines that have been changed, and (2) updates to the tables 1 40 CFR 180.101 (c) INTRODUCTION

Pesticide Analytical Manual Vol. I PREFACE PREFACE TO PAM/3RD EDITION The third edition of PAM I follows by the publication of th e secor edition. During that period, 29 revisions were made, reflecting new or revised methods, new technologies, and periodic updates of tables describing the capabili ties of PAM I methods Preparation of PAM I 3rd edition was motivated by three major deficiencies in the oft-revised 2nd edition: outdated material, obsolete or ganization of methods, and lack of consistent style Changes in multiresidue methods(MRMs)over the past 26 years have been sig- nificant. Among the most notable changes are those related to instrumental deter- minative techniques. Capillary columns and improved detectors have enhanced GLC applications; HPLC, with its various operating modes, has extended multiresidue capabilities to pesticides not amenable to GlC determination; and mass spectrometry, in the form of compact, automated instruments readily com- bined with GLC, has replaced many cumbersome, less sensitive, and less definitive techniques. PAM I 3rd edition attempts to provide a more up-to-date picture of the status of instrumentation currently used in FDA Pesticide laboratories. D dvances in instrumentation, the basic approach to determination of trace level residues has not departed dramatically from that used in the 1960s. Residues are still extracted from the food commodity, isolated from co-extracted materials and determined by instrumental techniques that separate residues from one an- other. While these analytical steps continue to be part of any MRM, methods research, coupled with advances in analytical technologies, has produced mrMs capable of determining a greater number of widely different types of pesticide residues in a single extract, i.e.,"multiclass MRMs. "Research has also produced other MRMs that determine multiple residues of chemically related pesticides, such as N-methylcarbamates; these types of methods are known as"selective MRMs PAM I 2nd edition organized methods according to the chemical class of the targeted residues, an organization that does not conform to modern methodology A major change in the PAM I 3rd edition is its grouping of methods into multiclass MRMs( Chapter 3)and selective MRMs( Chapter 4) Another change in method descriptions accommodates the choices available to the experienced residue analyst. Typically, the residue laboratory chooses from among several validated options within basic methodology; choices are dictated by the particular commodity, available instrumentation, and targeted residues. Thus, PAM I 3rd edition method descriptions consist of individual extraction, cleanup, and determinative step modules, with indications of which combinations are vali- dated. This organization permits easier reference to the precise combination of steps used in an analysis and facilitates sharing particular methods with colleagues Future addition or revision of methods will be simplified by adding or replacin only the necess sections or modules. The numbering system used in Chapter 8 and 4 is explained in the Guide to PAM I Finally, PAM I 3rd edition incorporates a new and consistent design. A new num- bering system is used, in which chapter and subsection numbers avoid the restric- tive 2nd edition decimal system. Pages are numbered within major subsections Four indices are included: (1)to methods applicable for individual residues,(2) to preferred names for pesticides, (8)to Chemical Abstracts Service(CAs)Regis- try Numbers for the chemicals, and (4)to subjects by key word. An introductor Guide to PAM I, on the following pages, explains the organization of chapte FDA 2905a(6/92

Transmittal No. 94-1 (1/94) Form FDA 2905a (6/92) vii Pesticide Analytical Manual Vol. I PREFACE PREFACE TO PAM I 3RD EDITION The third edition of PAM I follows by 26 years the publication of the second edition. During that period, 29 revisions were made, reflecting new or revised methods, new technologies, and periodic updates of tables describing the capabilities of PAM I methods. Preparation of PAM I 3rd edition was motivated by three major deficiencies in the oft-revised 2nd edition: outdated material, obsolete organization of methods, and lack of consistent style. Changes in multiresidue methods (MRMs) over the past 26 years have been significant. Among the most notable changes are those related to instrumental determinative techniques. Capillary columns and improved detectors have enhanced GLC applications; HPLC, with its various operating modes, has extended multiresidue capabilities to pesticides not amenable to GLC determination; and mass spectrometry, in the form of compact, automated instruments readily combined with GLC, has replaced many cumbersome, less sensitive, and less definitive techniques. PAM I 3rd edition attempts to provide a more up-to-date picture of the status of instrumentation currently used in FDA pesticide laboratories. Despite advances in instrumentation, the basic approach to determination of trace level residues has not departed dramatically from that used in the 1960s. Residues are still extracted from the food commodity, isolated from co-extracted materials, and determined by instrumental techniques that separate residues from one another. While these analytical steps continue to be part of any MRM, methods research, coupled with advances in analytical technologies, has produced MRMs capable of determining a greater number of widely different types of pesticide residues in a single extract, i.e., “multiclass MRMs.” Research has also produced other MRMs that determine multiple residues of chemically related pesticides, such as N-methylcarbamates; these types of methods are known as “selective MRMs.” PAM I 2nd edition organized methods according to the chemical class of the targeted residues, an organization that does not conform to modern methodology. A major change in the PAM I 3rd edition is its grouping of methods into multiclass MRMs (Chapter 3) and selective MRMs (Chapter 4). Another change in method descriptions accommodates the choices available to the experienced residue analyst. Typically, the residue laboratory chooses from among several validated options within basic methodology; choices are dictated by the particular commodity, available instrumentation, and targeted residues. Thus, PAM I 3rd edition method descriptions consist of individual extraction, cleanup, and determinative step modules, with indications of which combinations are validated. This organization permits easier reference to the precise combination of steps used in an analysis and facilitates sharing particular methods with colleagues. Future addition or revision of methods will be simplified by adding or replacing only the necessary sections or modules. The numbering system used in Chapters 3 and 4 is explained in the Guide to PAM I. Finally, PAM I 3rd edition incorporates a new and consistent design. A new numbering system is used, in which chapter and subsection numbers avoid the restrictive 2nd edition decimal system. Pages are numbered within major subsections. Four indices are included: (1) to methods applicable for individual residues, (2) to preferred names for pesticides, (3) to Chemical Abstracts Service (CAS) Registry Numbers for the chemicals, and (4) to subjects by key word. An introductory Guide to PAM I, on the following pages, explains the organization of chapters

Transmittal No. 94-1 (1/94) x Form FDA 2905a (6/92) GUIDE TO PAM I Pesticide Analytical Manual Vol. I 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 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 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 Chapter 1 provides information and directions that reflect FDA regulatory policy. PAM I is not the authoritative source for publication of FDA policy, but policy decisions that directly affect the application of pesticide analytical methodology are included here as a service to the manual user. Chapter 3 includes multiclass multiresidue methods (MRMs), those that are capable of determining pesticide residues of many chemical types. The actual number and identity of the residues determinable by the methods are usually dependent on the number and variety of different determinative steps used to examine the extract. Each method in this chapter is presented as a series of modules for the extraction, cleanup, and determinative steps; a complete method is defined as a combination of one or more modules from each step. Complete methods that have been validated in interlaboratory studies, including collaborative studies performed under the auspices of AOAC International, are listed; these are sanctioned for use in regulatory analyses. Other combinations of modules must be treated as experimental methodology; additional supporting data for the validity of the analysis are required when such combinations are used in regulatory analyses. Chapter 2 is a collection of data and directions on a variety of unrelated topics, each of which provides background information needed to perform methods of Chapters 3 and 4. Where information in Chapters 1 and 2 appears to overlap (e.g., Sections 102, Preparation of Analytical Samples; and 203, Equipment and Procedures for Comminuting), the material in Chapter 1 reflects the agency policy that must be followed for enforcement of regulations, and Chapter 2 provides information and hints found useful by FDA pesticide chemists