item D Number °3516 n Author Sherma, J. Corporate Author Report/Article Title JOUrnal/BOOk Title Manual of Analytical Quality Control for Pesticides and Year 1^1 Month/Day April Color D Number of linages 468 Descrlpton Notes PBSI-222721. EPA-6oo/2-si-o59 Friday, December 07, 2001 Page 3516 of 3585 PB81-222721 MANUAL OF ANALYTICAL QUALITY CONTROL FOR PESTICIDES AND RELATED COMPOUNDS , IN HUMAN AND ENVIRONMENTAL SAMPLES- - SECOND REVISION 2, J. Sherma, at al U.S. Environmental Protection Agency Research Triangle Park, North Carolina 1981 U.S. DEPARTMENT OF COMMERCE National Technical Information Service NTIS United States Health Effects Research EPA-600/2-81-059 Environmental Protection Laboratory April 1981 Agency Research Triangle Park NC 27711 Research and Development P331-222721 Manual of Analytical Quality Control for Pesticides and Related Compounds In Human and Environmental Samples—Second Revision REPRODUCED BY NATIONAL TECHNICAL INFORMATION SERVICE U.S. DEPARTMENT OF COMMERCE SPRINGFIELD, VA, 22161 EPA 600/2-^31-059 April 1981 MANUAL OF ANALYTICAL QUALITY CONTROL FOR PESTICIDES AND RELATED COMPOUNDS IN HUMAN AND ENVIRONMENTAL SAMPLES A Compendium of Systematic Procedures Designed To Assist in the Prevention and Control of Analytical Problems By Qr. .Tnaonli Shoi-ma Department of Chemistry Lafayette College Easton, Pennsylvania • Revisions by: The Association of Official Analytical Chemists _P_r.Joseph Sherma DrT~Morton Beroza Contract No. 68-02-2474 Project Officer . - Editor Randall R. Watts Environmental Toxicology Division Health Effects Research Laboratory Research Triangle Park, N.C. 27711 Revised: 1981 U.S. ENVIRONMENTAL PROTECTION AGENCY OFFICE OF RESEARCH AND DEVELOPMENT HEALTH EFFECTS RESEARCH LABORATORY RESEARCH TRIANGLE PARK, N.C. 27711 NOTICE THIS DOCUMENT HAS BEEN REPRODUCED FROM THE BEST COPY FURNISHED US BY THE SPONSORING AGENCY. ALTHOUGH IT IS RECOGNIZED THAT CERTAIN PORTIONS ARE ILLEGIBLE, IT IS BEING RELEASED IN THE INTEREST OF MAKING AVAILABLE AS MUCH INFORMATION AS POSSIBLE. DISCLAIMER This report has been reviewed by the Health Effects Research Laboratory,'U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation, for use. ii FOREWORD The many benefits of our modern developing, industrial society are accompanied by certain hazards. Careful assessment of the relative risk of existing and new man-made environmental hazards is necessary for the estab- lishment of sound regulatory policy. These regulations serve to enhance the quality of our environment in order to promote the public health and welfare and the productive capacity of our Nation's population. The Health Effects Research Laboratory, Research Triangle Park, con- ducts a coordinated environmental health research program in toxicology, epidemiology, and clinical studies using human volunteer subjects. These studies address problems in air pollution, non-ionizing radiation, environ- mental carcinogenesis and the toxicology of pesticides as well as other chemical pollutants. The Laboratory participates in the development and revision of air quality criteria documents on pollutants for which national ambient air quality standards exist or are proposed, provides the data for registration of new pesticides or proposed suspension of those already in use, conducts research on hazardous and toxic materials, and is primarily responsible for providing the health basis for non-ionizing radiation standards. Direct support to the regulatory function of the Agency is pro- vided in the form of expert testimony and preparation of affidavits as well as expert advice to the Administrator to assure the adequacy of health care and surveillance of persons having suffered imminent and substantial en- dangerment of their health. This manual provides the pesticide chemist with a systematic protocol for the quality control of analytical procedures and the problems that arise in the analysis of human or environmental media. F.G, Hueter, Ph.D, Director Health Effects Research. Laboratory iii ABSTRACT This manual provides the pesticide chemist with a systematic protocol for the quality control of analytical procedures and the problems that arise in the analysis of human or environmental media. It also serves as a guide to the latest and most reliable methodology available for the analysis of pesticide residues in these and other sample matrices. The sections.dealing with inter- and intra-laboratory quality control, the evaluation and stand- ardization of materials used, and the operation of the gas chromatograph are intended to highlight and provide advice in dealing with many problems which constantly plague the pesticide analytical chemist. Many aspects of the problem areas involved in extraction and isolation techniques for pesticides in various types of samples are discussed. Techniques for confirming the presence or absence of pesticides 'in sample materials are treated at some length. This highly important area provides validation of data obtained by the more routine analytical procedures. The gas chromatograph, being the principal instrument currently used in pesticide analysis, often requires simple servicing or troubleshooting, A section addressing some of these problems is included. Last, but by no means least in importance, is a short , dissertation of the value and need for systematic training programs for 'pesticide chemists. iv TABlf OF CONTENTS Section In-Sec.tion Number ' • Section Page FOREWORD AND ABSTRACT GENERAL DESCRIPTION OF PESTICIDE RESIDUE ANALYTICAL METHODS A. Sampling 1 B. Extraction Procedures 2 C. Cleanup Procedures 3 D. Final Determination Methods 5 E. Confirmatory Techniques . 9 F. Automation and Computer Processing 10 6. References 10 INTERLABORATORY QUALITY ASSURANCE A. Quality Assurance Program of the EPA Environ- 14 mental Toxicology Division B. Program Objectives 15 C. Program Activities IS D. Types and Preparation of Sample Media 16 E. Reporting Forms 17 F. Evaluation of Reported Data 18 6. Summary of Results Tables and Results of Check 21 Sample Analyses H. Relative Performance Ranking 37 I. Private Critiques 50 J. Progression of Performance 59 K. Statistical Terms and Calculations 53 L. References 59 M. Additional Sources of Information on 59 Pesticide Quality Assurance Programs INTRALABORATORY QUALITY CONTROL A. Purpose and Objectives 61 B. Purpose and Objectives of SPRM's 61 C. Nature of SPRM's 62 D. Frequency of SPRM Analysis 63 E. Record Keeping 64 F. Quality Control Charts 69 G. Benefits of the In-House SPRM Program 73 H. Analytical Balances 74 I. Purity of Solvents 75 J. Distillation of Solvents 79 K. Contamination from Reagents and Materials 79 L. GC Retention Data for Common Interferences 82 Section In-Section Number Section Page, 3 M. Cleaning of Glassware .. 84 N. Housekeeping 84, 0. Analytical Pesticide Reference Standards 85 P. Calibration and Maintenance of the Gas 101 Chromatograph and Accessories Q. Adherence to Official or Standardized Methodology 103 R. Implications of an Intralaboratory Quality 104 Control Program S. References 105 EVALUATION, FTANDARDIZATION, AND USE OF MATERIALS FOR PESTICIDE RESIDUE ANALYSIS 4 A. Adsorbents 107 B. Introduction and Column Technology 113 C. Column...Efficiency and Peak Resolution 115 D. Sensitivity and Retention • 118 E. Column Stability 119 , ...... F. Resistance to On-Column Compound Decomposition 119 G. Homemade vs. Precoated Packings 124 H. Packing the Column 126 1. Column Conditioning 128 J. Support Bonded Carbowax 20M Columns 131 K. Evaluation of the Column 132 L. Maintenance and Use of GC Columns 133 M. Capillary GC Columns 136 N. References 138 5 ••' INSTRUMENTATION AND PROCEDURES FOH GAS CHROMATOGRAPHY A. Temperature Selection and Control 140 B. Selection and Control of Carrier Gas Flow Rate 143 C. Electron Capture Detector 147 D. Microcoulometric Detector 158 E. Thermionic Detectors 159 F. Flame Photometric Detector (FPD) 164 G. Electrolytic Conductivity Detector 171 H. Other Detectors and Detector Combinations 178 I. Electrometer and Recorder 180 J. Sample Injection and the- Injection Port 181 K. Erratic Baselines 186 L. Recommended GC Columns for Pesticide Analysis 187 M. Sensitivity of the GC System 196 N. Qualitative Analysis 197 0. Quantitative Analysis 200 P. References 215 vi Section In-Section Number Section Page 6 MAINTENANCE, TROUBLESHOOTING, AND CALIBRATION OF THE GAS CHROMATOGRAPH AND DETECTOR SYSTEMS A. Daily Operational Considerations for Gas 220 Chromatographic Instrumentation B. Check List When Instrument1 Repair is Indicated 221 C. General Approach to Troubleshooting 222 D. Gas Chromatograph Service Block Diagram 225 E. Gas Inlet System of the Gas Chromatograph 226 F. Procedure for Isolating Problems in Flow Systems 228 of Electron Capture Equipped Gas Chromatographs G. General Information - Flow System 232 H. Temperature Control and Indication in the Gas 233 Chromatograph I. Detector and Electrometer . 234 J. Observation of Problems on Chromatograms 236 K. Detector Background Signal (BGS) Response 237 L. Troubleshooting Coulson Electrolytic 238 Conductivity System M. Troubleshooting the Flame Photometric Detector 241 (FPD) N. Epilog 243 7 OTHER CHROMATOGRAPHIC DETERMINATIVE TECHNIQUES HIGH PERFORMANCE LIQUID COLUMN CHROMATOGRAPHY (HPLC) AND THIN LAYER CHROMATOGRAPHY A. Introduction to HPLC 244 B. Theory and Principles