Transcription
EPA-600/4-79-019HANDBOOK FOR ANALYTICAL QUALITY CONTROLIN WATER AND WASTEWATER LABORATORIESMarch 1979ENVIRONMENTAL MONITORING AND SUPPORT LABORATORYU.S. ENVIRONMENTAL PROTECTION AGENCYOFFICE OF RESEARCH AND DEVELOPMENTCINCINNATI, OHIO 45268OCR(6/2001) by RYA-R10
DISCLAIMERThe mention of trade names or commercial products in this handbook is for illustrationpurposes and does not constitute endorsement or recommendation for use by the U.S.Environmental Protection Agency.iiOCR(6/2001) by RYA-R10
ABSTRACTOne of the fundamental responsibilities of water and wastewater management is theestablishment of continuing programs to insure the reliability and validity of analyticallaboratory and field data gathered in water treatment and wastewater pollution controlactivities.This handbook is addressed to laboratory directors, leaders of field investigations, and otherpersonnel who bear responsibility for water and wastewater data. Subject matter of thehandbook is concerned primarily with quality control (QC) for chemical and biological testsand measurements. Chapters are also included on QC aspects of sampling, microbiology,biology, radiochemistry, and safety as they relate to water and wastewater pollutioncontrol. Sufficient information is offered to allow the reader to inaugurate or reinforceprograms of analytical QC that emphasize early recognition, prevention, and correction offactors leading to breakdowns in the validity of water and wastewater pollution controldata.iiiOCR(6/2001) by RYA-R10
ACKNOWLEDGMENTSThis handbook was prepared by the Environmental Monitoring and Support Laboratory(EMSL) of the United States Environmental Protection Agency. The contributions of thefollowing individuals in preparing the handbook are gratefully acknowledged:J. B. AndersonD. G. BallingerE. L. BergR. L. BoothR. H. BordnerP. W. BrittonJ. F. KoppH. L. KriegerJ. J. LichtenbergL. B. LobringJ. E. LongbottomC. I. WeberJ. A. WinterTechnical editing and preparation of the final manuscript were performed under contract toJohn F. Holman & Co. Inc., 1346 Connecticut Avenue, N.W., Washington, D.C. 20036.Inquiries regarding material contained in the handbook should be made to EnvironmentalProtection Agency, Environmental Research Center, Environmental Monitoring and SupportLaboratory, Cincinnati, Ohio 45268.ivOCR(6/2001) by RYA-R10
TABLE OF CONTENTSPagePREFACE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iiiACKNOWLEDGMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vChapter1IMPORTANCE OF QUALITY CONTROL . . . . . . . . . . . . . . . . . . . .1.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.2 Quality Assurance Programs . . . . . . . . . . . . . . . . . . . . . . . . . . .1.3 Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.4 Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-11-11-11-21-42LABORATORY SERVICES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.2 Distilled Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.3 Compressed Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.4 Vacuum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.5 Hood System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.6 Electrical Services . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-12-12-12-52-52-52-62-63INSTRUMENT SELECTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-13.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-13.2 Analytical Balances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-13.3 pH/Selective-lon Meters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-33.4 Conductivity Meters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-63.5 Turbidimeters (Nephelometers) . . . . . . . . . . . . . . . . . . . . . . . . . 3-73.6 Spectrometers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-83.7 Organic Carbon Analyzers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-133.8 Gas Chromatographs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-143.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-144GLASSWARE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.2 Types of Glassware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.3 Volumetric Analyses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.4 Federal Specifications for Volumetric Glassware . . . . . . . . . . .4.5 Cleaning of Glass and Porcelain . . . . . . . . . . . . . . . . . . . . . . . . .4.6 Special Cleaning Requirements . . . . . . . . . . . . . . . . . . . . . . . . .4.7 Disposable Glassware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.8 Specialized Glassware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.9 Fritted Ware . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5REAGENTS, SOLVENTS, AND GASES . . . . . . . . . . . . . . . . . . . . . 5-15.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-15.2 Reagent Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1v4-14-14-24-34-44-54-64-74-74-84-9OCR(6/2001) by RYA-R10
5.3 Elimination of Determinate Errors . . . . . . . . . . . . . . . . . . . . . . . 5-45.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-46QUALITY CONTROL FOR ANALYTICAL PERFORMANCE . . . 6-16.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-16.2 The Industrial Approach to QC . . . . . . . . . . . . . . . . . . . . . . . . . 6-16.3 Applying Control Charts in Environmental Laboratories . . . . . 6-26.4 Recommended Laboratory Quality Assurance Program . . . . . . 6-96.5 Outline of a Comprehensive Quality Assurance Program . . . . 6-106.6 Related Topics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-136.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-137DATA HANDLING AND REPORTING . . . . . . . . . . . . . . . . . . . . . . 7-17.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-17.2 The Analytical Value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-17.3 Glossary of Statistical Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-37.4 Report Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-57.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-118SPECIAL REQUIREMENTS FOR TRACE ORGANIC ANALYSIS 8-18.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-18.2 Sampling and Sample Handling . . . . . . . . . . . . . . . . . . . . . . . . . 8-18.3 Extract Handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-48.4 Supplies and Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-58.5 Quality Assurance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-78.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-109SKILLS AND TRAINING . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9.2 Skills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9.3 Training . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10WATER AND WASTEWATER SAMPLING . . . . . . . . . . . . . . . . .10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10.2 Areas of Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-110-110-210-611RADIOCHEMISTRY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11.2 Sample Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11.3 Laboratory Practices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11.4 Quality Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .11-111-111-111-211-411-512MICROBIOLOGY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12.2 Specific Needs in Microbiology . . . . . . . . . . . . . . . . . . . . . . .12.3 Intralaboratory Quality Control . . . . . . . . . . . . . . . . . . . . . . . .12.4 Interlaboratory Quality Control . . . . . . . . . . . . . . . . . . . . . . . .12.5 Development of a Formal Quality Assurance Program . . . . . .12.6 Documentation of a Quality Assurance Program . . . . . . . . . 001) by RYA-R10
12.7 Chain-of-Custody Procedures for Microbiological Samples . . 12-312.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-1013AQUATIC BIOLOGY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13.1 Summary of General Guidelines . . . . . . . . . . . . . . . . . . . . . . . .13.2 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13.3 Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13-113-113-213-414LABORATORY SAFETY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14-114.1 Law and Authority for Safety and Health . . . . . . . . . . . . . . . . 14-114.2 EPA Policy on Laboratory Safety . . . . . . . . . . . . . . . . . . . . . . 14-514.3 Laboratory Safety Practices . . . . . . . . . . . . . . . . . . . . . . . . . . . 14-714.4 Report of Unsafe or Unhealthful Condition . . . . . . . . . . . . . 14-1514.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14-15Appendix A-Suggested Checklist for the Safety Evaluation of EPA Laboratory Areas A-1viiOCR(6/2001) by RYA-R10
LIST OF FIGURESFigure No.Page4-1Example of Markings on Glassware . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-56-16-26-3Essentials of a Control Chart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-2Shewhart Control Chart for Percent Recovery Data . . . . . . . . . . . . . . . . 6-5Procedure for Evaluating QC Data From a Monitoring Study . . . . . . . 6-127-1 Example of Bench Sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-87-2 Example of Summary Data Sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-97-3 Example of STORET Report Form . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-107-4 Flow Chart of the Sequence of Events During a Controlled Series ofLaboratory Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1212-1 Example of Chain-of-Custody Sample Tag (a) Front, (b) Back . . . . . 12-512-2 Example of a Sample Log Sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12-612-3 Example of a Chain-of-Custody Record . . . . . . . . . . . . . . . . . . . . . . . 12-714-1 Health and Safety Inspection Checklist . . . . . . . . . . . . . . . . . . . . . . . . 14-814-2 Report of Unhealthful or Unsafe Condition . . . . . . . . . . . . . . . . . . . 14-1614-3 Notice of Unhealthful or Unsafe Condition . . . . . . . . . . . . . . . . . . . 14-17LIST OF TABLESTable No.Page2-1 Water Purity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-12-2 Requirements for Reagent Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-22-3 Comparison of Distillates From Glass and Metal Stills . . . . . . . . . . . . . 2-33-1 Performance Characteristics of Typical pH/Selective-Ion Meter . . . . . . 3-53-2 Electrical Conductivity of Potassium Chloride Reference Solutions . . . 3-74-1 Tolerances for Volumetric Glassware . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-44-2 Fritted Ware Porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-86-1Analyses of Total Phosphate-Phosphorus Standards, in Milligrams PerLiter of Total PO4 -P . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-46-2 Estimates of the Range (R A - B ) and the Industrial Statistic (I A B (A B) of Three Different Parameters for Various ConcentrationRanges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-76-3 Shewhart Upper Control Limits UCL and Critical Range Rc Values forthe Differences Between Duplicate Analyses Within Specific Concentration Ranges for Three Parameters . . . . . . . . . . . . . . . . . . . . . . . 6-86-4 Critical Range
J. J. Lichtenberg L. B. Lobring J. E. Longbottom C. I. Weber J. A. Winter Technical editing and preparation of the final manuscript were performed under contract to
