Trace Environmental Quantitative Analysis Principles, Techniques, and Applications SECOND EDITION © 2006 by Taylor & Francis Group, LLC A CRC title, part of the Taylor & Francis imprint, a member of the Taylor & Francis Group, the academic division of T&F Informa plc. Trace Environmental Quantitative Analysis Principles, Techniques, and Applications SECOND EDITION Paul R. Loconto Boca Raton London New York © 2006 by Taylor & Francis Group, LLC Published in 2006 by CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2006 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 987654321 International Standard Book Number-10: 0-8247-5853-6 (Hardcover) International Standard Book Number-13: 978-0-8247-5853-0 (Hardcover) Library of Congress Card Number 2005048512 This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. 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ISBN 0-8247-5853-6 (alk. paper) 1. Environmental chemistry. 2. Trace analysis. 3. Chemistry, Analytic Quantiative I. Title. TD193.L63 2005 628.5′028′7 dc22 2005048512 Visit the Taylor & Francis Web site at and the CRC Press Web site at Taylor & Francis Group is the Academic Division of T&F Informa plc. © 2006 by Taylor & Francis Group, LLC For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC) 222 Rosewood Drive, http://www.taylorandfrancis.com http://www.crcpress.com Dedication To my five points of light. Each added a new dimension to my life. Jennifer Ann Michelle Ann Allison Marie Julia Marie Elizabeth Marie In memory of Taylor Renee Hamel (1995–2005) whose light was extinguished much too early. © 2006 by Taylor & Francis Group, LLC Preface to the Second Edition The rapid pace in which trace analysis is changing has warranted the writing of a second edition in a relatively short period. What is new? The second edition attempts to move the reader from the most elementary of principles of trace environmental quantitative analysis (TEQA) to those techniques and applications currently being practiced in analytical laboratories dedicated to trace environmental chemical and trace environmental health quantitative analysis while adding new significant topics. The increasing importance of mass spectrometry will become apparent to the reader primarily as a low-resolution hyphenated technique. The principles that under- determinative techniques. alternatives to liquid–liquid extraction are introduced. Column chromatographic cleanup, virtually ignored earlier, and gel permeation chromatography have been introduced along with additional applications to biological sample matrices of envi- ronmental health and toxicological interest. Matrix solid-phase dispersion as applied to the isolation and recovery of persistent organic pollutants from fish tissue has been added. The prolific growth of SPME as evident in the analytical literature over the past 5 years has warranted an enlarged section on this technique. More than two dozen new topics not previously discussed in the original book have been added to the second edition. Any author, upon reviewing the finished product of a first book, has a most immediate desire to rewrite all of it. I have resisted this temptation and have modified only those sections of the original book that I felt enlarge and enhance the environ- mental analytical chemist’s understanding of TEQA. Who should read the second edition? Scientists, in addition to analytical chem- ists, such as organic chemists, biochemists, molecular biologists, geologists, toxi- cologists, epidemiologists, food scientists, and chemical and environmental engi- neers will find that the second edition might enhance their understanding of TEQA. Laboratory technicians of various skill and knowledge levels should also find the content of this edition beneficial. The style for the second edition has remained the same. Section headings continue to be cast in the form of a question. New terms have been italicized when they appear for the first time. Beneath each chapter title is a brief “Chapter at a Glance” so that the reader can more quickly find topics of immediate interest. Figures and tables are both separated and numbered in sequence and integrated in the text without numbering, as before. Digressions from the main topics have also occurred in a manner similar to that in the original book. Graphs are either sketches that I drew to illustrate a principle or carefully drawn from experimental data (I’m a pretty good chemist; an artist, I am not). To reiterate from the preface to the original book, © 2006 by Taylor & Francis Group, LLC lie GC-MS, GC-MS-MS, LC-MS, and ICP-MS can now be found in Chapter 4 on Chapter 3 on sample preparation techniques has been enlarged so that even more I have tried very hard to make this text readable, interesting, and relevant, and at the same time, introduce sound principles and practices of TEQA. I express my gratitude to the Division of Chemistry and Toxicology, Bureau of Laboratories, Michigan Department of Community Health; the Michigan Public Health Institute; and the Biomonitoring Planning Grant, National Center for Envi- ronmental Health, Centers for Disease Control and Prevention. These institutions and grants enabled me to find the time to write, edit, and rewrite. Barbara Mathieu and colleagues at Taylor & Francis have painstakingly, for a second time, turned this author’s rough draft into a book. My wife, Priscilla, has graciously endured her husband’s passion for writing. And my motivation to write is rooted in and summa- rized by the ancient Chinese Proverb: I hear and forget; I see and I remember; I write and I understand. © 2006 by Taylor & Francis Group, LLC About the Author Paul R. Loconto is currently a laboratory scientist specialist with the Michigan Department of Community Health, Bureau of Laboratories, Lansing. Dr. Loconto is the author of 24 peer-reviewed publications and 33 oral and poster presentations in trace analysis and chemical education. He combines various work experiences that include teaching at a community college, managing an environmental engineer- ing research laboratory within a large university, and conducting analytical method development for an independent environmental testing laboratory. All have given the author many unique insights over the years into the principles, techniques, and applications of TEQA. © 2006 by Taylor & Francis Group, LLC Table of Contents 1. Introduction to Trace Environmental Quantitative Analysis (TEQA) 1 2. Calibration, Verification, Statistical Treatment of Analytical Data, Detection Limits, and Quality Assurance/Quality Control 37 3. Sample Preparation Techniques to Isolate and Recover Organics and Inorganics 119 4. Determinative Techniques to Measure Organics and Inorganics 323 5. Specific Laboratory Experiments 547 Appendix A: Glossary 651 Appendix B: QA/QC Illustrated 679 Appendix C: TEQA Applied to Drinking Water/Computer Programs for TEQA 689 Appendix D: Instrument Designs 705 Appendix E: Useful Internet Links for Environmental Analytical Chemists 711 Appendix F: Useful Potpourri for Environmental Analytical Chemists 717 © 2006 by Taylor & Francis Group, LLC 1 1 Introduction to Trace Environmental Quantitative Analysis (TEQA) If you teach a person what to learn, you are preparing him for the past. If you teach him how to learn, you are preparing him for the future. —Anonymous CHAPTER AT A GLANCE Case study from trace enviro-health quantitative analysis 2 Case study from trace enviro-chemical quantitative analysis 4 Extent of chemical contaminants in humans 7 Analytical chemistry approaches to biomonitoring 11 Environmental chemistry 11 EPA regulations 15 Analytical methods that satisfy EPA regulations 20 Physical/chemical basis for EPA’s methods protocols 32 References 35 As we approached the new millennium, the news media and related mass media speculated on what would be different. The 20th century was gone. The 21st century was upon us. The tragic events of 9/11 in the U.S. provided one such answer. Since 9/11, questions such as “If we have a terrorist event, can we measure trace concen- tration levels of terrorist-related chemical substances and attempt to evaluate expo- sure over relatively large numbers in the population?” have shifted the dialogue. Public health laboratories are beginning to respond to this terrorist-related threat. These laboratories are moving toward having a capability in trace environmental health quantitative analysis (also abbreviated TEQA). At the same time, biomonitoring- related initiatives are expanding. Federal laboratories such as the National Center for Environmental Health and the Centers for Disease Control and Prevention (NCEH/CDC) are assisting state labs in the transfer of both bioterroism- and biomon- itoring-related analytical methods. These methods are designed to measure trace © 2006 by Taylor & Francis Group, LLC 2 Trace Environmental Quantitative Analysis, Second Edition concentration levels of chemical substances that either persist (persistent organic pollutants (POPs)) or are eliminated rather quickly by the body, i.e., nonpersistent organic pollutants (NPOPs). Bioterrorism and biomonitoring are key initiatives that are currently driving the changing nature of trace quantitative organics and inorganics analysis. The second edition of this book attempts to reflect these changes. This new emphasis, when analysis, has led this author to adopt a new term: trace enviro-chemical/enviro-health quantitative analysis, whose acronym is also TEQA. I have tried to add those analytical concepts that are most relevant to conducting trace enviro-health quanti- tative analysis. Sampling, sample preparation, determinative technique, and data reduction/interpretation are very similar to both trace enviro-chemical and trace the enviro-health aspects of trace quantitative organics and inorganics analysis while discerning the similarities and differences in both. One starts with an understanding of the chemical nature of the sample or human or animal specimen received. A client needs to understand just what analytes are to be measured and how these two pathways lead to four steps in the process shown in Scheme 1.1. There is no substitute for effective communication between the client and the analytical laboratory. Sam- determinative techniques, often referred to as instrumental analysis (introduced in data (introduced in Chapter 2) comprise the important aspects of successfully imple- menting TEQA. This second edition introduces principles and practices of trace enviro-health quantitative analysis while expanding on the previous treatment of trace enviro- chemical quantitative analysis where the emphasis was placed only on environmental samples. 1 Two case studies drawn from the recent literature introduce the practice of contemporary TEQA. The first case study demonstrates that a possible endocrine disrupter can be isolated and recovered from human urine. 1. CAN AN EXAMPLE PROVIDE INSIGHT INTO TRACE ENVIRO-HEALTH QA? Yes, we start by briefly introducing results from a published study. Bisphenol A (BPA), 2,2-bis(4-hydroxyphenyl)propane, is an industrial chemical used in a variety of plastic materials, some of which are used in packaging, and hence is believed to leach out into consumable items such as food and dental fillings. One way to better assess human exposure to BPA despite the source of exposure being largely unknown is to biomonitor, i.e., to measure, trace BPA in human urine. Brock and coworkers 2 at the NCEH/CDC have developed a quantitative analytical method to determine just how much BPA might be present in a urine sample obtained from a person believed to be exposed to BPA. 2 BPA is apparently excreted either unmetabolized © 2006 by Taylor & Francis Group, LLC combined with the more established methods of trace environmental quantitative enviro-health quantitative analysis. Scheme 1.1 depicts both the enviro-chemical and pling (introduced in Chapter 2), sample preparation (introduced in Chapter 3), Chapter 4), and data reduction, statistical treatment, and interpretation of analytical [...]... Urine Urine Urine 318 9 318 9 248 679 912 779 10 07 10 07 10 06 10 07 10 07 904 10 07 974 892 10 06 µg/L µg/dL µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/dL µg/L µg/L µg/L µg/L µg/L —a 1. 6 (1. 4 1. 8) 0.3 (0.2–0.4) 1. 2 (0.9 1. 6) 0 .1 (0.09–0 .12 ) 1. 6 (1. 5 1. 7) —a 0.32 (0.30–0.33) 4.7 (4.2–5.2) 0.36 (0.36–0.40) 0.80 (0.68–0. 91) 48.4 (43.6–53.2) —a 0 .19 (0 .17 –0.20) 0 .10 (0.09–0 .12 ) 0.008 (0.006–0.0 01) a Not calculated;... 703 703 703 703 10 29 10 29 10 29 10 29 µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L µg/L 1. 84 (1. 10–2.59) 2. 61 (1. 77–3.45) 2.55 (1. 33–3.78) 0. 81 (0.69–0.94) 0. 51 (0.39–0.62) 0 .19 (0 .14 –0.23) 17 .4 (14 .1 20.7) 26.7 (23.9–29.4) 17 6.0 (13 2–220) 3.5 (3.0–4.0) Source: Adapted from the National Health and Nutrition Examination Survey (NHANES), U.S., 19 99 CDC, National Report on Human Exposure to Environmental. .. Taylor & Francis Group, LLC MCL (mg/L) 0.006 0.05 2 0.004 0.005 0 .1 1.3 0.2 4 0. 015 0.002 1. 1 10 1 0.05 20 0.002 MDL (mg/L) 0.0008–0.003 0.0 01 0 .1 0.00002–0.0003 0.00 01 0.0 01 0.0 01 0.007 0.0 01 0.05 0.005–0.02 0.0 01 0.0002 0.006–0.005 0. 01 1 0.004–0.05 0.002 0.0007–0.0 01 Introduction to Trace Environmental Quantitative Analysis (TEQA) TABLE 1. 4 Primary Drinking Water Monitoring Requirements for Semivolatile... the NPDES, and this analytical testing has been © 2006 by Taylor & Francis Group, LLC 17 18 Trace Environmental Quantitative Analysis, Second Edition TABLE 1. 5 Primary Drinking Water Monitoring Requirements for Volatile Organics Contaminant Benzene Carbon tetrachloride Chlorobenzene p-Dichlorobenzene o-Dichlorobenzene 1, 2-Dichloroethane 1, 1-Dichloroethylene Cis -1 , 2-dichlorethylene Trans -1 , 2-dichloroethylene... Figure 1. 2 The mass spectrum shown on top in Figure 1. 2 is for a backgroundsubtracted standard or clofibric acid methyl ester, while the mass spectrum shown below is for a background-subtracted mass spectrum obtained from the effluent © 2006 by Taylor & Francis Group, LLC 6 Trace Environmental Quantitative Analysis, Second Edition 10 0 12 8 Rel abundance 80 60 40 13 0 16 9 20 12 7 10 0 15 4 m/z 18 1 12 8 Rel... Trans -1 , 2-dichloroethylene Dichloromethane 1, 2-Dichloropropane Ethylbenzene Styrene Tetrachloroethylene (PCE) Toluene 1, 2,4-Trichlorobenzene 1, 1 , 1- Trichloroethane 1, 1,2-Trichloroethane Trichloroethylene (TCE) Vinyl chloride Total xylene MCL (mg/L) MDL (mg/L) 0.005 0.005 0 .1 0.075 0.6 0.005 0.007 0.07 0 .1 0.005 0.005 0.7 0 .1 0.005 1 0.005 0.2 0.2 0.005 0.002 10 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005... 0.04 0.2 0.0002 0.0005 0.0 01 0.006 0.5 0.004 0.003 0.00000003 0.05 0 .1 0.006 0.002 0.0 01 0.009 0.0002 0.0 01 0.00002 0.0 01 0.0002 0.0004 0.009 0.000 01 0.000 01 0.006 0.0004 0.0 01 0.00 01 0.00002 0.00 01 0.002 0.00002 0.00 01 0.00004 0.0006 0.00 01 0.00007 0.0 01 0.000000005 0.0002 0.0005 The Clean Water Act, which was last amended in 19 87, provides for grants to municipalities to build and upgrade treatment facilities... levels varied from 0 .11 to 0. 51 parts © 2006 by Taylor & Francis Group, LLC 4 Trace Environmental Quantitative Analysis, Second Edition EI+ 573 (M-CH3)+ Relative abundance 10 0 F O 80 F F F F F 211 20 588 (M)+ 299 200 300 400 500 600 407 10 0 Relative abundance F O F 60 40 F F 700 NCI F 80 F O O F 60 F F 40 20 408 350 400 450 500 m/z 550 600 650 FIGURE 1. 1 Electron impact (top) and negative chemical... to Figure 1. 4, the sample prep lab may give to the analyst a complete sample extract along with a signed chain-of-custody form to provide evidence as to where the extract is headed next This five-step approach to biomonitoring is also applicable to trace enviro-chemical quantitative analysis We leave for the moment trace enviro-health quantitative analysis and pick up trace enviro-chemical quantitative. .. Supelcoport coated with 1. 5% SP-2250 /1. 95% SP-24 01 packed into a 1. 8-m-long × 4-mm-inner-diameter tube (the essence of Method 608) However, during the late 19 80s, labs, including the one this author worked in, began to investigate megabore capillary columns as alternatives to packed columns Megabore capillary columns made from fused silica could be easily connected to the common ¼-in injection port used . enviro-health. FIGURE 1. 2 EI mass spectra for clofibric acid methyl ester. 10 0 80 60 40 20 Rel abundance 12 7. 12 8 13 0 16 9 15 4. m/z 18 1. 10 0 80 60 40 20 Rel abundance 12 7. 12 8 13 0 16 9 15 4. m/z 18 1. ©. States of America on acid-free paper 10 9876543 21 International Standard Book Number -1 0 : 0-8 24 7-5 85 3-6 (Hardcover) International Standard Book Number -1 3 : 97 8-0 -8 24 7-5 85 3-0 (Hardcover) Library. µg/L 0 .19 (0 .14 –0.23) Monobenzyl phthalate Blood 10 29 µg/L 17 .4 (14 .1 20.7) Monobutyl phthalate Blood 10 29 µg/L 26.7 (23.9–29.4) Monoethyl phthalate Blood 10 29 µg/L 17 6.0 (13 2–220) Mono-2-ethyl