RESEA R C H R E P O R T HE A L TH HE A L TH Development and Application of a EFF E CTS EFF E CTS Sensitive Method to Determine INSTITUTE INSTITUTE Concentrations of Acrolein and 101 Federal Street, Suite 500 Other Carbonyls in Ambient Air Boston, MA 02110, USA Number 149 May 2010 +1-617-488-2300 Thomas M. Cahill, M. Judith Charles, and www.healtheffects.org Vincent Y. Seaman RESEA R CH REPO R T Number 149 May 2010 Development and Application of a Sensitive Method to Determine Concentrations of Acrolein and Other Carbonyls in Ambient Air Thomas M. Cahill, M. Judith Charles, and Vincent Y. Seaman with a Critique by the HEI Health Review Committee Research Report 149 Health Effects Institute Boston, Massachusetts Trusted Science · Cleaner Air · Better Health Publishing history: The Web version of this document was posted at www.healtheffects.org in May 2010. Citation for document: Cahill TM, Charles MJ, Seaman VY. 2010. Development and Application of a Sensitive Method to Determine Concentrations of Acrolein and Other Carbonyls in Ambient Air. HEI Research Report 149. Health Effects Institute, Boston, MA. © 2010 Health Effects Institute, Boston, Mass., U.S.A. Cameographics, Belfast, Me., Compositor. Printed by Recycled Paper Printing, Boston, Mass. Library of Congress Number for the HEI Report Series: WA 754 R432. Cover paper: made with at least 55% recycled content, of which at least 30% is post-consumer waste; free of acid and elemental chlorine. Text paper: made with 100% post-consumer waste recycled content; acid free; no chlorine used in processing. The book is printed with soy-based inks and is of permanent archival quality. CONTENTS About HEI v About This Report vii HEI STATEMENT 1 INVESTIGATORS’ REPORT by Cahill et al. 3 ABSTRACT 3 INTRODUCTION 4 SPECIFIC AIMS 5 METHODS AND STUDY DESIGN 6 Mist Chamber Methodology 6 Carbonyl-Bisulfite Adduct Formation 7 Preparation of the 0.1 M Bisulfite Solution 9 Selection of the Derivatization Agent 10 Instrumental Analysis and Mass Spectral Characterization 10 Derivatization Optimization 12 Extraction Optimization 15 Selection of Internal Standards 17 Selection of Injection Standards 18 Mist Chamber Collection Efficiency Optimization 18 Evaluation of a Wide Range of Carbonyls 19 Evaluation of Possible Interference from Ozone 21 Field Sampling 22 RESULTS 25 Optimization of the Analytical Technique 25 Collection Efficiency and Spike Recovery 27 Possible Interference from Ozone 29 Field Sampling 30 DISCUSSION AND CONCLUSIONS 34 Method Development 34 Peace Bridge Sampling in Buffalo 35 Ambient Sampling in California 36 Directions for Future Research 37 Epilogue 38 IMPLICATIONS OF FINDINGS 38 ACKNOWLEDGMENTS 39 REFERENCES 39 Research Report 149 APPENDIX A. Standard Operating Procedures for Carbonyl Collection and Analysis 42 APPENDIX B. Clayton Group Services Laboratory Report for the Analysis of Acrolein from HMP-Coated Cartridges 44 ABOUT THE AUTHORS 45 OTHER PUBLICATIONS RESULTING FROM THIS RESEARCH 45 ABBREVIATIONS AND OTHER TERMS 45 CRITIQUE by the Health Review Committee 47 INTRODUCTION 47 SCIENTIFIC BACKGROUND 47 Chemistry 47 Exposure and Health Effects 48 Current Techniques for Measuring Acrolein 48 STUDY DESIGN AND SPECIFIC AIMS 49 METHODS AND RESULTS 49 Development and Optimization of Mist Chamber Methodology 49 Evaluation of Mist Chamber Collection Efficiency, Recovery, and Retention 51 Field Testing 52 HEI REVIEW COMMITTEE EVALUATION 52 Method Development 52 Field Studies 53 Conclusions 54 REFERENCES 54 ACKNOWLEDGMENTS 55 Related HEI Publications 57 HEI Board, Committees, and Staff 59 ABOUT HEI The Health Effects Institute is a nonprofit corporation chartered in 1980 as an independent research organization to provide high-quality, impartial, and relevant science on the effects of air pollution on health. To accomplish its mission, the institute • Identifies the highest-priority areas for health effects research; • Competitively funds and oversees research projects; • Provides intensive independent review of HEI-supported studies and related research; • Integrates HEI’s research results with those of other institutions into broader evaluations; and • Communicates the results of HEI research and analyses to public and private decision makers. HEI receives half of its core funds from the U.S. Environmental Protection Agency and half from the worldwide motor vehicle industry. Frequently, other public and private organizations in the United States and around the world also support major projects or certain research pro- grams. HEI has funded more than 280 research projects in North America, Europe, Asia, and Latin America, the results of which have informed decisions regarding carbon monoxide, air toxics, nitrogen oxides, diesel exhaust, ozone, particulate matter, and other pollutants. These results have appeared in the peer-reviewed literature and in more than 200 comprehensive reports published by HEI. HEI’s independent Board of Directors consists of leaders in science and policy who are com- mitted to fostering the public–private partnership that is central to the organization. The Health Research Committee solicits input from HEI sponsors and other stakeholders and works with sci- entific staff to develop a Five-Year Strategic Plan, select research projects for funding, and oversee their conduct. The Health Review Committee, which has no role in selecting or overseeing studies, works with staff to evaluate and interpret the results of funded studies and related research. All project results and accompanying comments by the Health Review Committee are widely dis- seminated through HEI’s Web site (www.healtheffects.org), printed reports, newsletters and other publications, annual conferences, and presentations to legislative bodies and public agencies. v ABOUT THIS REPORT Research Report 149, Development and Application of a Sensitive Method to Determine Concentrations of Acrolein and Other Carbonyls in Ambient Air, presents a research project funded by the Health Effects Institute and conducted by Dr. Thomas M. Cahill of the Department of Integrated Natural Sciences, Arizona State University, Phoenix, and his colleagues. This report contains three main sections. The HEI Statement, prepared by staff at HEI, is a brief, nontechnical summary of the study and its findings; it also briefly describes the Health Review Committee’s comments on the study. The Investigators’ Report, prepared by Cahill et al., describes the scientific background, aims, methods, results, and conclusions of the study. The Critique is prepared by members of the Health Review Committee with the assistance of HEI staff; it places the study in a broader scientific context, points out its strengths and limitations, and discusses remaining uncertainties and implications of the study’s findings for public health and future research. This report has gone through HEI’s rigorous review process. When an HEI-funded study is completed, the investigators submit a draft final report presenting the background and results of the study. This draft report is first examined by outside technical reviewers and a biostatistician. The report and the reviewers’ comments are then evaluated by members of the Health Review Committee, an independent panel of distinguished scientists who have no involvement in selecting or overseeing HEI studies. During the review process, the investigators have an opportunity to exchange comments with the Review Committee and, as necessary, to revise their report. The Critique reflects the information provided in the final version of the report. vii HEI STATEMENT Synopsis of Research Report 149 Development and Application of a Sensitive Method for Determination of Acrolein Concentrations in Ambient Air BACKGROUND bisulfite, with which it forms a stable chemical Acrolein is a reactive aldehyde that injures the reaction product. The overall aim of the study was airways in humans and other species, and the U.S. to develop and optimize a method for the collection Environmental Protection Agency lists it among the and analysis of acrolein and to evaluate the perfor- mobile-source air toxics that pose the greatest mance of the method by three different measures. health risk. Information on the acrolein concentra- One measure was collection efficiency, calculated tions to which people are exposed is an important as the concentration of acrolein in the first of two prerequisite for assessing the risk to human health. mist chambers in series relative to that in the Despite some technological improvements, it second chamber, expressed as a percentage. The remains difficult to accurately measure acrolein at second measure was “spike recovery” (also defined low levels because, upon collection, it rapidly as the mass balance), a measure of the overall car- forms unstable intermediates that are difficult to bonyl recovery, from collection to analysis. It was differentiate and quantify. determined by adding a known carbonyl mass to a In 2001 Dr. Judith Charles of the University of “spiking tube” placed upstream of the mist California–Davis responded to HEI Request for Pre- chamber and delivering it to the chamber by liminary Applications 00-3 with a proposal to blowing pure nitrogen through the tube to simulate develop a new method for measuring low levels of ambient collection conditions. Recovery was calcu- acrolein, crotonaldehyde, and other unstable alde- lated as the percentage of the carbonyl mass in both hydes and apply the new method to assess expo- chambers and remaining in the spiking tube rela- sure