Longitudinal stability in cigarette smokers of urinary biomarkers of exposure to the toxicants acrylonitrile and acrolein

Menglan Chen, Steven G. Carmella, Chistopher Sipe, Joni Jensen, Xianghua Luo, Chap T. Le, Sharon E. Murphy, Neal L. Benowitz, F. Joseph McClernon, Ryan Vandrey, Sharon S. Allen, Rachel Denlinger-Apte, Paul M. Cinciripini, Andrew A. Strasser, Mustafa Al’Absi, Jason D. Robinson, Eric C. Donny, Dorothy Hatsukami, Stephen S. Hecht

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20 Scopus citations


The urinary metabolites cyanoethyl mercapturic acid (CEMA) and 3-hydroxypropyl mercapturic acid (3-HPMA) have been widely used as biomarkers of exposure to acrylonitrile and acrolein, respectively, but there are no published data on their consistency over time in the urine of cigarette smokers. We provided, free of charge over a 20 week period, Spectrum NRC600/601 research cigarettes to cigarette smokers in the control arm of a randomized clinical trial of the reduced nicotine cigarette. Urine samples were collected at weeks 4, 8, 12, 16, and 20 and analyzed for CEMA and 3-HPMA, and total nicotine equivalents (TNE) using validated methods. Creatinine-corrected intra-class correlation coefficients for CEMA, 3-HPMA, and TNE were 0.67, 0.46, and 0.68, respectively, indicating good longitudinal consistency for CEMA, while that of 3-HPMA was fair. A strong correlation between CEMA and TNE values was observed. These data support the use of CEMA as a reliable biomarker of tobacco smoke exposure. This is the first report of the longitudinal stability of the biomarkers of acrylonitrile and acrolein exposure in smokers. The data indicate that CEMA, the biomarker of acrylonitrile exposure, is consistent over time in cigarette smokers, supporting its use. While 3-HPMA levels were less stable over time, this biomarker is nevertheless a useful monitor of human acrolein exposure because of its specificity to this toxicant.

Original languageEnglish (US)
Article numbere0210104
JournalPloS one
Issue number1
StatePublished - Jan 2019

Bibliographical note

Funding Information:
This work was supported by National Institute on Drug Abuse and Food and Drug Administration grant U54 DA-031659 (ECD, DKH, CTL, and SSH). The funders had no role in the design and conduct of the study; collection, management, analysis, and interpretation of the data; preparation, review, or approval of the manuscript; and decision to submit the manuscript for publication. The authors are indebted to the contributions of the Masonic Cancer Center Analytical Biochemistry Shared Resource, which provided mass spectrometry support essential for this study.


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