Using Honey Bees and Thermal Desorption/Gas Chromatography
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University of Montana ScholarWorks at University of Montana Graduate Student Theses, Dissertations, & Professional Papers Graduate School 2001 Using honey bees and thermal desorption/gas chromatography/ mass spectrometry to assess the regional distribution of bioavailable volatile organic compounds in northeast Maryland David C. Jones The University of Montana Follow this and additional works at: https://scholarworks.umt.edu/etd Let us know how access to this document benefits ou.y Recommended Citation Jones, David C., "Using honey bees and thermal desorption/gas chromatography/mass spectrometry to assess the regional distribution of bioavailable volatile organic compounds in northeast Maryland" (2001). Graduate Student Theses, Dissertations, & Professional Papers. 9148. https://scholarworks.umt.edu/etd/9148 This Thesis is brought to you for free and open access by the Graduate School at ScholarWorks at University of Montana. It has been accepted for inclusion in Graduate Student Theses, Dissertations, & Professional Papers by an authorized administrator of ScholarWorks at University of Montana. For more information, please contact [email protected]. The University of Montana Permission is granted by the author to reproduce this material in its entirety, provided that this material is used for scholarly purposes and is properly cited in published works and reports. **Please check "Yes” or ”No" and provide signature** Yes, I grant permission No, I do not grant permission Author’s Signature: ^ Date: _ r Any copying for commercial purposes or financial gain may be undertaken only with the author’s explicit consent. 8/98 Using Honey Bees and Thermal Desorption / Gas Chromatography / Mass Spectrometry to Assess the Regional Distribution of Bioavailable Volatile Organic Compounds in Northeast Maryland by David C. Jones B.S. Idaho State University, Pocatello, Idaho, 1986 Presented in partial fulfillment of the requirements of the degree Masters in Science in Chemistry The University of Montana August, 2001 Approved by Board of Dean, Graduate School Date UMI Number: EP39949 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI Dissârlation Publish«f>g UMI EP39949 Published by ProQuest LLC (2013). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code uest ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, MI 48106- 1346 Jones, David C. M.S. August, 2001 Chemistry Using Honey Bees and Thermal Desorption/Gas Chromatography/Mass Spectrometry to Assess the Regional Distribution of Bioavailable Volatile Organic Compounds in Northeast Maryland Advisor: Garon C. Smith G a s Honey bee colonies were used to identify potential sources of bioavailable, priority pollutant, volatile organic compounds. Bioavailable pollutants are those in the environment that can be assimillated by any organisms when contacted by them. Our objective was to determine if an army base-Aberdeen Proving Ground (APG) in Maryland-was the main source of these contaminants. Paired bee hives were set up on three, nine and twenty-one mile radii along three main transects: north, northwest and southwest. Using constant flow air pumps and carbon-based chemical traps, samples were taken from the hive air and outside air at each site. Samples were analyzed using thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS). Concentrations were quantified for ten compounds - four halogenated organics representing industrial solvents, and six aromatic hydrocarbons, representing four persistant petroleum fuel residues and two tear gas residues. The data was reduced using three methods: Chronic Exposure, Acute Exposure Ranking, and an Analysis of Variance. Results demonstrate that the army base is not the major source of the priority pollutants, but that the pollutants correlate directly with multiple, local sources. These include vehicle exhaust, fugitive fossil fuel emissions, household products, agrochemicals, and industrial reagents. Comparisons between the 1998 and 1999 field seasons are made. u Acknowledgements I’d like to thank and acknowledge the many individuals whose efforts went into the completion of this thesis. Dr. Garon Smith for luring me into the “bee project”, for his years of patience and guidance, and for his mentorship. My committee members Dr. Jerry Bromenshenk for his enthusiasm, drive and support and Dr. Mark Craciolice for “Zen-like” calmness, good humor, and friendship. Thanks to Dr. Colin Henderson for his help setting up, running, and checking the statistics for this project. To my Lab 05 mates Tony Ward, Chris Wrobel, and Bruce King for their friendship and expertise, without whom the challenge of a project like this would have been unrealized. To Mark Mencel for his sample analysis, enthusiasm for climbing and willingness to do the grunt work. To the BeeAlert! crew especially Lenny Hahn, Chief Bee Wrangler, Jason Volkman ’98 Maryland crew, ‘The Kiwis” Michelle and Byron Taylor the ’99 Maryland crew, David Hooper head work-study. To Dr. Edward Rosenberg, Department Chair of Chemistry, and the rest of the Department of Chemistry faculty and staff especially Bonnie Gatewood, Barbara McCann, and Rosalyn Chaitoff, without whom no thesis would get done. To my Big Sky High School colleagues Jim Harkins, Brett Taylor, Robin Anderson and David Oberbillig for their support and understanding of my absent-mindedness through these past few years. To Steve Earle for sharing his yawlp and diverse musical talent these last several write-it-up weeks. To Jennifer Carey my Production Editor, life-partner and best friend. Thanks for helping me keep it all in perspective .. .and fun. Most importantly, I thank the many bees who consistently went about their business completely oblivious to my efforts. This work was supported by Contract DAMD17-95-C-5072, U.S. Army Medical Research and Matériels Command, Ft. Detrick, MD, and a Partners in Science Grant from The Research Corporation / M.J. Murdock Charitable Trust. m Table o f Contents Abstract .......................................................................................................................................... li Acknowledgements ......................................................................................................................iii Table of Contents .........................................................................................................................iv List of Tables ................................................................................................................................. v List of Figures .............................................................................................................................. vi Chapter 1: Introduction and Statement of the Problem ............................................................. 1 Chapter 2: Experimental Method ...............................................................................................11 Chapter 3: Results .......................................................................................................................29 Chapter 4: Discussion, Conclusions and Suggestions for Further Study ........................... 65 References .................................................................................................................................... 84 Appendices ...................................................................................................................................90 IV List of Tables 1.1 Estimated Global Anthropogenic Emissions of Nonmethane Volatile Organic Compounds ...................................................................................................................... 8 2.1 Description of sampling sites ........................................................................................ 13 2.2 Sampling dates for 1998 and 1999 field seasons .........................................................14 2.3 Dynatherm MTDU 910 Parameters .............................................................................. 19 2.4 Tekmar LCS 2GGG/ALS 2016 Parameters....................................................................19 2.5 Hewlett Packard 5890/5971 GC/MS Parameters ........................................................ 20 2.6 Mass Spectrometer Calibration Parameters .................................................................. 21 2.7 Method 502 Analytes (Mixes 1-6) .................................................................................23 2.8 Standard Checks (200 ng) and % Relative Uncertainty ..............................................26 3.1 1998 Target Analytes ....................................................................................................30 3.2 1999 Target Analytes ....................................................................................................31 3.3 1998 and 1999 mean hive/air concentrations (ppt) by site ........................................37 3.4 1998 Hive Acute Exposure Index ................................................................................43 3.5 1998 Air Acute Exposure Index ...................................................................................45