AN ABSTRACT OF THE DISSERTATION OF Daniel R. Oros for the degree of Doctor of Philosophy in Environmental Sciences presented on September 24. 1999. Title: Application of Biomarker Compoundsas Tracers for Sources and Fates of Natural and Anthropogenic Organic Matter in the Environment. Redacted for Privacy Abstract approved: Bernd R.T. Simoneit Determination of the source and fate of natural (higher plant lipids, marine lipids, etc.) and anthropogenically (e.g., petroleum, coal emissions) derived hydrocarbons and oxygenated compounds in the environment was accomplished using gas chromatography (GC) and gas chromatography-mass spectrometry (GC- MS) to characterize or identify molecular biomarkers to be utilized as tracers. The distributions and abundances of biomarkers such as straight chain homologous series (e.g., n-alkanes, n-alkanoic acids, n-alkan-2-ones, n-alkanols, etc.) and cyclic terpenoid compounds (e.g., sesquiterpenoids, diterpenoids, steroids, triterpenoids) were identified in epicuticular waxes from conifers of western North America (natural emissions). These biomarkers and their thermal alteration derivativeswere also identified in smoke emissions from known vegetation sources (e.g., conifers, deciduous trees and grasses) and were then applied as tracers in soils, soils that contained wildfire residues and soillriver mud washout after wildfire burning. Where possible, the reaction pathways of transformation from the parentprecursor compounds to intermediate and final alteration products were determined from GC- MS data. In addition, molecular tracer analysis was applied to air, water and sediment samples collected from a lacustrine setting (Crater Lake, OR) in order to determine the identities, levels and fates of anthropogenic (i.e., petroleum hydrocarbon contamination from boating and related activities) hydrocarbons ina pristine organic matter sink. This work demonstrated that biomarker tracer analysis is a useful tool for developing environmental management and pollution mitigation strategies. ©Copyright by Daniel R. Oros September 24, 1999 All Rights Reserved APPLICATION OF BIOMARKER COMPOUNDS AS TRACERS FOR SOURCES AND FATES OF NATURAL AND ANTHROPOGENIC ORGANIC MATTER IN TILE ENVIRONMENT Daniel R. Oros A DISSERTATION submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Presented September 24, 1999 Commencement June 2000 Doctor of Philosophy Dissertation of Daniel R. Oros presented September 24. 1999 :.x'i Redacted for Privacy Major Professor, representing Environmental Sciences Redacted for Privacy Chair of the Environmental Sciences Program Redacted for Privacy Dean of the Gradu.td School I understand that my dissertation will become part of the permanent collection of Oregon State University libraries. My signature authorizes release of my dissertation to any reader upon request. Redacted for Privacy Daniel R. Oros ACKNOWLEDGMENTS I express my gratitude to Professor Dr. Bernd R.T. Simoneit for his guidance and support throughout my graduate study at Oregon State University. I am grateful to Professors Dr. Jesse Ford, Dr. Evelyn Sherr, Dr. John Baham and Dr. James Liburdy for participating as members of my graduate committee. Thank you all very much for your advice and for making the education process a very challenging and rewarding experience. I would also like to acknowledge my family for showing endless love and patience throughout this time. This research was funded in part by grants to Dr. Bernd R.T. Simoneit from the U.S. Environmental Protection Agency (Grant CR 823990-01-0) and the U.S. Department of the Interior, National Park Service (Grant CA-9000-8-0006). The author was awarded a graduate student fellowship by the Oregon State University Faculty Diversity Initiative - Minority Graduate Student Pipeline Support Fellowship Program for the final year of study. CONTRIBUTION OF AUTHORS Dr. Bernd R.T. Simoneit assisted in the conception and revision of each manuscript. Dr. Laurel J. Standley and Xiaojing Chen each assisted with the data collection for Chapter II. Dr. Laurel J. Standley and Dr. Monica A. Mazurek each assisted with the data collection for Chapter V. Dr. John E. Baham assisted in the conception and revision of Chapter V. Dr. Robert W. Collier assisted with the data collection for Chapter VI. TABLE OF CONTENTS Page CHAPTER I. INTRODUCTION 1 CHAPTER II. EPICUTICULAR WAX COMPOSITIONS OF CONIFERS FROM WESTERN NORTH AMERICA 10 ABSTRACT 11 INTRODUCTION 12 EXPERIMENTAL METHODS 12 Sampling 12 Extraction and Fractionation 13 Instrumental Analyses 13 Compound Identification and Quantitation 14 RESULTS AND DISCUSSION 14 Hydrocarbons 15 Alcohols 18 Fatty Acids 18 Carbonyl Compounds 19 Wax Esters 20 Molecular Biomarkers 21 CONCLUSIONS 24 ACKNOWLEDGMENTS 25 REFERENCES 25 CHAPTER III. IDENTIFICATION AND CONCENTRATIONS OF MOLECULAR TRACERS IN ORGANIC AEROSOLS FROM BIOMASS BURNING OF TEMPERATE CLIMATE CONIFERS 30 ABSTRACT 31 INTRODUCTION 32 BACKGROUND 33 EXPERIMENTAL METHODS 34 Sampling 34 Extraction and Fractionation 34 Instrumental Analyses 36 TABLE OF CONTENTS (Continued) Page Compound Identification and Quantitation 36 RESULTS AND DISCUSSION 37 Homologous Compound Series 37 Molecular Biomarkers 44 Polycyclic Aromatic Hydrocarbons 51 Unresolved Complex Mixture 52 Volatile and Elemental Carbon 53 Major Compound Groups 54 Major and Unique Biomarker Tracers 55 CONCLUSIONS 57 ACKNOWLEDGMENTS 58 REFERENCES 59 CHAPTER IV. IDENTIFICATION AN]) CONCENTRATIONS OF MOLECULAR TRACERS IN ORGANIC AEROSOLS FROM BIOMASS BURNING OF DECIDUOUS TREES 64 ABSTRACT 65 INTRODUCTION 66 BACKGROUND 67 EXPERIMENTAL METHODS 68 Sampling 68 Extraction and Fractionation 69 Instrumental Analyses 70 Compound Identification and Quantitation 70 RESULTS AND DISCUSSION 70 Homologous Compound Series 71 Molecular Biomarkers 78 Polycyclic Aromatic Hydrocarbons 82 Unresolved Complex Mixture 83 Volatile and Elemental Carbon 83 Major Compound Groups 84 Major and Unique Biomarker Tracers 85 CONCLUSIONS 88 TABLE OF CONTENTS (Continued) Page ACKNOWLEDGMENTS 89 REFERENCES 89 CHAPTER V. ORGANIC TRACERS FROM WILD FIRE RESIDUES IN SOILS AND RAIN/RIVER WASH-OUT 95 ABSTRACT 96 INTRODUCTION 97 EXPERIMENTAL METHODS 98 Sampling 98 Extraction and Fractionation 98 Instrumental Analyses 100 RESULTS AND DISCUSSION 101 Grass Field and Prairie Burning 101 Prairie Soil After Wildfire 109 Mixed ForestlChapanal Soil After Wildfire Burning and Forest Litter 112 Soil Erosion After Wildfire 118 Comparisons of Natural, Burned and Water Washed Soil Compositions 122 CONCLUSIONS 127 ACKNOWLEDGMENTS 128 REFERENCES 128 CHAPTER VI. INVESTIGATION OF THE EXTENT AND SIGNIFICANCE OF PETROLEUM HYDROCARBON CONTAMINATION IN CRATER LAKE, CRATER LAKE NATIONAL PARK, OREGON, U.S.A. 133 ABSTRACT 134 INTRODUCTION 135 BACKGROUND 137 Crater Lake 137 Natural Hydrocarbon Sources 140 Anthropogenic Hydrocarbon Sources 142 TABLE OF CONTENTS (Continued) Page Acute Hydrocarbon Input Events 146 EXPERIMENTAL METHODS 147 Sample Collection and Treatment 147 GC and CC-MS Analyses 152 Hydrocarbon Parameters 154 Quality Assurance/Quality Control (QA/QC) 156 RESULTS AND DISCUSSION 158 Petroleum Hydrocarbon Use 158 Sampling Sites and Analyses Conducted 159 Water Column Hydrocarbons 159 Surface Slick Hydrocarbons 160 Sediment Hydrocarbons 166 Atmospheric Hydrocarbons 173 SUMMARY OF MAJOR FINDINGS 177 ACKNOWLEDGMENTS 180 REFERENCES 181 CHAPTER VII. SUMMARY 187 BIBLIOGRAPHY 191 APPENDICES 207 RELATED WORK BY AUTHOR 252 LIST OF FIGURES (labeled by their respective chapters) Figure Fge I. 1. Major pathways of biomarker cycling in the environment. 2 111.1. GC-MS total ion current traces of Douglas Fir smoke particulate matter (numbers refer to carbon chain length on n-alkanes, A = n- alkanoic acids, OH = n-alkanol, U unknown, UCM = unresolved complex mixture). 38 111.2. GC-MS total ion current traces of Mountain Hemlock smoke particulate matter (abbreviations as in Fig. 111.1 and IS = internal standard). 39 111.3. GC-MS total ion current traces of Ponderosa Pine smoke particulate matter (abbreviations as in Fig. 111.1). 40 111.4. GC-MS total ion current traces of Sitka Spruce smoke particulate matter (abbreviations as in Fig. IH. 1). 41 111.5. Diterpenoid thermal alteration pathways. 46 111.6. Abietane to pimarane (NP) ratios for conifer smoke samples. 47 111.7. Phytosterol thermal alteration pathways. 50 IV. 1. GC-MS total ion current traces of Eucalyptus smoke particulate matter (numbers refer to carbon chain length of n-alkanes, A=n- alkanoic acid, OH=n-alkanol). 72 IV.2. GC-MS total ion current traces of Oregon Maple smoke particulate matter (abbreviations as in Fig. IV.1). 73 IV.3. GC-MS total ion current traces of Red Alder smoke particulate matter (abbreviations as in Fig. IV.1). 74 IV.4. GC-MS total ion current traces of Silver Birch smoke particulate matter (abbreviations as in Fig. IV.1). 75 IV.5. GC-MS total ion current traces of Dwarf Birch smoke particulate matter (abbreviations as in Fig. IV.1). 76 V.1. GC-MS total ion current traces of Ryegrass Field Soil before prescribed field burning (numbers refer to carbon chain length of n-alkanes, A = n-alkanoic acid, OH = n-alkanol, K= n-alkanone, X = contaminant and U = unknown). 103 V.2. GC-MS total ion current traces of Ryegrass Field Soil after prescribed field burning (abbreviations as in Fig. V.1). 104 LIST OF FIGURES (Continued) (labeled by their respective chapters) Figure Page V.3. GC-MStotal ion current traces of Ryegrass Wax (abbreviations as in Fig.V.1). 105 V.4. GC-MStotal