AN ABSTRACT OF THE THESIS OF

Xiaojing Chen for the degree of Master of Science in Oceanography presented on November 8. 1991

Title: Oxygenated Natural Products in Tropospheric AerosolsSources and Transport

Abstract approved: Redacted for Privacy Bernd R. T. Simoneit

A systematic study of the composition and chemotaxonomy of oxygenated natural organic compounds in rural aerosols within Oregon is presented. Correlation with source vegetation provided useful information for understanding the formation, transport, and fate of aerosol particles in the troposphere. Distributions and concentrations of lipid classes and oxygenated straight-chain homologous series such as n-alkanols, w-hydroxy alkanoic acids,-a1kanol acetates,-a1kan-2-ones, -a1kan- 10- ones, saturated and unsaturated aldehydes, in-chain alcohols and wax esters were analyzed in rural aerosol particles and their source vegetation. Oxygenated cyclic di- and triterpenoids, with relatively complicated chemical structures, were also determined and provided more definitive correlations between source vegetation and aerosols. Results included: (1) an increase inCrnaxof -a1kanol homologs in aerosols from the cooler coast to the warmer desert climates; (2) geographical and environmental variation of wax lipids from source vegetation; (3) the emission mechanisms involved do not include any significant gas-particle partitioning; (4) long range transport of higher plant derived aerosol particles has been confirmed. CCopyright by Xiaojing Chen November 8, 1991

All Rights Reserved OXYGENATED NATURAL PRODUCTS IN TROPOSPHERIC AEROSOLS - SOURCES AND TRANSPORT

by

Xiaojing Chen

A THESIS

submitted to Oregon State University

in partial fulfillment of the requirements for the degree of

Master of Science

Completed November 8, 1991

Commencement June 1992 APPROVED: Redacted for Privacy

Dr. Bernd .( Simoneit, Professor of Oceanography in charge of major Redacted for Privacy Dr. Douglas R.4aldweil, Dean of Co1le-Oeanography

Redacted for Privacy

Graduate

Date thesis is presented November 8, 1991

Typed byjajjng Chen ACKNOWLEDGEMENTS

I wish to thank Dr. Bemd R. T. Simoneit for giving me the opportunity to work in the organic geochemistry group and his continuous advice and encouragement, and to Dr. Fredrick G. Prahi for his valuable suggestions and providing the latroscan, and to Dr. Alan C. Mix and Dr. Donald R. Buhier for serving on my committee and reviewing my dissertation. I would like to acknowledge Dr. Laurel J. Standley whose work provided the sample fractions for this thesis. I am also grateful to many past and present members of the organic geochemistry group for useful discussions, assistance and suggestions, particularly Dr. Orest E. Kawka, Mr. Roald N. Leif and Mr. Luis A. Pinto. I thank Dr. Alan W. A. Jeffrey for his valuable discussion and proofreading. I also would like to thank Mr. Kelly A. Dunnahoo for drawing some of the figures and Ms. Rosario D.

Pichay and Mrs. Barbara McVicar for formatting my thesis. Finally, to my dear parents, sister and brother, many thanks for your patience and support. TABLE OF CONTENTS Page CHAPTER I.INTRODUCTION

CHAPTER II. AN APPLICATION OF IATROSCAN THIN- 3 LAYER CHROMATOGRAPHY WITH FLAME IONIZATION DETECTION-LIPID CLASSES OF EPICUTICULAR WAXES OF VASCULAR PLANTS AS BIOMARKERS IN THE LOWER TROPOSPHERIC ENVIRONMENT INTRODUCTION 3 EXPERIMENTAL METhODS 4 Sample Locations and Descriptions 4 Lipid Isolation 7 Lipid Analysis 8 RESULTS AND DISCUSSION 8 Lipid Concentrations and Distributions of Transect Aerosols 9 Lipid Distributions of Epicuticular WaxesofSource Vegetation 9 Lipid DistributionofSurface Soil 17 Source CorrelationsofTransect Aerosols 18 CONCLUSIONS 18

CHAPTER III. CHARACTERIZATION AND CORRELATION 19 OF OXYGENATED COMPOUNDS IN AEROSOL PARTICLES AND SOURCE VEGETATION: I-ALCOHOL FRACTION INTRODUCTION 19 EXPERIMENTAL METHODS 19 Sample Locations and Descriptions 19 Lipid Isolation and Separation 20 Lipid Analysis 21 RESULTS AND DISCUSSION 21 Homolog Distributions: Concentrations and Reproducibility 22 Homolog Distributions: Correlation with Source Signatures 30 Parameter Analysis: Sources and Transport 34 Molecular Markers: Sources and Transport 37 Diterpenoids 37 Phytosterols and Triterpenoids 44 CONCLUSIONS 52

CHAPTER IV. CHARACTERIZATION AND CORRELATION 55 OF OXYGENATED COMPOUNDS IN AEROSOL PARTICLES AND SOURCE VEGETATION: II - KETONES (ALDEHYDES) AND MISCELLANEOUS TERPENOIDS INTRODUCTION 55 EXPERIMENTAL METhODS 55 Ketone Fraction Analysis 55 Page

RESULTS AND DISCUSSION 56 Homolog Distributions: Correlation with Source Signatures 56 Ketones 56 In-Chain-Alcohols 61 Saturated Aldehydes 61 Unsaturated Aldehydes 63 Unknown Homologs 63 n-Alkanol Acetates 63 Wax Esters 63 Molecular Markers 74 Procedure Contaminants 74 CONCLUSIONS 77 CHAPTER V. SUMMARY 79 BIBLIOGRAPHY 81 APPENDIX I. Relevant Formulas and Calculations 89 APPENDIX II. Histograms of -Alkano1 (-) and U-Hydroxy 90 Alkanoic Acid()Distributions in Aerosols and Source Vegetation Wax Collected Along a Transect From the State of Oregon

APPENDIX III. Histograms of Phytosterols(-: C27:i, C281, C291; 100 --:C282; C292)Distributions in Aerosols and Source Vegetation Wax Collected Along a Transect From the State of Oregon

APPENDIX IV. Histograms of Wax Ester Distributions in Vegetation 105 Wax Extracts Collected Along a Transect From the State of Oregon

APPENDIX V. Chemical Structures of Diterpenoids and Triterpenoids 109 Cited(With CAS Registry Number Listing) APPENDIX VI. Mass Spectral Reference File of Compounds Cited 115 in This Study LIST OF FIGURES

Figure Page

II. 1. Location map of the sampling sites of the aerosol particles 6 in the transect across the State of Oregon.

11.2. Examples of Iatroscan analyses for aerosols from the transect 11 regions (A: hydrocarbons; B: wax esters; C: carboxylic acid methyl esters; D: ketones; E: alcohols; F: polar unknown lipids): (a) standard lipid mixture (A: octadecane; B: stearyl stearate; C: methyl stearate; D: 2-nonadecanone; E: 1-nonadecanol); (b) aerosol from the Coast Range; (c) aerosol from the Wiflamette National Forest; (d) aerosol from the Columbia Basin;(e) aerosol from the Umatilla National Forest. The chromarod was developed, from right to left in the figure, for 30 mm in hexane-diethyl ether (96:4).

11.3. Concentration distribution diagrams of lipid classes 12 (A: hydrocarbons; B: wax esters; C: carboxylic acid methyl esters; D: ketones; E: alcohols; F: polar unknown lipids) in aerosols from the transect regions: (a) Coast Range; (b) Wilamette National Forest; (c) Columbia Basin; (d) Umatilla National Forest.

11.4. Examples of lairoscan analyses for the source vegetation 15 (A: hydrocarbons; B: wax esters; C: carboxylic acid methyl esters; D: ketones; E: alcohols; F: polar unknown lipids): (a) standard lipid mixture (A: octadecane; B: stearyl stearate; C: methyl stearate; D: 2-nonadecanone; E: 1-nonadecanol); (b) Grass from the Columbia Basin; (c) 'Green Waxy Bush" from the Umatilla National Forest; (d) Douglas Fir from the Coast Range; (e) Douglas Fir from the Umatilla National Forest; (f) Brewer Spruce from the Coast Range; (g) Red Alder Bark from the Coast Range; (h) Alder from the Umatilla National Forest; (i) Mountain Hemlock from the Willamette National Forest. The chromarod was developed, from right to left in the figure, for 30 mm in hexane-diethyl ether (96:4).

11.5. Concentration distribution diagrams of lipid classes 16 (A: hydrocarbons; B: wax esters; C: carboxylic acid methyl esters; D: ketones; E: alcohols; F: polar unknown lipids) in the source vegetation wax and soil of the transect regions.

111.1. Histogram (carbon number versus concentration) 26 distributions of -a1kanols and tu-hydroxy alkanoic acids (-) in the aerosols and source vegetation waxes collected from the Coast Range. Figure Page

111.2. Histogram (carbon number versus concentration) distributions 27 of-alkanols and co-hydroxy alkanoic acids () in the aerosols and source vegetation waxes collected from the Willamette National Forest.

111.3. Histogram (carbon number versus concentration) distributions 28 of -alkanols and co-hydroxy alkanoic acids(S")in the aerosols, source vegetation waxes and soil collected from the Columbia Basin.

111.4. Histogram (carbon number versus concentration) distributions 29 of -a1kanols and co-hydroxy alkanoic acids in the aerosols and source vegetation waxes collected from the Umatilla National Forest.

111.5. Examples of: (a) mass spectrum of methyl 14-hydroxytetradecanoate 32 trimethylsilyl ether, (b) mass spectrum of methyl 16-hydroxyhexa- decanoate trimethyl silyl ether, (c) mass fragmentograms of methyl 14-hydroxytetradecanoate and methyl 16-hydroxyhexadecanoate trimethyl silyl ethers (1 and 2, respectively) from the transect aerosol (Coast Range II).

111.6. Example of: (a) mass spectrum of methyl 3-oxohexacosanoate; 33 (b) fragmentogram offl-C25toC293-oxo-alkanoic acid methyl esters.

111.7. Mass fragmentograms of diterpenoids (m/z 237; 239) from the 42 transect aerosols: (a) Coast Range ifi; (b) Wilamette National Forest II; (c) Columbia Basin II; (d) Umatilla National Forest II (I: 1 3-isopropyl-5a-podocarpa-6,8, 11,1 3-tetraen- 1 6-oic acid methyl ester,I*: isomer of 1 3-isopropyl-5a-podocarpa-6, 8,11,13- tetraen- 1 6-oic acid trimethylsilyl ester, II: dehydroabietic acid methyl ester, 11*: isomer of dehydroabietic acid trimethylsilyl ester, III: 7-hydroxydehydroabietic acid methyl ester, Roman numbers indicate chemical structures cited in Appendix V, cf. Table ffl.5).

111.8. Mass fragmentograms of diterpenoids (m/z 251; 253) from the 43 transect aerosols: (a) Coast Range I; (b) Willamette National Forest II; (c) Columbia Basin II; (d) Umatilla National Forest II (IV: Calocedrin, V: methyl 7-oxodehydroabietate, *: trimethylsilyl 7-oxodehydroabietate, VI: methyl 7-oxo- 1 3-isopropylpodocarpa- 5,8,11,1 3-tetraen- 1 5-oate, VII: methyl 3-oxodehydroabietate, 1: Unknown 111.3, 2: Unknown 111.4, 3: Unknown 111.5; Roman numbers indicate chemical structures cited in Appendix V, cf. Table 111.5).

111.9. Histogram (carbon number versus concentration) distributions 45 of phytosterols (-:C27:l, C28:l, C29:i; --: C28:2; ---: C29:2) in the aerosols and source vegetation waxes collected from the Coast Range. Figure Page

111.10. Histogram (carbon number versus concentration) distributions 46 of phytosterols (-: C27:1, C28:1, C291; C28:2; ---: C29:2) in the aerosols and source vegetation waxes collected from the Willamette National Forest.

111.11. Histogram (carbon number versus concentration) distributions 47 of phytosterols (-: C27:1, C281, C291;--S:C282. C29:2) in the aerosols, source vegetation waxes and soil collected from the Columbia Basin.

111.12. Histogram (carbon number versus concentration) distributions 48 of phytosterols (-: C27:1, C281, C29:1;-S-:C28:2; : C29.2) in the aerosols and source vegetation waxes collected from the Umatilla National Forest.

111.13. Mass fragmentograms of phytosterols (m/z 129) and arnyrins 49 (m/z 218) from the transect aerosols: (a) Coast Range ifi; (b) Willamette National Forest II; (c) Columbia Basin II; (d) Umatila National Forest II (Vifi: cholesterol, IX: brassicasterol, X: campesterol, XI: stigmasterol, XII: 3-sitosterol, XIV: f3-amyrin, XVI: a-amyrin, n30: C30 -a1kanol; Roman numbers indicate chemical structures cited in Appendix V, cf. Table 111.5).

111.14. Ternary diagram of phytosterols (C27, C28, C29) in the aerosols 50 collected from a transect across the State of Oregon: (1) Coast Range I; (2) Coast Range II; (3) Coast Range ifi; (4) Willamette National Forest I; (5) Willamette National Forest II; (6) Columbia Basin I; (7) Columbia Basin II; (8) Umatilla National Forest I; (9) Umatila National Forest II.

111.15. Ternary diagram of phytosterols (C27, C28, C29) in the source 51 vegetation waxes and soil collected from a transect across the State of Oregon: Coast Range (1) Moss; (2) Salmonberry; (3) Alder Bark; Wood Fern; Sword Fern; Norway Spruce; (4) Brewer Spruce; Wilamette National Forest (1) Rhododendron; (5) Big-cone Douglas Fir; (6) Brewer Spruce; Columbia Basin (7) Juniper; (8) Juniper/Sage Litter; (9) Grass; (10) Wilson Ranch Soil; Umatilla National Forest (3) Douglas Fir; Elm; (11) Alder; (12) Ponderosa Pine; (13) White Fir; (1) Douglas Fir (14) Pacific Silver Fir.

111.16. Mass fragmentograms of oleanolic and ursolic acids (ni/z 203) 53 from the transect aerosols and source vegetation wax: (a) Coast Range ifi; (b) Wilamette National Forest II; (c) Columbia Basin II; (d) Umatila National Forest II; (e) Laurel (XX: Friedelin, XXI: methyl 3-oxo-olean-12-en-28-oate, XXIII: methyl oleanolate, XXIV: methyl 3-oxo-urs- 12-en-28-oate, XXV: methyl ursolate, TI': triterpenoid, Roman numbers indicate chemical structures cited in Appendix V, cf. Table HI.5). Figure Page

IV. 1. Examples of homolog mass spectra: (a) C27 -a1kan-2-one; 60 (b) C31n-alkan-10-one; (c)C27in-chain alcohol. IV.2. Examples of homolog mass spectra: (a)-Triacontana1; 62 (b)-octacos-6-enal.

IV.3. Example of: (a) mass spectrum of the cluster ofC32wax esters 66 with acid/alcohol moieties ofC14118, C16116, C18/14,andC22110 in laurel wax; (b) GC trace of the ketone fraction of alder wax showing theC34toC46wax esters, with a, b, and c indicating the C27,C29 and C31 n-alkanes, d and e indicating theC31andC33 n-alkan- 10-ones. IV.4. Histogram (carbon number versus concentration) distributions 70 of wax esters in the source vegetation wax collected from the Coast Range. IV.5. Histogram (carbon number versus concentration) distributions 71 of wax esters in the source vegetation wax collected from the Willamette National Forest. IV.6. Histogram (carbon number versus concentration) distributions 72 of wax esters in the source vegetation wax collected from the Columbia Basin. IV.7. Histogram (carbon number versus concentration) distributions 73 of wax esters in the source vegetation wax collected from the Umatilla National Forest. LIST OF TABLES

Table Page

II. 1. Sample locations and environmental data for the transect aerosols 5

11.2. Source vegetation for aerosols in Table 11.1 7

11.3. Analytical data for lipids in the transect aerosol particles 10

11.4. Analytical data of wax lipids in vegetation from the transect 13 regions

111.1.Analytical data for transect aerosols 23

111.2.Analytical data for -alkanols in vegetation waxes from the transect 25 regions

111.3.The ACL parameters of-a1kanes and -a1kanols in the transect 35 aerosols

111.4.The ACL parameters of-a1kanes and -alkanols in vegetation 36 waxes from the transect

111.5.Molecular marker concentrations in the transect aerosols 38

111.6.Concentrations of molecular markers in source vegetation wax 40 (normalized to C of n-alkanols)

IV. 1.Analytical data for the homologous compounds in the transect 57 aerosols

IV.2.Sources of the homologous compounds from the transect regions 58

IV.3.Ketone molecular marker concentrations in the transect aerosols 64

IV.4.Analytical data for wax esters in vegetation waxes from the 68 transect regions

IV.5.Sources of molecular markers in the transect aerosols 75 (cf. Table P1.3) OXYGENATED NATURAL PRODUCTS IN TROPOSPHERIC AEROSOLS

SOURCES AND TRANSPORT

CHAPTER 1: INTRODUCTION

Biogenic organic matter, in the form of lipids solvent soluble organic matter and soot (Wolff et al., 1982), is a major contributor to the tropospheric load of organic matter (Went, 1955; 1960) and thereby has an impact upon visibility, health, and even climate (Morgan and Ozolins, 1970). However, compared to the relatively extensive studies that have been carried out on the anthropogenic input to aerosols from urban areas, only limited information is available on the natural background ofatmospheric aerosols from rural areas. Thus, the study of the specific sources, compositions, and transport of organic matter in the atmosphere are essential to understand theformation and transformation of aerosols. Moreover, the study of the organic natural products in the atmosphere should be helpful in understanding the formation, transformation and depositional mechanisms of organic material in aerosols, in defining the anthropogenic organic aerosols (Went, 1960; Davies, 1974; Simoneit, 1977a; 1984; 1989; Simoneit and Mazurek, 1982a), and in providing a baseline for environmental control (air quality management). The purpose of this thesis is to further characterize the extractable organic matter in tropospheric aerosols, with an emphasis on the naturally occurring oxygenated compounds. The quantitation of the lipid classes and their molecular signatures derived from these aerosols would be useful for source correlations and for the determination of transport and fate. Utilizing latroscan thin-layer chromatographywithflame ionization detection, the total methylated extracts were separated and analyzed for the compositions of five classes (fractions) of neutral lipids, such as hydrocarbons, acid methyl esters, alcohols, ketones (aldehydes), and wax esters, and polar residual lipids. Using capillary gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS), the major naturally occurring lipid fractions were analyzed for oxygenated homologous series such as-alkanols, w-hydroxy acids, n-in-chain-ketones, saturated and unsaturated aldehydes, n-alkanol acetates, 11-in-chain alcohols, wax esters, and cyclic components such as hydroxy- andlor oxo- diterpenoids (originating from conifers and 7 their resins) and triterpenoids. Details on the total hydrocarbons and carboxylic acids in the same samples were reported by Standley (1987). Samples were collected from four rural regions along a transect across the State of Oregon that traced the predominant air mass trajectories from the central west, off the Pacific Ocean, toward the northeast of Oregon. The regions studied provide an excellent location for acquiring the major naturally occurring lipid classes of compounds. Two general types of samples were collected: (1) aerosols in an extensive coverage of four rural regions of Oregon along a transect which traced the predominant wind trajectories of the season, and (2) extracts of source waxes with duplicate samples of the major representative vegetation from the same regions. One j.j, soil sample was also included. This study resulted in the determination of reproducibility between replicate samples and between aerosols and their source vegetation. Long range transport was also evaluated by the correlation of oxygenated molecular markers of aerosols with sources. 3

CHAPTER II: AN APPLICATION OF IATROSCAN THIN-LAYER CHROMATOGRAPHY WITH FLAME IONIZATION DETECTION - LIPID CLASSES OF EPICUTICULAR WAXES OF VASCULAR PLANTS AS BIOMARKERS IN THE LOWER TROPOSPHERIC ENVIRONMENT

INTRODUCTION

The lower troposphere, composed of gases, lipids, and macromolecular organic matter originating from natural products, of anthropogenic components, and of geological components from sediments and soil erosion (Simoneit and Mazurek, 1981), is of great interest for atmospheric chemists and geochemists to study and model the global organic carbon budget. Lipids are useful tracers for source correlation, transport pathways, and transformation mechanisms of organic compounds in the troposphere (Simoneit, 1977a; Simoneit and Eglinton, 1977; Simoneit et al., 1977; Peltzer and Gagosian, 1989; Kawamura and Gagosian, 1987). Lipid studies of aerosols, that are characterized at the molecular level, have been reported largely in locations such as urban

(Ketseridis et al., 1976; Lamb etal.,1980; Matsumoto and Hanya, 1980; Ramdahl et al., 1982; 1984; Sheng et al., 1991b; Simoneit, 1984; Simoneit et al., 1991a; Broddin et al., 1980), rural (Simoneit, 1980; 1989; Simoneit et al., 1980; 1983; 1991b; Simoneit and Mazurek, 1982a, b; Standley, 1987) and remote (Gagosian et al., 1981; 1982; 1987; Kawamura and Gagosian, 1987; Peltzer and Gagosian, 1989; Shaw, 1979; Simoneit, 1977 a; Simoneit et al., 199 ic) areas. Characterization of molecular markers in rural areas includes many from biomass combustion (both natural and residential wood combustion) (Ayers and Gillett, 1988; Edgerton et al., 1984; Quraishi, 1985; Ramdahl, 1983; 1985; Ramdahl and Becher, 1982; Standley and Simoneit, 1987; 1990; Wesley et al., 1988; Simoneit et al., 1991a) and few natural background studies (Simoneit and Mazurek, 1982a, b; Simoneit et al., 1988; 1990; 1991b). Vascular plant detritus, mainly epicuticular waxes, are a quantitatively important source of carbon and a progenitor of much of the organic matter present in the troposphere (Went, 1955; 1960) through a direct or indirect emission pathway. The knowledge of the input, transport, and fate of this material is necessary to determine the sources, transport and fate of tropospheric organic matter and to model the global carbon budgets. However, studies of compounds of the lipid mixtures have been few for any particular class because of the complexity of GC and/or GC/MS methods, which make ru detailed analysis of the whole lipid fractions time consuming. latroscan with its unique character of rapidity and sensitivity has been developed and used as an alternative new approach for lipid analysis. This new approach has been used extensively in the analysis of neutral and poiar lipid classes in the marine environment including monospecific cultures of microorganisms (Ohman, 1988; Goutx et al., 1990), bacteria (Goutx et al., 1990), and seawater and sediment (Volkman et aL, 1986). In contrast to the relatively intensive studies of lipids in the marine environment, no application has been made to lipids in tropospheric aerosols and their source vegetation. In this paper we report a preliminary study of lipid classes in tropospheric aerosols and epicuticular waxes of representative vegetation along a transect across the State of Oregon by the latroscan method.

EXPERIMENTAL METHODS

Sample Locations and Descriptions

The sample locations and environmental conditions for the transect aerosols are given in Table 11.1 and Fig. 11.1, respectively. Two samples were collected (about 24 hours) simultaneously on each of five consecutive days to give aerosol data both on a day-to-day basis and between samples collected side-by-side. Aerosols (>0.3 mm) were collected on precombusted quartz fiber filters (Pallflex QAS) using high volume air samplers (Simoneit and Mazurek, 1982a; Standley, 1987) on platforms approximately 2 m in height to minimize contamination from resuspension of soil and debris. After collection, the sample filters were stored in annealed glass jars with 5-10 ml of dichioromethane at 4°C until analysis (Standley, 1987). Representative samples of source vegetation are given in Table 11.2. They were collected around the sampling sites from the transect locations to provide a composite for the in plant lipid signatures. Different parts of plants (leaves, bark and sap) from the same species in the transect regions belonging to the Filicineae, Gymnospermeae and Angiospermeae families (27 specimen) by Standley (1987), and one surface soil sample were collected by F. Prahi. Table 11.1. Sample locations and environmental data for the transect aerosols.*

Sample Ambient Designation Location TemperatureSite Description (cf. Fig. 11.1)

A-I The Oregon 10-23 Canopy of a mixed coniferous Coast Range forest, 5-10 km from the Pacific Ocean, east of a two-lane highway, 10 km northeast of a small town.

A-il The Oregon 10-23 Canopy of an homogeneous alder Coast Range grove, and in the same environment as A-I.

A-rn The Oregon 10-23 Open range, and in the same Coast Range environment as A-I.

B-I Willamette 20 Above tree line, near top of a ridge National Forest on the west of the Cascades, east of a populated region with agriculture and industries such as wood and paper, electronics and rare earth metals processing.

B-il Wifiamette 20 Canopy of a mixed coniferous National Forest forest, 10 m below B-I, east of the same populated agricultural and industrial region as B-I.

C-I Columbia Basin 25 Rowe Creek valley.

C-il Columbia Basin 6-28 Wilson Ranch, a cattle ranch and wheat farm on a high plain.

D-I Umatilla 5-13 Open range, surrounding National Forest mountains with sites logged by clear cutting and relatively clear or grown over with small trees and brush.

D-il Umatilla 13-28 Edge of a mixed coniferous forest, National Forest within a few km of a four-lane highway.

*Adapted from Standley, 1987. 0D11 Portland OCI'

Salem OBI&ll A 1,11 & HI CI 0 Corvallis

ill

Ashland

Figure 11.1. Location map of the sampling sites of the aerosol particles in the transect across the State of Oregon. 7

Table 11.2. Source vegetation for aerosols in Table 11.1.

Sample location Major regional vegetation

Coast Range 1, II and III Red Alder, Norway Spruce, Brewer Spruce, Douglas Fir, Salmonberry, Moss, Wood Fern and Sword Fern. Willamette National Forest I and II Brewer Spruce, Big-cone Douglas Fir, Mountain Hemlock, Rhododendron and Moss/Lichen. Columbia Basin I and II Juniper, Sage, Brush and Grass. Umatila National Forest I and II Douglas Fir, Elm, Alder, Laurel, Maple, Ponderosa Pine, White Fir, Pacific Silver Fir and Fern.

Lipid Isolation

Sample filters were extracted by ultrasonic agitation for three fifteen-minute periods using each of the following solvent mixtures: one aliquot of pure benzene, three aliquots of a 2:1 mixture of toluene: chloroform mixture, and one aliquot of a 1:2 mixture of toluene: chloroform. The extractions were carried out within the filter storage jars and the solvent extracts were combined and concentrated to volumes of approximately 2 ml (Mazurek, 1985; Standley, 1987). Vegetation samples were extracted by briefly dipping leaves or bark in dichioromethane to dissolve the external waxes and minimize the extraction of the internal cellular lipids. Bleed resin samples were simply dissolved in dichioromethane. All vegetation extracts were then filtered through annealed glass wool and concentrated to volumes of approximately 2 ml (Standley, 1987). Aliquots were taken for the determination of extract weights, derivatization (Standley, 1987) and latroscan analysis. The extracts were methylated by using diazomethane in benzene prepared from the precursor N-methyl-N'-nitro-N- nitrosoguanidine (Pierce Chemical Co.; Standley, 1987). Lipid Analysis

The total methylated extracts were separated into peaks (bands) of varying polarity and analyzed by using an latroscan TH-1O TLC/FID chromatographic analyzer (Newman-Howells Associates Limited, UK). The operating conditions of the flame ionization detector utilized a hydrogen flow rate of 160 mI/mm and an air flow rate of 2000 mi/mm. The scan speed of the chromarod was 0.6 cm/mm. Chromarods coated with silica gel Sil or its improved product Sffi (5mm particle size) were stored in a humidity tank. Before use, they were activated by passing through the flame twice. Samples were applied using a 1-mi syringe (Hamilton, Reno, NV) with single or multistep spotting. The chromarods were then developed by solvent elution in glass tanks lined with pre-extracted filter paper for 30 minutes. A number of solvent systems were investigated and the most useful for the analysis of neutral lipids was hexane-diethyl ether (96:4). For polar lipids, hexane-diethyl ether-acetic acid (60: 17:0.15) was used. After the chromarods were developed they were dried in an oven for 5 minutes at 100°C and analyzed immediately to minimize adsorption of atmospheric contaminants. After use, the chromarods were cleaned regularly by immersion overnight in chromic acid solution (typically after 4 analyses) followed by a 10-minute wash in running tap water and then in distilled water. Cleaned chromarods were stored in a dessicator when they were not in use. The above procedure ensured adequate humidity of the rods and reliable analytical conditioning. Lipids are determined by running a standard mixture (including 1: octadecane; 2: stearyl stearate; 3: methyl stearate; 2-nonadecanone; 1 -nonadecanol) with aerosol and/or vegetation samples during each time of analysis (ten chromarods per set). Lipids of aerosols were quantified with reference to calibration curves determined for each class of compounds in the range of 0.5 to 2.5 mg. For the vegetation wax and soil samples, lipids were estimated by adding up the scan areas of individual classes (peaks).

RESULTS AND DISCUSSION

The location map and sampling conditions of the aerosol particles and their representative source vegetation in the transect across the State of Oregon is given in Figure 11.1, Tables 11.1 and 11.2, respectively. The ambient temperatures at the sampling sites were 10 to 28°C, typical summer temperature, and the wind directions during sample acquisitions were from southwest to northeast except for site Willamette 11 which was from west to northeast with wind speeds ranging from 10 to 20 km/h (cf. Fig. 11.1; Standley, 1987). Analyses of the compound class distributions of lipids in aerosol particles and plant waxes yield information on the variability of their distribution patterns and how closely the compositions of aerosols from a region reflect those of the predominant vegetation. The amounts and compositions of epicuticular wax lipids vary a great deal from species to species (Kolattukudy, 1976). Therefore, the lipid classes can be used as tracers for the study of the input, transport, and fate of lipids in the tropospheric aerosols. Lipid classes in plant waxes have chemotaxonomic significance, which can be used in the documentation of environmental variability and trends, and for preliminary source correlations of some compounds.

Lipid Concentrations and DistributionsofTransect Aerosols

The analytical data for the lipid classes of the transect aerosols are presented in Table 11.3. Examples of latroscan, and concentration distribution diagrams of lipid classes for aerosols from the transect regions are given in Figs. 11.2 and 11.3, respectively. The total extract weights range from 2.0 to 4.6 ig/m3 and the highest loading is in the Wilamette Valley, which could be due to the regional natural input and anthropogenic impact (Table 11.1). It can be seen that an increasing trend of loading occurs as the air parcels move east from the Pacific Ocean toward the northeast of Oregon. The aerosols have relatively equal amounts of each class of neutral lipids, such as hydrocarbons, carboxylic acids, aldehydes and ketones, and alcohols. All aerosol particles from the four regions have a high percentage of polar fractions ranging from 34.2 to 64.9% and containing unknown compounds.

Lipid Distributions of Epicuticular Waxes of Source Vegetation

A summary of the analytical data for the lipid classes in the epicuticular waxes of vegetation sampled along the transect is presented in Table 11.4. Examples of latroscan and concentration distribution diagrams of lipid classes for the source vegetation are given in Figs. 11.4 and 11.5, respectively. Comparing the source vegetation wax with the transect aerosols and surface soil, the distribution patterns of neutral lipids in the TableSample 11.3. Analytical data for lipids in the transect aerosol particles. Total extract weight (jig/rn3) Hydrocarbons Carboxylic1 acids Lipid concentrations [%(j.tg/m3)] and ketonesAldehydes Alcohols lipidsPolar II.I.Coast Range Mixed coniferous forest 3.22.4 12.3(0.3) 18.2(0.4) - 11.4(0.3) - 15.0(0.4) - 43.1(1.0) - I.Willametteifi. Open range AbovetreelineAlder grove National Forest 4.62.0 12.4(0.3)7.9(0.4) 14.0(0.3)7.4(0.3) 11.9(0.2)5.9(0.3) 27.4(0.6)13.8(0.6) 64.9(3.0)34.2(0.7) II.I.Columbia WilsonMixedconiferousforestRowe Ranch Creek Basin 3.62.14.3 10.4(0.2)13.0(0.6) 22.8(1.0)7.0(0.1) 7.5(0.2)9.7(0.4) 17.7(0.4)17.1(0.7) 57.4(1.2)37.4(1.6) II.I.Umatilla National Forest OpenEdgeconiferous range of mixed forest 4.23.6 41.4(1.5)12.5(0.5)16.5(0.6) 15.7(0.6)10.2(0.4)9.5(0.4) 6.3(0.3)7.5(0.3)5.1(0.2) 20.8(0.7)15.1(0.6)9.4(0.3) 56.5(2.4)39.5(1.4)33.9(1.2) 2: 1:Not detected. As methyl esters. C 11

F F F

C

F

Elution

Figure 11.2. Examples of Jatroscan analyses for aerosols from thetransect regions (A: hydrocarbons; B: wax esters; C: carboxylic acid methyl esters; D: ketones; E: alcohols; F: polar unknown lipids): (a) standard lipid mixture (A: octadecane; B: stearylstearate; C: methyl stearate; D: 2-nonadecanone; E: 1-nonadecanol); (b) aerosol from theCoast Range; (c) aerosol from the Willamette National Forest; (d) aerosol from the Columbia Basin; (e) aerosol from the Umatilla National Forest. The chromarodwas developed, from right to left in the figure, for 30 mm in hexane-diethyl ether (96:4). 12

100 100

p C'nnii a Wjlhqmctie I b 71 CntI III 75 W,IImcite II

o ¶0 50 g U U LI 25 0 a U U

A Ii C 1) E P A B C 1) E P Lipid Class Lipid Class

I 00 100

Cnlnmhiiu I p Umiil1I d

75 CnItumI,iII 75 UmtjIla II

.g so 50 g U U g LI U 25

0

E P A B C D A B C I) E P Lipid Class Lipid Class

Figure H.3. Concentration distribution diagrams of lipid classes (A: hydrocarbons; B: wax esters; C: carboxylic acid methyl esters; D: ketones; E: alcohols; F: polar unknown lipids) in aerosols from the transect regions: (a) Coast Range; (b) Willamette National Forest; (c) Columbia Basin; (d) Umatilla National Forest. SampleTable 11.4. (Region) Analytical data of wax lipids in vegetation from the transect regions. Lipid concentrations (%) Coast Range Hydrocarbons Wax esters Carboxylic1 acids and ketonesAldehydes Alcohols lipidsPolar WoodAlderLeavesAlderBarkSalmonberryMoss Fern 0.46.40.51.0 79.338.8 2.40.60.5 0.80.61.71.8 7.35.70.44.5 38.510.2 6.15.51.7 83.082.591.014.2 DouglasBrewerNorwaySword Spruce Spruce FirFern 0.10.97.23.3 30.6 0.91.7- 0.98.40.81.1- 8.34.32.32.5 11.2 4.42.11.4 88.288.694.740.110.5 Moss/LichenWillamette National Forest - - - - 25.6 74.4 PlowedBrewerSpruceBig-coneDouglasFirMountainRhododendron Soil Hemlock 21.224.5 0.13.51.1 9.00.83.35.01.4 5.20.70.36.41.1 23.7 6.32.82.6 25.5 5.84.42.21.5 93.052.589.867.738.6 Table 11.4. continued Sample (Region) Hydrocarbons Wax esters Carboxylic1Lipid concentrations (%)acids and ketonesAldehydes Alcohols lipidsPolar SageColumbia Basin 0.15.7 0.10.4 0.10.2 0.50.2 1.1 92.4 UmatillaGrassJuniper/SageJuniper National Litter Forest 18.0 0.8 6.80.3 10.2 0.4 5.21.0 20.7 2.05.6 39.195.593.6 Douglas Fir 0.2 2.5 0.8- 0.7 2.6 93.2 AlderElm"Green WaxyBush" 2.95.40.6 18.0 0.51.4 0.1- 0.20.8 2.89.65.6 92.766.293.2 MapleLaurelFern 38.8 2.1 - 11.2 1.7- - 11.3 0.3- 22.3 3.6- 92.316.4 - PacificWhiteDouglasPonderosaPine Fir SilverFir Fir 0.11.5- 0.30.43.3- 0.80.42.91.2 0.60.14.21.5 5.85.47.24.7 92.491.492.383.4 2: : As methylNot esters. detected. - 15

a b F

EF D J\)\JL(JJJL

D EF

Elution Figure 11.4. Examples of latroscan analyses for the source vegetation (A: hydrocarbons; B: wax esters; C: carboxylic acid methyl esters; D: ketones; E: alcohols; F: polar unknown lipids): (a) standard lipid mixture (A: octadecane; B: stearyl stearate; C: methyl stearate; D: 2-nonadecanone; E: 1-nonadecanol); (b) Grass from the Columbia Basin; (c) "Green Waxy Bush" from the Umatilla National Forest; (d) Douglas Fir from the Coast Range; (e) Douglas Fir from the Umatilla National Forest; (f) Brewer Spruce from the Coast Range; (g) Red Alder Bark from the Coast Range; (h) Alder from the Umatilla National Forest; (i) Mountain Hemlock from the Willamette National Forest. The chromarod was developed, from right to left in the figure, for 30 mmin hexane-diethyl ether (96:4). 16

100 -....-...--- Moss * Salznorsbeny 75 Alder Bark a Alder Leaves Wood Fern 50 a--- Swoni Fan i. Norway Spruce i. Brewer Spruce Douglas Fir

0 100

- 75 c--- Moss/Lichen Rhododersfron a--- Mountain Hemlock so Big-enne Douglas Fir

I BrewerSpnsce Plowed Sod 25 a---

0

100

Columbia Basin -' 75 a---- Sage 0 p Juniper 5° a- Juniper/S age Litter 1) # Grass 0 25

0

100 --a- Douglas Fir Green Waxy Bush -' 75 -+-- Elm 0 Fan 50 a--- Maple U U j. Ponderosa Pine 0 J. 25 \VhiieFir Douglas Fir

I Pciuic Silver Fir 0 A B C D E F

Lipid Class

Figure 11.5. Concentration distribution diagrams of lipid classes (A: hydrocarbons; B: wax esters; C: carboxylic acid methyl esters; D: ketones; E: alcohols; F: polar unknown lipids) in the source vegetation wax and soil of the transect regions. 17 source vegetation are much more complicated (Table 11.4; Figs. 11.4 and 11.5). The distribution pattern of classes of lipids in the epicuticular wax of vegetation differs between and within species. All species have relatively higher amounts of alcohols than other neutral lipid classes. Salmonberry, wood fern, and sword fern have very high amounts of wax esters, which range from 31% to 80% of the total lipids of the species. Variations among the species of vegetation are much larger than in the aerosols and soil (Figs. 11.3 and 11.5). Of all species, rhododendron and maple have the highest amounts of hydrocarbons, which comprise 25% and 39% of the total lipids, respectively. Red alder leaves from both the Coast Range and Umatilla areas have a higher amount of wax esters and hydrocarbons, and a lesser amount of alcohols than the red alder bark. Grass is the only species which has a relatively uniform distribution of neutral lipids and a lower percentage of polar lipids. The conifers have a relatively higher alkanoic acid lipid concentration, especially Brewer spruce in the Coast Range area. Alder has a low alkanoic acid concentration. This is consistent with the data observed in the transect aerosols. Variations are also observed within the same species, such as Brewer spruce, Douglas fir, and alder. This may be due to the influence of geographic and environmental factors.

Lipid Distribution of Surface Soil

For comparison, one plowed soil sample from the Willamette National Forest area was analyzed (sample from F. Prahl). The neutral lipid distribution was 2 1.2% hydrocarbons, 9.0% wax esters, 5.2% fatty acids, 6.3% aldehydes and ketones, and 5.8% alcohols, and 52.5% of polar unknown material (Table 11.4; Figs. 11.4 and 11.5). The soil sample contains a relatively higher hydrocarbon concentration than most aerosols and source vegetation, and a smaller amount of polar material than source vegetation. This may be due to the humification (Nicolaus, 1968) of polar organic materials and the "Maillard" (browning) Reaction, which is a reaction of the amino groups of amino acids, peptides or proteins with the "glycosidic" hydroxyl group of sugars ultimately resulting in the formation of brown products (Ellis, 1959; Neumann and Henseke, 1974). Source Correlations of Transect Aerosols

The aerosols above the coniferous forests in the regions of the Coast Range and the Wilamette National Forest have higher proportions of carboxylic acid fractions than in other areas (Table 11.3; Figs. II.3a, b, d). This may be due to the contribution of diterpenoid acids from conifers, and to photooxidative degradation of wax esters and other poiar unknown lipid material. However, an unexpected high value is observed in an open area of the Umatila National Forest (Fig. II.3d), which may indicate transport of aerosol particles by the updraft and/or predominant trade wind from the Pacific Ocean. The aerosols from all regions contain a much higher proportion of hydrocarbons than the source vegetation, which may reflect a contribution from fossil fuel combustion. The high proportion of hydrocarbons in the aerosols of Wilson Ranch in the Columbia Basin may be due to the additional regional contribution of surface soil particles. The wax esters, which are widely present in the source vegetation, are not detected in the aerosols. This is discussed in more detail in chapter IV and may be due partly to the photooxidative reaction of wax esters with ozone which decomposes them into their constituent fatty acids and alcohols, and partly to their low volatility. The aerosols also have smaller proportions of polar materials than the source vegetation, which may also be due to photooxidation and transformation of the polar materials.

CONCLUSIONS

The transect aerosols have a relatively uniform distribution of the four classes of neutral lipids, namely hydrocarbons, carboxylic acids, aldehydes and ketones, and alcohols. All aerosol particles from the four regions have a high percentage, ranging from 34 to 65%, of polar fractions containing unknown compounds. Wax esters, which are one of the major classes of neutral lipids in the source vegetation, are not detectable in the aerosols. This may partly be due to their photooxidative degradation and to their low volatility. Also, the transect aerosols have lower proportions of polar unknown material than their source vegetation, which may also be due to photo-oxidative degradation and transformation of the polar material. 19

CHAPTER III: CHARACTERIZATION AND CORRELATION OF OXYGENATED COMPOUNDS IN AEROSOL PARTICLES AND SOURCE VEGETATION: I - ALCOHOL FRACTION

INTRODUCTION

The previous work has concentrated on the hydrocarbon and carboxylic acid fractions of the lipids in a set of the transect aerosols and waxes from representative vegetation across Oregon (Standley, 1987). The biomarkers, such as diterpenoid and triterpenoid hydrocarbons and acids, have been widely used by organic geochemists as definitive tracers to correlate sources of organic matter in sediments (Simoneit, 1977b; 1978a, b), coals (Sheng et al., 1991a, c), and aerosol particles (Simoneit et al., 1988; 1991a, b, c). They are the final products of the diagenesis and/or catagenesis of natural products in the environment. For example, retene is an alteration or incomplete combustion product derived from compounds with the abietane skeleton found in conifer resins (Ramdahl, 1983). This section deals with the alcohol fraction of the lipids from the transect aersols and representative vegetation waxes across Oregon. The -a1kanols, w-hydroxy alkanoic acids, and oxygenated terpenoids, especially di- and triterpenoid alcohols, comprise the largest fraction of neutral lipids (Table 11.3; Figs. 11.2 and 11.3). Therefore, the study of the oxygenated biomarkers could provide an alternative method for aerosol source correlations.

EXPERIMENTAL METHODS

Sample Locations and Descriptions

The sample locations and environmental conditions for the transect aerosols are described in Chapter II. Aerosols (>0.3 J.Lm) were collected on precombusted quartz fiber filters (Pailfiex QAS) using high volume air samplers (Simoneit and Mazurek, 1982a; Standley, 1987). Representative samples of source vegetation were also collected around the sampling sites from the transect locations to providea composite for the j plant lipid signatures (Table 11.2). Different parts of plants (leaves, bark and sap) from the same species in the transect regions belonging to the Filicineae, Gymnospermeae and Angiospermeae families (27 specimen), andone in surface soil sample were collected by Standley (1987). 20

Lipid Isolation and Separation

Sample filters were extracted by ultrasonic agitation for three fifteen-minute periods using each of the following solvent mixtures: one aliquot of pure benzene, three aliquots of a 2:1 mixture of toluene : chloroform mixture, and one aliquot of a 1:2 mixture of toluene : chloroform. The extractions were carried out within the filter storage jars and the solvent extracts were combined and concentrated to volumes of approximately 2 ml (Mazurek, 1985; Standley, 1987). Vegetation samples were extracted by briefly dipping leaves or bark in dichioromethane to dissolve the external waxes and minimize the extraction of the internal cellular lipids. Bleed resin samples were simply dissolved in dichloromethane. All vegetation extracts were then filtered through annealed glass wool and concentrated to volumes of approximately 2 ml (Standley, 1987). This procedure of lipid isolation and separation facilitated the study of free fatty alcohols and carbonyl compounds as well as wax esters, thus providing more accurate source information. Aliquots were taken for the determination of extract weights and derivatization (Standley, 1987). The extracts were methylated by using diazomethane in benzene prepared from the precursor N-methyl-N'- nitro-N-nitrosoguanidine (Pierce Chemical Co.; Standley, 1987). Aliquots of the methylated extracts were separated into four fractions on silica gel by thin layer chromatography using a mixture of 19:1 hexane:chloroform as the mobile phase (Standley, 1987). The four fractions collected were: (1) alkanes with saturated and unsaturated terpenoid hydrocarbons, (2) alkanones, saturated and unsaturated aldehydes, alkanyl acetates, terpenoid ketones and wax esters, (3) alkanoic acid methyl esters and terpenoid ketone methyl esters, and (4) alkanols, terpenoid alcohols, lignans and other polar compounds. A more detailed description of the sample locations and lipid isolation procedures is given in Standley (1987). The first and third of the four fractions collected were discussed by Standley (1987). The fourth fraction (alcohols) collected is discussed in this chapter. The alcohols were converted to trimethylsilyl ethers by reaction with N, 0 bis (trimethylsilyl)trifluoroacetamide (BSTFA) plus 1% trimethylchlorosilane: anhydrous pyridine (1: 1) for approximately 30 minutes at 70°C under a nitrogen atmosphere. 21

Lipid Analysis

The trimethylsilyl ethers of the alcohol fraction were analyzed by capillary gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The GC analyses were carried out on a Hewlett-Packard Model 5840A gas chromatograph using a 25 m x 0.20 mm i.d. flexible fused silica capillary column coated with DB-5 (J & W, Inc.). The GC-MS analyses were performed on a Finnigan Model 4021 quadrupole mass spectrometer interfaced directly with a Finnigan Model 9610 gas chromatograph and equipped with a flexible fused silica capillary column coated with DB-5 (30m x 0.25 mm i.d.). The GC temperature program was 65°C for 1 minute, 65 to 130°C at a rate of 15°C/mm, 130 to 310°C at a rate of 4°C/mm, then held isothermal at 310°C for 60-120 minutes. The GC-MS temperature program was 65°C for 2 minutes, 65 to 310°C at a rate of 4°C/mm, and then held isothermal at 3 10°C for 60-120 minutes. Mass spectrometric data were acquired and processed with a Finnigan-Incos Model 2300 data system.-Alkano1s were identified by a stardard mixture (including C10 to C30) on GC and GC-MS. Molecular markers were identified by GC and GC-MS comparison with authentic standards, reference literature, or by interpretation of mass spectra. Quantitation of the homologous series was carried out by comparison of the GC peak area with a co-injected known standard, hexamethylbenzene. Molecular markers were quantitated on GC-MS by comparison with the peak area of the same standard.

RESULTS AND DISCUSSION

The sampling locations and environmental data for the transect aerosols and their representative source vegetation are given in Fig. 11.1, Tables 11.1 and 11.2, respectively, and additional details are described by Standley (1987). The ambient temperatures at the sampling sites were 10 to 28°C, typical summer temperatures, and the wind directions during sample acquisitions were from southwest to northeast except for site Willamette II which was from west to northeast with wind speeds ranging from 10 to 20 km/h (cf. Fig. 11.1; Standley, 1987). Analyses of the distribution patterns of the homologous series of -alkanols in aerosols and plant waxes provided information on fmgerprinting their signatures in aerosols from the predominant vegetation in that area (e.g. Simoneit and Mazurek, 1982a; Simoneit 1989). Homologous series of-alkanoIs in plantwaxes and in aerosol particles exhibit pronounced even carbon number preferences (generally expressedas 22

CPI, the measure of the even-to-odd chain length predominance in-a1kanols; Appendix I) and specific carbon number maxima (Cm; Mazurek and Simoneit, 1984). This can be used in the evaluation of variability and trends within and among vegetation species, and in preliminary correlations of aerosols with sources. The phytosterols and terpenoids present in the aerosols and vegetation have structures with a higher degree of complexity than-a1kano1s, and are thus specific and representative for species of plants. They are, consequently, more useful in chemotaxonomic correlations. These components are known as molecular markers (Simoneit, 1978a, b; 1982; 1986a) and are used as supportive indicators.

Homolog Distributions: Concentrations and Reproducibility

The summaries of the analytical data of the-a1kanol homologs present in aerosol particles and in vegetation wax extracts are presented in Tables 111.1 (a, b and c, d or e, f, samples collected side-by-side; a, b to c, d or to e, f, samples collected day-to- day; Standley, 1987) and 111.2, respectively. For comparison, regional averages are presented for all parameters of aerosols and vegetation waxes. Histogram distributions of -a1kanols and w-hydroxy alkanoic acids in the aerosols and source vegetation collected from each sampling region are given in Figs. 111.1 to 111.4. Complete files of the histogram distributions of -a1kanols and phytosterols of the aerosol and vegetation waxes are presented in Appendices II and III, respectively. Total -alkanol concentrations in the transect aerosols range from 0.38 to 3.03 ng/m3, which is lower than most aerosols from urban and rural areas (Simoneit, 1989; Simoneit et al., 1988; 1991a) but one order of magnitude higher than in aerosols from remote areas (Simoneit et al., 1991c; Gagosian et al., 1981; 1982). These concentrations are also at the low end of the range observed in other rural aerosols which range from 10.6 to 2200 ng/m3 (Simoneit, 1989; Simoneit et al., 1991b). The aerosols collected over the alder grove in the Coast Range have the highest reproducibilities of the concentrations (Table 111.1 and Fig. 111.1). This is consistent with the -a1kane and -a1kanoic acid concentrations data of the same samples discussed before by Standley (1987). These data give a good evaluation of the reproducibility of the high-volume air filtration method used here. The high concentration reproducibilities of the aerosols collected side-by-side (a, b and c, d or e, fin Table 111.1) but day-to-day (a, b to c, d or to e, fin Table 111.1) over the mixed coniferous forest in the Coast Range reflect a large influence from the air mass transported versus a small influence from the Table 111.1. Analytical data for transect aerosols. Sample Total yield (ng/m3) (ng/m3) -AlkanoIs1 Cge2 C1 (C1632) CPI co-Hydroxy Alkanoic (pg/rn3) C14 (pg/rn3) C16 Acids1 I.Coast Range Mixed coniferous forest a. 0.66 0.14 14-32 22 11.2 - 3 - d.c.b. 0.691.301.27 0.200.210.16 14-3214-30 2620 11.8 7.94.7 - - HI.II. Open range Alder grove b.a.C. 0.740.450.811.161.05 0.310.180.210.20 12-34 24202632 10.211.7 5.24.46.2 139.46 50.25 7.229.142.81 123.89 44.6121.0416.62 6.47 I.Wiflgmette Above tree National line Forest Regional average b.a.c. 2.290.890.722.20 0.520.200.170.46 14-3612-34 2625.224 5.54.68.1 115.67 21.1654.0918.72 102.73 42.9552.5648.53 e.d.c.a.f. 0.530.520.730.56 Q.400.370.450.44 14-36 26 16.714.119.2 7.3 0.960.131.761.98 4.082.184.590.26 II. Mixed coniferous forest Regional average d.C.b. 3.032.242.201.611.81 0.450.470.330.49i.52 14-3414-3614-34 2225.626 4.59.14.87.56.5 147.53130.0540.5664.0919.24 404.11175.49356.13 52.6810.91 SampleTable 111.1. continued -A1kanols1 o-Flydroxy Atkanoic Acids' Columbia Basin Total yield (ng/m3) (ng/m3) Cmax cange2 Cmax (C1&32) CPI (pg/rn3) C14 (pg/rn3) C16 II.I. Wilson Ranch Rowe Creek d.a.b.C. 0.600.760.750.730.49 0.200.130.160.230.12 14-3414-32 282830 13.3 9.66.07.48.5 2.388.845.578.746.26 12.8412.70 5.028.109.11 f.e.d.C.b. 0.630.470.700.570.38 0.230.190.14 14-34 28 15.216.613.712.2 2.784.373.040.841.65 5.919.273.506.461.79 I. OpenUmatilla range National Forest Regional average c.b.a. 2.20.611.321.62 0.640.330.430.18 12-3412-3414-34 2628.4 14.012.812.511.5 17.98 7.567.784.45 33.1513.9614.41 7.47 II. Edge of mixed coniferous forest b.C.a.d. 0.930.91.9 0.170.430.21 12-34 26 10.212.615.3 20.2313.38 8.77 38.3216.6424.74 Regional average f.e.d. 0.801.411.571.471.17 0.370.420.400.380.27 12-34 26.42628 20.313.210.414.7 8.9 20.2412.8519.28 9.503.73 24.1138.3036.5218.01 7.05 2:1: : Not detected.DeterminedAs trimethylsilyl by GC/MS. ethers. 25

Table 111.2. Analytical data for -aIkanols in vegetation waxes from the transect regions.

Sample (Region) n-Alkanols1

Cge2 Cm CPI (Ci3

Coast Range Moss 16-32 28 7.0 Salmonberry 12-36 26 29.6 Alder Bark 15-28 22 8.3 Alder Leaves 14-32 24 9.7 Wood Fern 14-32 24 14.2 Sword Fern 16-32 24 6.2 Norway Spruce 18-35 26 4.0 Norway Spruce Sap ..3 - - Brewer Spruce 14-32 24 3.0 Brewer Spruce Sap DouglasFir 12-32 26 11.0 Regional Average 24.9 10.3 Willamette National For MosfLichen 16-30 26 32.5 Rhododendron 16-30 22 4.5 Mountain Hemlock 15-34 26 6.5 Big-cone Douglas Fir 16-30 26 4.0 Brewer Spruce 16-30 24 4.0 Regional Average 24.8 10.3 Columbia Basin Sage 16-30 22 9.4 Juniper 12-32 26 4.4 Juniper/Sage Litter 14-30 22 4.3 Grass 16-34 26 24.3 Wilson Ranch Soil 12-32 28 19.2 Regional Average 24.8 12.3 Umatilla National Forest Douglas Fir 16-30 28 5.6 Elm 14-30 24 21.0 Alder 16-34 24 9.5 Fern 16-30 26 13.3 Laurel 14-30 26 7.1 Maple 14-30 26 8.7 Ponderosa Pine 12-34 24 10.6 White Fir 16-30 22 8.2 Douglas Fir 14-32 26 8.2 Pacific Silver Fir 12-30 24 3.2 Regional Average 25.0 9.5

1: As trimethylsilyl ethers. 2: Determined by GC/MS. : Not detected. cq. °' 04 02? Ic 020 Id 02? i 2t C.I l dccc 24 lb dccc 22 020 q. 00 I. lb 1. lb 4414

00? 0:

0 __:1 02 21 Co4I4.nq.0 20 24 O? Ccc Cc..? 24 d.c..? c. 00Cc.. 4.cc 00 24 dcc Ic I. II Ic

.4 .4

30

°:L11L.°:t. L

00 C.cmc.c. 24 COOc, ccc. I 'rL

30 30

0 _____ 0 4 0 20 30 '0

Cc,ce 2ccc 24 00.1 20 Ccc 4..,. 00 24 Cc... 4.cc Occc b I?3' I .4

30

1J1 L IOT.O

Figure 111.1. Histogram (carbon number versus concentration) distributions of alkanols and co-hydroxy alkanoic acids () in the aerosols andsource vegetation waxes collected from the Coast Range. 27

044 00* 044 040 037 040 W4O4I.is H 2 2 2

023- 024 023 023 Or, 020

O .i OJIihII. 0 o.J 0

O0i °' wui....., is ii su..,,s ... zs ' ii '-4...--, I. I Ii 24 I

:. I

O____ 0

s.o. is is

I 2. O..r.. ' I TL

Figure 1112. Histogram (carbon number versus concentration) distributions of alkanols and o-hydroxy alkanoic acids () in the aerosols and source vegetation waxes collected from the Willamette National Forest. ° 0 Z3 OI 020 C4401 24 C 21 C104 21 co1., 2. I0.* I 9..., I. 3 14 to ,_' Id I . I 4

0041 0001 004 00 007

0 0 ___ 0 01 0 0 I o 20 20 30 40 IIII C 0 30C30 0 II'[I CI.'I. 2! 0031 C 0201 023 Co4 2! 01 01 I 22 24 0.001 0.... 0100 !434 110. .qiJ 111

I

0,2_I 0

0Lr.ijid.jii 0 I 01 0 20C10 40 0 30C30 40 0 101 011 2? C11. C..9. 20 00__ 0.. 20 Oo. 0.3.. 00._I 0.n. 6 S

110 110 110

0 Jh111.. 0. 0 20 30 40

Figure 1111.3. Histogram (carbon number versus concentration) disthbutions of- alkanols and ci-hydroxy alkanoic acids (") in the aerosols, source vegetationwaxes and soil collected from the Columbia Basin. 29

OS 027 21 022 01 03 lb 033 z 21 l4l42 t-.,42. 1 lb 1 'a I. lb I II 'I,-, 'I,-, 2* 'III

02l 0 o zz 04 032

0 .l.ItI.,o 0I 0 20 30 110 10 20 30 40 IiI C C- 200 200 027 21 031 0110 21 24.10W 25 Ik,141111 24 * 711 (11. Id

0.

0,, 020 022 501 U UJL :' I(24 i..n. 21

:.. 3 10

00 30l4l. 00 47 22 1242. 230 lk1Wl. 24 7-- a..111 - 7-. 711 I

50 50 50 2

it;i. ; .,tII 00J. 0 20 30 42

Figure 111.4. Histogram (carbon number versus concentration) distributions of alkanols and co-hydroxy alkanoic acids () in the aerosols and source vegetation waxes collected from the Umatilla National Forest. local vegetation. High reproducibilities of -a1kane ACL and -alkano1 ACL (described below) of the transect aerosols have also been observed (Table 111.3).

Homolog Distributions: Correlations with Source Signatures

Recent work by Gagosian et al. (1987) discussed the tracing of the regional source of aerosols collected at a remote oceanic site by correlating the homologous terrestrial compounds (aliphatic hydrocarbons, fatty alcohols and fatty acids) and air parcel trajectory analysis. The present work correlates aerosol composition with a chemotaxonomic analysis of the alcohol fraction of waxes in source vegetation. Both studies result in similar conclusions. A progressive increase in the averageCm(25.2 to 28.4) for n-alkanols is observed in aerosols derived from the cooler climate of the Oregon coast to those from the desert climate of eastern Oregon (Table ifi. 1; Figs. ifi. 1 to 111.4). This is consistent with the data for n-alkanes and n-alkanoic acids in the samples of the same transect (Standley, 1987), and may be the result of cimatological adaptations by specific plant communities, whereby the higher molecular weight epicuticular wax components are preferentially synthesized in response to higher ambient temperatures. The carbon number range of -a1kanols in waxes from representative source vegetation covers fromC12toC36with homologs >C20predominant (Table 111.2, Figs. ifi. 1 to 111.4). TheCmof ji-alkanols in representative vegetation varies from species to species withC26andC28predominating. The averageCmof the transect vegetation vary from 24.9 to 25.0. There is no significant increase inCmfrom the cooler coast to the warmer desert areas. This could also be due to fact that the indicative desert vegetation was not collected for study.Inorder to examine the climatic adaptation of plants, three species of source vegetation were collected in duplicate from different climatic areas (Standley, 1987). The geographical and environmental variations of terpenes in plants have been reported before (Hanover, 1966; Zavarin et al., 1970; Wilkinson and Hanover, 1972). However, the results for these examplesare obscured by geographical and environmental factors. For example, Douglas fir from the Coast Range(C26)and from Umatilla National Forest (area I) (C) does showan increase in from the cooler coast to warmer desert climate, but Douglas fir from Umatilla National Forest (area II)(C26)does not show a similar increase in Cm. Brewerspruce from the Coast Range and Willamette National Forest exhibits thesameCm (C24), 31

which is probably due to the minor climatic variation of the areas. Thus these species exhibit variable geographical and environmental effects in their plant wax compositions.

In the corresponding transect aerosols, the carbon number range for then- alkanols is from C12 toC36with the regionalCmaverages ranging from 25.2 to 28.4 (Table 111.1, Figs. 111.1 to 111.4), which directly reflects the source vegetation. The homologsmolecules of 0-hydroxy C12, C14,C16,andC18alkanoic acids, have been described only for Gymnosperms, which contain co-hydroxy alkanoic acids in the cutin (Caldicott and Eglinton, 1973; Tulloch, 1976). 3-Oxo-alkanoic acids are major components of wax from mountain hemlock, and are not found in any other vegetation waxes. They range fromC25toC29with aCm of C27 (Fig. 111.6). They are not present in the regional aerosols which may be due to their unstabiity in the atmospheric environment and lack of source input. 32

283 130.3 a

50.3- 75 103 -L5 89 II 315 99 131 185 257 299 lF'IFr'1r1FIl 58 188 158 280 250 388 358

311 tee. a b

58.3 73 55 103 343 122 175 192 289 231 25: 327k IL ) i P11r 1F F 50 180 158 280 250 388 350

UI! z-- C

UI! Z 283

UI! z 311

7 758 883 850 S0i0 558 1888 SCAN±

Figure 111.5. Examples of: (a)mass spectrum of methyl 14-hydroxytetradecanoate trimethyl silyl ether, (b) mass spectrum of methyl 16-hydroxyhexadecanoate trimethyl silyl ether; (c) mass fragmentograms of methyl 14-hydroxytetradecanoate and methyl 16-hydroxyhexadecanoate thmethyl silyl ethers (1 and 2, respectively) from the transect aerosol (Coast Range II). 33

116 188.3

57 73 131 129

I 143 1St ies 227 243 ., 35 58 [00 150 200 258 28.1

10.8 489424

4O 8 nil z+ C7 1 Jc3I C29

tii/ Z

LJ (i 25 C28 A C 1933 I 9:32 ' 1.33! 2878

2047

Ri

1933 1831 2812;Li 1260 1891 1 1361 1 rtA_ I-r 2038 2)58 210 18')8 '50 1OO 1950

SCAN-+

Figure 1116. Example of: (a) mass specnumof methyl 3-oxohexacosanoate; (b) fragmentogram of-Cto C29 3-oxo-alkanoicacid methyl esters. 34

Parameter Analysis: Source and Transport

Recently, Poynter and Eglinton (1990) defined a parameter, they called -alkane ACL (average chain length), which describes the average number of carbon atoms per molecule based on the abundance of the C27, C29, and C31 "higher plant"-a1kanes (see formula in Appendix I), to assess the paleoenvironmental and diagenetic influence on lipid distributions in three sediments from the Ocean Drilling Program Hole 717C in the

Bengal Fan. It has been found that the carbon number maximum of a higher plantn- alkane distribution is broadly related to latitude (Simoneit, 1977a; Poynter et al., 1989), with higher carbon numbers occurring at lower latitudes and warmer climates. A further analysis of the distribution of the-allcane ACL parameter has linked this relationship to the geographical distribution of fluvial and eolian inputs (Poynter, 1989). By analyzing the distribution of the-alkane ACL parameters of sediments (ranging from 29.8 to 30.0) and comparing them to the Saharan air layer dust from the Saharan/Sahel boundary (29.9 to 30.1) and material transported south by the northeasterly trade winds (29.3 to 29.5), Poynter and Eglinton (1990) concluded that the -alkane ACLs of the sediments are indicative of a warmer (tropical) source region, which is consistent with the likely source, i.e., the Ganges Brahmaputra river system. In the present study, the ACL parameter is used to compare the transect aerosols with their representative source vegetation. Tables ffl.3 and 111.4 give the ACL parameters (defined by the formulas in Appendix I) of -alkanes (data from Standley, 1987) and -a1kanols in the transect aerosols and representative source vegetation and soil of the region, respectively. The -a1kane ACLs of each region of the transect aerosols match well with the predominant source vegetation. The -a1kane ACLs of the aerosols collected in an alder grove in the Oregon Coast Range are highly reproducible in signature but do not quite match the source vegetation sample of alder wax. However, it is likely that the aerosols contain contributions from the conifers to the west of thearea carried in by the dominant westerly wind during the sampling period, and possibly from ground vegetation, especially moss. The analysis of the -alkano1 ACL data confirms this conclusion. The n-alkanols in aerosols from the Willamette National Forestare consistent with an origin from mainly conifer trees and dilution by material from brush with moss and lichen. The n-alkane and n-alkanol ACLs of the aerosols in the Columbia Basin match more closely with the signature of juniper,sage and grass, with sage dominant in the Rowe Creek area. For comparison, aerosols from the Umatilla National Forest have an average n-alkane ACL of 29.1 and n-alkanol ACL of 27.5, whichare 35 Table 111.3. The ACL parameters of-alkanes and -a1kanols in the transect aerosols.

Sample -A1kane ACL* -A1kanol ACL Coast Range I. Mixed coniferous foresta. 28.7 26.6 b. 28.9 26.8 c. 28.8 27.0 d. 28.5 27.3 11.Alder grove a. 28.7 28.2 b. 28.7 27.7 c. 28.7 27.2 III. Open range a. 29.0 27.8 b. 29.0 27.8 c. 29.1 27.3 Regional average 28.8 27.4 Willamette National Forest I.Above tree line a. 28.6 27.4 b. 28.6 27.2 c. 29.8 26.3 d. 29.6 26.4 e. 29.3 26.4 f. 29.9 26.4 11. Mixed coniferous forest a. 28.7 27.4 b. 28.6 27.3 c. 28.4 27.6 d. 28.6 27.6 Regional average 29.0 27.0 Columbia Basin I.Rowe Creek a. 29.0 28.3 b. 29.1 28.8 c. 28.7 27.8 d. 28.6 27.7 H. Wilson Ranch a. 28.8 28.0 b. 28.8 28.0 c. 28.7 27.7 d. 28.7 27.7 e. 28.8 27.7 f. 28.9 27.5 Regional average 28.8 27.9 Umatilla National Forest I.Open range a. 29.3 27.7 b. 29.0 27.6 c. 29.3 27.6 d. 29.1 27.5 11. Edge of mixed a. 29.0 27.4 coniferous forest b. 29.2 27.5 c. 28.9 27.5 d. 28.8 27.4 e. 29.2 27.2 f. 29.0 27.3 Regional average 29.1 27.5 ta of Standley, 1987. Table 111.4. The ACL parameters of-a1kanes and -a1kanols in vegetation waxes from the transect.

Sample (Region) -A1kane ACL* -A1kanol ACL

Coast Range Moss 28.1 27.9 Salmonberry 29.5 26.7 AlderBark 27.7 Alder Leaves 27.4 27.1 Wood Fern 28.2 26.9 Sword Fern 30.1 26.7 Norway Spruce 30.5 27.3 Norway Spruce Sap Brewer Spruce 28.6 28.2 Brewer Spruce Sap - - Douglas Fir 28.7 27.6 Regional Average 28.9 27.3 Willamette National Forest Moss/Lichen 27.5 26.1 Rhododendron 30.5 28.3 Mountain Hemlock 29.8 28.0 Big-cone Douglas Fir 28.5 27.0 Brewer Spruce 28.1 27.5 Regional Average 28.9 27.4 Columbia Basin Sage 29.2 27.4 Juniper 28.7 27.0 Juniper/Sage Litter 29.6 26.7 Grass 26.2 Wilson Ranch Soil 28.9 27.9 Regional Average 29.1 27.0 Umatilla National Forest Douglas Fir 28.4 28.4 "Green Waxy Bush" 28.9 - Elm 29.0 27.8 Alder 30.0 27.2 Fern 29.2 27.7 Laurel 29.0 26.9 Maple 27.4 27.2 Ponderosa Pine 28.2 27.8 White Fir 28.5 27.8 Douglas Fir 28.6 26.7 Pacific Silver Fir 27.9 27.1 Regional Average 28.7 27.5 -: Not detected. *: Calculated from data of Standley, 1987. 37

close to the signatures of elm, alder, laurel, fern, and brush of the clear-cut ridges. This conclusion is consistent with that from analysis of the homolog distributions of the alkanes (Standley, 1987).

Molecular Markers: Sources and Transport

Diterpenoids

Diterpenoids, mainly abietic acids (resin acids) and their oxygenated derivatives, are derived from conifers (Finder, 1960; Thomas, 1969). The diterpenoids present in the transect aerosols are given in Table ffl.5 and the source vegetation and soil in Table 111.6, respectively. Figs. 111.7 and 111.8 are mass fragmentograms of typical resin acids (m/z 237; 239; 251; 253). The presence of diterpenoids in the transect aerosols strongly confirm a source of conifers in the state wide region. 7-Hydroxydehydroabietic acid (Structure III, all structures are given in Appendix V; Fig. 111.7, m/z 237) has been detected for the first time in aerosols. 7 and 3-Oxodehydroabietic acids (Structures V and VII; Fig. 111.8, m/z 253) are present in the transect aerosols and are also found in the representative conifer source vegetation. The occurrence of 1 3-isopropyl-5a- podocarpa-6,8,1 1,13-tetraen-16-oic acid (Structure I) and dehydroabietic acid (Structure 11; Fig. 111.7) in this fraction of the aerosols is due to incomplete separation on silica gel by thin layer chromatography and more efficient derivatization to the trimethylsilyl esters. Trace amounts of compounds tentatively identified as lignans including calocedrin (Structure IV; Fig.ffi.8) and a lignan mixture with molecular weight of 386 were detected in the transect aerosols. The lignans comprise a group of naturally occurring compounds which are composed of two phenyipropanoid units joined by carbon-carbon bonds at the middle carbons of the side chain, and are generally dimers of coniferyl and syringyl alcohols (Hathway, 1962; Miller, 1973; Grimshaw, 1976). These compounds are uniquely distributed in woody tissues of plants as supportive material (Grimshaw, 1976). The occurrence of the probable lignans in the transect aerosols is probably due to direct volatilization from wood during burning, logging, and processing which are major industries of the State of Oregon. Recently, Hawthorneet al. (1988; 1989) reported more than 30 methoxylated phenolic species in the polar fractions of organic matter extracted from wood smoke particles. These compounds include the pyrolysis products of wood lignin (polymer of coniferyl and syringyl alcohols; Sarkanen and Ludwig, 1971) and the combustion products (PAHs and Table 111.5. Molecular marker concentrations in the transect aerosols. Compound' Concentration(pg/m3) Name Molecularweight2 Compositioncompoundof parent I Coast WillametteI H ColumbiaI Basin UmatillaI Diterpenoids ? - II - III - - - II - - II Unknown1 3-Isopropyl-5a-podocarpa- 111.16,8,11,13tetraen16oicacid*(I)6,8,1L13-tetraen-16-oic acid (I)3(L)4 312322 C20H2602 4.73.6 9.9 0.9 34.4 2.3 15.3 11.7 364.6 2.6 159.7 9.7 18.611.6 Calocedrin(IV)(I)7-Hydroxydehydroabieticacid(llI)(L)UnknownDehydroabieticacid*(II)Dehydroabietic 111.2 acid (H)(S) 368402358314 C20H,607C20H2803C20H2802? 48.8 4.10.15.81.5 11.30.23.71.8 43.4 0.10.33.4 137.1 55.1 0.28.41.4 390.8 40.8 0.99.71.6 551.4 71.4 2.91.71.3 4409.0 0.63.49.01.5 66.7 0.30.27.71.2 484.2 14.2 0.41.40.8 7-Oxo-Lignan7-Oxodehydroabieticacid(V)(S) 1(mixture) 3-isopropylpodocarpa-5,8,1l,13-teiraen-15-oicacid(V1)(I) 326386328 C22H2606C20H260-3 3.28.9- 12.2 4.4 - 0.30.92.2 14.718.7 1.1 17.2 3.23.0 27.1 1.01.3 12.3 0.4- 12.1 3.90.4 14.4 3.0 - Unknown3-Oxodehydroabietic 111.3 (Mixture) acid(VII)(I) 328 ? ?C20112603C2oHO3 0.20.9 1.2-1.2 tr.0.3 0.21.4 0.76.5 0.32.4 0.42.1 0.50.9 0.70.7 1 PhytosterolsUnknown 111.5111.4 398380 ? 0.10.8 3.6 tr.0.2 0.20.5 0.13.3 0.51.3 0.47.3 0.52.8 4.61.2 2 BrassicasterolCholesterol(VH1)3(S)4 (LX)(I) 470458 C2811460C27H460 3.55.5 - 11.8 6.6 0.81.0 27.510.8 28.416.8 0.81.7- 0.90.8 0.88.4 0.44.0 643 StigmasterolCampesterol-Sitosterol (X1)(S)(X)(S) (XII)(S) 486484472 C29H500C29H480C28H480 4.9 - 4.91.8- 0.70.10.5 50.218.4 - 14.0 3.4 - 0.8 - 0.5 - 0.3 - - 0.30.1 Table 111.5. continued Compound1 Concentration(pg/m3) Name Molecularweight2 Compositioncompoundof parent I Coast II III WillametteI H Columbia Basin H UmatillaI II 75 TaraxeroneTriterrenoids (XIII)(L) 424 C30H500C30H480 - - 98 a-Amyrin(XVI)(S)y-Taraxasterol-AmyrinUV)(S) (XV)(S) 498 C30H500 0.10.3 1.21.9- 0.20.3- 6.08.4 0.9 0.9 0.7 0.5 0.3 121110 Diplopterol3ct-Lupeol (XVH)(S)(XVHI)(S) 500498 C30H5002C3011520C30H500 - - - 0.5 0.6 1413 FriedelinErythrodiolOleanonic (XX)(S) (XIX)(S) acid (XXI)(L) 468426586 C30H4603C30H500 - - 0.8 - - 1615 Oleanolicacid(XXIII)(S)Betulinic acid (XXII)(S) 542 C30114603C30H4803 0.5 2.1 0.3 2.6 1.7- 0.6 1.6 0.4 191817 MorolicUrsolicUrsonic acidacid (XXV)(S)(XXIV)(I)(XXVI)(S) 542468 C30H4803 0.9- 3.7 1.2 3.0 2.1 0.7 1.5 0.6 2:1: AcidsCompounds are given are aslisted methyl in the or ordertrimethylsilyl that they ester elute derivatives on a DB-5 and (J & alcohols W Scientific) as trimethylsilyl 0.25mm x ethers. 30m capillary column -tr.*: = Total not detected. amount: ReferI =Interpreted, fromto chemical both L acid = structures Literature (cf. Table cited reference V.5, in Standley,Appendixtrace. and S = 1987)V. Standard and alcoholcompound fractions. retention and mass spectrum. SampleTable 111.6. (Region) Concentrations of molecular markers in source vegetation wax (normalized to Molecular markers (cf. Table 111.5) Cmax of n-alkanols) 1 2Phytosterols 3 4 6 5 7 8 9 10 11 Triterpenoids 12 13 14 15 16 17 18 19 Coast Range ------AlderSalmonberryMoss LeavesBark --' -0.3 -0.01 0.03 0.4 - - -0.6 -0.3 0.6-1.3 -0.20.9 -0.4- 6.0-1.5 ------6.21.62 ------tr. - DouglasBrewerNorwayWoodSword Fern Spruce SpruceFirFern - 2.28.89.3-- - - 0.5-0.41.0 - 0.1-0.20.60.30.10.20.2-0.4 - - -0.50.30.02- - -1.7------Moss/Lichen illamette National For BrewerBig-coneMountainRhododendron Spruce DouglasHemlock Fir - 29.9-0.619.3- 25.0 40.5- 3.0- - 8.2- - -4.9 -9.1 - -10.4------1.4 - -0.2 SampleTable ffl.6. (Region) continued Molecular markers (cf. Table 111.5) 1 2Phytosterols 3 4 6 5 7 8 9 10 11 Triterpenoids 12 13 14 15 16 17 18 19 Columbia Basin ------JuniperSage -.1 9.8 12.5-- 10.0 0.5 - 1.12 - - 0.7- - - - WilsonRanchSoilGrassJuniper/Sage Litter 0.2- 0.23.2 0.80.02 0.01 0.4 3.20.06-6.7 tr. 0.03 0.01 0.01 - - 0.01 Umatilla National Forest ------"GreenDouglas Waxy Fir Bush" 7.9 - - - - FernAlderElm - 0.6 0.1 1.00.5 0.11.1 - 0.010.4 0.1 - 0.1- 0.2 - PonderosaMapleLaurel Pine 0.4 0.8- - -0.7-0.1 0.20.1- 11.2- - 0.1 -12.5 0.2 22.3-- PacificDouglasWhite Fir SilverFir Fir 2.43.15.91.1 1.52.2 0.21.4 0.21.4- 0.04 - 0.2 - - - - - 2: 1: Not detectable.Bold numbers designate highest concentration. 3.1 42

it! a .1: mit

(t,

ii

mit 235

I b ti! mit

mit .1: *

ii

iW ?S % urns uie 255 1 I2 SCAM SCA$

Figure 111.7. Mass fragmentograms of diterpenoids (rn/z 237; 239) from the transect aerosols: (a) Coast Range III; (b) Willamette National Forest 11; (c) Columbia Basin 11; (d) IJmatilla National Forest 11 (I: 13-isopropyl-5a-podocarpa-6,8,l l,13-tetraen- 16-oic acid methyl ester, 1*: isomer of 13-isopropyl-5a-podocarpa-6,8,l 1,13- tetraen-16-oic acid trimethylsilyl ester, 11: dehydroabietic acid methyl ester, 11*: isomer of dehydroabietic acid trimethylsilyl ester, Ill: 7-hydroxydehydroabietic acid methyl ester; Roman numbers indicate chemical structures cited in Appendix V, cf. Table 111.5). 43

57 a

It

V

.12 2/2

Vt, it'

1285 1355 VNN IlI t2 13S L tINS it Vt b d I

2/2 .12 3 'V I

LW'V .1: .1:

Vt'

JI ' teas ties 1215 1355 l55 liNe 1285 SCAN. SCAN

Figure 1118. Mass fragmentograms of diterpenoids (rn/z 251; 253) from the transect aerosols: (a) Coast Range I; (b) Willamette National Forest 11; (c) Columbia Basin 11; (d) Umatilla National Forest 11.(IV: Calocedrin, V: methyl 7-oxodehydroabietate, *: trimethylsilyl 7-oxodehydroabietate, VI: methyl 7-oxo-13-isopropylpodocarpa- 5,8,1 1,13-tetraen-15-oate, VII: methyl 3-oxodehydroabietate, 1: Unknown 111.3, 2: Unknown 111.4, 3: Unknown ffl.5; Roman numbers indicate chemical structures cited in Appendix V, cf. Table m.5). oxy-PAHs). They are unique to wood smoke in urban atmospheres and are therefore suggested as tracers for atmospheric wood smoke pollution (Hawthorne et al., 1988; 1989). The present study did not determine this particular group of compounds.

Phytosterols and Triterpenoids

Phytosterols are the sterols of higher plants which derived biosynthetically from squalene (Heftmann, 1973; Nes, 1977; Nes and McKean, 1977; Goodwin, 1980), and are characteristic biomarkers of higher plants. Cholesterol is a principal animal sterol (Myant, 1981) and has been found in lesser amounts in plants and fungi (Mead et al., 1986). Cholesterol has also been reported in various algae (Patterson, 1971). The phytosterols in the transect aerosols and representative vegetation range fromC27to C29,and include cholesterol (C27:1, VIII), brassicasterol (C28:2, IX), campesterol (C28:1, X), stigmasterol (C29:2, XI), and 3-sitosterol (C29:1, XII). Figs. 111.9 to 111.12 give the histograms of the phytosterols(C27:1, C28:2, C28:1; C29:2; C29:1)in the aerosols, source vegetation and soil. Fig. 111.13 shows some typical mass fragmentograms of phytosterols in the transect aerosols. The distribution patterns of phytosterols in the epicuticular waxes of representative vegetation differ from species to species (Table 111.6; Figs. 111.9 to 111.12), and are therefore of utility to trace sources. Cholesterol has been identified in the needles (Schaefer et aL, 1965) and bark (Rowe, 1965) of pine trees. In this study, cholesterol is detected in only a trace amount in the wax lipids of Ponderosa pine, and is not found in any other source vegetation (cf. Table ffl.6). The wide occurrence of cholesterol in the transect aerosols at a proportion from 26% to 88% of the total phytosterols (Table 111.5; Figs. 111.9 to 111.12) indicatesan additional source input. Cholesterol in the transect aerosols may be derived from algae, which have different phytosterol distributions from those of vascular plants, with cholesterol generally predominant (Goad, 1977), from cooking and processing ofmeats and other animal products (Rogge et aL, 1991), and/or soils and fauna existing therein. The total phytosterol contents in the aerosols along the transect showa general decrease from the coast to the northeastern desert (Table 111.5). Thismay be due to a progressive decrease in the phytosterol input from the forests. Ternary diagrams of phytosterols (C27, C28, C29)of aerosols and source vegetation and of soilare given in Figs. 111.14 and ffl.15, respectively. Clearly, the distribution patterns of the aerosols differ from those of the source vegetation and the aerosol patterns from the Umatilla NationalForest are quite different from the others of the transect. This may be indicate an additional 45

55 isi Rooq. i 11.8 1.0 CoccI Rang.

3 pg/rn3 pg/rn pg/rn

2.7 5.9 0.5

III 0 0 0 l I 25 C- 30 25 C 30 25 C- 30 00 CooReie. 00 00 Coosl Rang. Mou Aldei 8oA

50 I 50 50

0-j- 0 0-f- I i I I 25 C- 30 25 C- 30 25 C- 30

00 100 001Coasl Ronq. CoccI Ronq. Co 00 Range Wood Fein S,.od Fun 81.,Iu Spucs 6

50 50 50

I 01 I i I I I I I 01 I I I I i 01 25 C.- 30 25 C 30 25 C 30 25 C 30

Figure 11L9. Histogram (carbon number versus concentration) distributions of phytosterols (_..:C27:1, C28:1, C29:1; --:28:2; --: 29:2) in the aerosols and source vegetation waxes collected from the Coast Range. 50.2 28.4

25.1 14.2

0 0 25 C- 25 C - 30 I00 100 WiHomelts 100 WIllamells Willamette Rhododandron Bq.cons Douqlas Fir Brewer Spruce %1 6

50-i I 50 50

01 V I i 1 01 i I I i It I 25 C 30 25 C 30 25 C 30

Figure ffl.1O. Histogram (carbon number versus concentration) distributions of phytosterols (: C27:1, C28:1, C29:1; 28:2; 29:2) in the aerosols and source vegetation waxes collected from the Willamette National Forest. 1.70 0.90 Columbia Basin I

pg/iTs pg/rn3

0.85 0.45

0 01- 25 30 C C

00 l0( Co4urnbla Bairn Columbia Basin Columbia Bairn 001 ColumbIa Basin JurA,ev/Soqs Lillar Grass Wilson Ranch Soil

50-I 5< 50

g I; lI 0J I 01 i I 0 O 25 C 30 25 C 30 25 C 30 25 C 30

Figure Iii 11. Histogram (carbon number versus concentration) distributions of phytosterols (-: C27:1, C:1, C29:1; ----: 28:2; ---: 29:2) in the aerosols, source vegetation waxes and soil collected from the Columbia Basin. B.4 4.0

pq/rT pq/rn

4.2 2.0

0 0 25 30 C C-

100 L)noIIIIo 00 100 Daqlon Fir I. f. 1.

50 50 50

0-j- 25 C- 30 25 C 30 25 C 30 I00 100 00 thnotIIIo Umoillia Pnsdsro,a Pins Douqias Fir PocIlic Sllsr Fir .1

50 50

It Ii 0J 01 I I 't i i I i i 01 i I 1 01 i I i 25 C 30 25 C 30 25 C 30 25 C 30

Figure IlL 12. Histogram (carbon number versus concentration) distributions of phytosterols (_:C27:1, C28:1, C29:i; ---:28:2; --: 29:2) in the aerosols and source vegetation waxes collected from the Umatilla National Forest C

U/ 'Jo XIX jx X XZX

XIV XIV

:

I4 I9S II t I4I IS IX 'XXX b vtil

141 l4 II 14a1 I4 IS SCM

Figure IlL 13. Mass fragmentograms of phytosterols (m/z 129) and amyrins (m/z 218) from the transect aerosols: (a) Coast Range ifi; (b) Willamette National Forest II; (c) Columbia Basin 11 (d) Umatilla National Forest ll.(V1III: cholesterol, IX: brassicasterol, X: campesterol, XI: stigmasterol, XII: J3-sitosterol, XIV: f3-amyrin, XVI: a-amyrin, n30: C30 -a1kanol; Roman numbers indicate chemical structures cited in Appendix V, cf. Table 111.5). 50

C28

t oo

100w. C27 80 60 40 20 C29 Re1ativ C27

Figure ifi. 14. Ternary diagram of phytosterols (C27, C, C) in the aerosols collected from aansect across the State of Oregon: (1) Coast Range I; (2) Coast Range II; (3) Coast Range ifi; (4) Willamette National Forest 1 (5) Wifiamette National Forest II; (6) Columbia Basin I; (7) Columbia Basin II; (8) Utnatiula National Forest I; (9) Umatilla National Forest II. 51

C28

loo, C27 80 60 40 20 C29 Retau C27

Figure IlL 15. Ternary diagram of phytosterols (Cr, C, C29) in the source vegetation waxes and soil collected from a transect across the State of Oregon: Coast Range (1) Moss; (2) Salmonberry; (3) Alder Bark; Wood Fern; Sword Fern; Norway Spruce; (4) Brewer Spruce; Willamette National Forest (1) Rhododendron; (5) Big-cone Douglas Fir; (6) Brewer Spruce; Columbia Basin (7) Juniper; (8) Juniper/Sage Litter; (9) Grass; (10) Wilson Ranch Soil; Umatilla National Forest (3) Douglas Fir; Elm; (11) Alder, (12) Ponderosa Pine; (13) White Fir; (1) Douglas Fir, (14) Pacific Silver Fir. 52 source input besides the inputs from the local source vegetation and the aerosols transported from the west by the predominant wind trajectory. Seven oxygenated triterpenoids have been detected in the alcohol fractions of the transect aerosols (Table 111.5). They are a- and 3-amyrins (XVI, XIV, Fig. 111.13) which are common in many species of the representative vegetation (Table 111.6), oleanonic acid, oleanolic acid, ursonic acid and ursolic acid (XXI, XXIII, XXIV, XXV, Fig. ifi. 16) which are detected as major triterpenoids only in wax of laurel from the Umatilla National Forest, and friedelin (XX). The ubiquitous occurrence of oleanolic and ursolic acids in the transect aerosols implies a contribution from a source other than the representative vegetation (laurel). Traces of these compounds werealsodetected in the j surface soil of the Columbia Basin. Triterpenoids (primarily amyrins) are present in variable amounts both in the Harmattan aerosols and in the composited vegetation wax of Nigeria (Simoneit et al., 1988). Traces of a- and 13- amyrins, and oleanolic and ursolic acids are present in some aerosols of the South Atlantic, and are major constituents of composited plant waxes from the Punta Arenas area of South

America (Simoneit etal.,1991c). These compounds are also present in aerosols from the Blue Mountains and southeastern coast of Australia (Simoneit et al., 1991b). They generally are not detectable in aerosols transported over longer distances (e.g. across the Pacific, Gagosian et al., 1982). Other oxo- and hydroxy-triterpenoid acids were detected in the representative vegetation (Table 111.6). They are minor constituents of vegetation waxes, except in laurel wax, and may be characteristic for specific vegetation. These compounds are not detected in the transect aerosols probably due to their instability and lack of source input.

CONCLUSIONS

The molecular marker signatures of the alcohol fractions of waxes from representative source plants were used to identify the origins of the corresponding aerosols collected in a transect across the State of Oregon. These aerosols are dominated by plant wax components with minor constituents from oceanic and anthropogenic sources. An increase inCm in the -a1kanol homologs of the aerosols is observed along the transect from the cooler coast to the warmer desert areas. The regionalaverage ACL parameters of the -a1kanes and -a1kanols in the transect aerosols range from 28.8 to 29.1 and 27.0 to 27.9, respectively. These values are typical of temperate climates 53

LXV a

283 LXIII

LX

rr bi LXV cait 283

LXV LXIII C1

2831 R

d

z 283

LXIII e

283 I L I I 152a 1548 158 1588 18 1528 1548 1663

SCAN-

Figure [tLl6. Mass fragmentograms of oleanolic and ursolic acids (m/z 203) from the transect aerosols and source vegetation wax: (a) Coast Range Ill; (b)Willamette National Forest II; (c) Columbia Basin II; (d) Umatilia National Forest II; (e) Laurel. (XX: Friedelin, XXI: methyl 3-oxo-olean-12-en-28-oate, XXIII: methyl oleanolate, XXIV: methyl 3-oxo-urs-12-en-28-oate, XXV: methyl ursolate, iT: triterpenoid, Roman numbers indicate chemical structures cited in Appendix V, cf. Table ffl.5). 54 when compared with ACL parameters of -alkanes of 29.9 to 30.1 in tropical Saharan dust from Africa (Poynter and Eglinton, 1990). Free o-hydroxyC14andC16alkanoic acids have been found in the waxes of both the Gymnosperms and the Angiosperms of the source vegetation, and in the corresponding aerosols. 3-Oxo-alkanoic acids are found as major components of mountain hemlock only. They are not present in the regional aerosols which may be due to their instability in the atmospheric environment and lack of source input. Phytosterols and triterpenoids are major components of the transect aerosols and are representative of an origin from the source vegetation. Phytosterols are more stable in the environment than oxygenated triterpenoids and are therefore more useful tracers for the study of aerosols. Cholesterol in the aerosols is derived from marine sources, e.g. algae, from anthropogenic activities associated with cooking and processing of meats, andJor soils and fauna existing therein. 55

CHAPTER IV. CHARACTERIZATION AND CORRELATION OF OXYGENATED COMPOUNDS IN AEROSOLPARTICLES AND SOURCE VEGETATION: II - KETONES (ALDEHYDES) AND MISCELLANEOUS TERPENOIDS

INTRODUCTION

The presence of higher plant waxes in tropospheric aerosols has been reported for rural and remote areas (Simoneit, 1977a; 1980; 1989; Simoneit and Mazurek, 1982a,

b; Simoneit et al., 1980; 1983; 1991b,C;Standley, 1987; Gagosian et al., 1981; 1982; 1987; Kawamura and Gagosian, 1987; Peltzer and Gagosian, 1989; Shaw, 1979). However, in comparison to the relatively extensive studies that have been conducted on the hydrocarbon, carboxylic acid, and alcohol fractions, few systematic investigations have been made of the rural conthbutions of ketones and aldehydes to the troposphere (Simoneit and Mazurek, 1982a; Simoneit et al., 1991a). In order to quantify the air/source exchange of materials and to understand the processes that control this exchange, it is necessary to identify as many tracers as possible to assess the origins of the air parcels and source materials, their transport mechanisms over a transect and the processes affecting their fate (exchange). Thus, the ketone fractions of extracts from aerosols and representative vegetation wax samples are characterized here to evaluate additional molecular markers to complement the established tracers.

The sampling, extraction and separation procedures are described in Chapters II and Ill.

Ketone Fraction Analysis

The ketone fraction was analyzed by capillary gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The GC analyses were carried out on a Hewlett-Packard Model 5840A gas chromatograph using a 25 m x 0.20 mm i.d. flexible fused silica capillary column coated with DB-5 (J & W, Inc.). The GC-MS analyses were performed on a Finnigan Model 4021 quadrupole mass spectrometer interfaced directly with a Finnigan Model 9610 gas chromatograph and equipped with a flexible 56 fused silica capillary column coated with DB-5 (30 m x 0.25 mm i.d.). The GC temperature program was 65°C for one minute, 65 to 130°C at a rate of 15°C/mm, 130 to 310°C at a rate of 4°C/mm, then held isothermal at 310°C for 60-120 minutes. The GC- MS temperature program was 65°C for 2 minutes, 65 to 310°C at a rate of 4°C/mm, then held isothermal at 3 10°C for 60-120 minutes. Mass spectrometric data were acquired and processed by a Finnigan-Incos Model 2300 data system. Molecular markers were identified by GC and GC-MS comparison with authentic standards, reference literature, or interpretation of mass spectra. Quantitation of the homologous series was carried out by comparison of the GC peak area with a co-injected known standard, hexamethylbenzene. Molecular markers were quantitated on GC-MS by comparison with the peak area of the same standard.

RESULTS AND DISCUSSION

Homolog Distributions: Correlation with Source Signatures

Ketones

The analytical data for the homologous compounds in the transect aerosols and the source vegetation are given in Tables IV. 1 and P1.2, respectively. In-chain ketones, which are present in the epicuticular wax of many plants, have been shown to be biosynthesized by oxidation of secondary alcohols derived from alkanes (Kolattukudy et al., 1968; 1976). The ketone functional groups are usually located in the middle or toward the end of the carbon chain. Therefore, the ketones usually are present in lower amounts than the alkanes, and they have odd carbon number predominances with the same distribution and Cmas the alkanes. There are two main groups of in-chain ketones present in the transect aerosols and in the representative source vegetation studied. The -a1kan-2-one homologs are major components of grass wax from the transect vegetation (Table IV.2; Fig. IV.la) and have not been found in any other source vegetation of this region. They range from C25 to C35 withCm at C27 and have a CPI of 5.7. The -a1kan-2-ones have been reported in smoke aerosols of prescribed slash bums in the Oregon Coastal Range area, and closely match the -alkane distributions withCmof C27 and an odd carbon number predominance attributable to a plant wax origin (Chapter II, Standley, 1987). It has also been observed that the ri-alkan-2-one Table IV. 1. Analytical data for the homologous compounds in the transect aerosols. Sample -Alkan-2-ones1 Cmax Cmax -Alkan-10-ones C(pg/m3) In-chain-alcohols Cmax AldehydesSaturated Cmax UnsaturatedAldehydes Cmax III.II.I.Coast Open Range range AlderMixed grove coniferous forest 29 253.4 35.2 8.7 II.I.Willamette Mixedconiferousforest National Forest Abovetreeline na3n.a. n.a.n.a. n.a. n.a. n.a. n.a.n.a. II.I.Columbia Wilson Basin Ranch Rowe Creek 29 10.6 6.5 II.I.Umatilla Edge ofNational mixed Forestconiferous forestOpen range 29 9.72.0 2: : DeterminedNot analyzed.Not by GCIMS.detected. Table IV.2. Sources of the homologous compounds from the transect regions CoastSample Range (Region) -AIkan-2-ones1 n-Alkan-10-ones In-chain-alcohols AldehydesSaturated UnsaturatedAldehydes Moss - - 25-29- 29 - - - - 28-30- 28(30)- AlderSalmonbeny Bark n.a.3- n.a. n.a. n.a. n.a.27-29 n.a.29 n.a. n.a. n.a.- n.a.- WoodSwordAlder Fern Leaves Fern n.a.- n.a.- n.a.27-31- n.a.29 29-31n.a.30-31 29n.a.31 n.a.17-26 n.a.24 na. n.a. DouglasBrewerNorwayNorway Spruce SpruceFir Spruce Sap Sap n.a. n.a. n.a.29 n.a.29 n.a.27-37 n.a.31 n.a.30 n.a.30 n.a.28-2928-30 n.a.n.a.28 RhododendronMoss/LichenWilbmette National Forest n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. BrewerBig-coneMountain Spruce DouglasHemlock Fir - 29 29 29 29 n.a. 30-34n.a. n.a.30 Table IV.2. continued Sample (Region) Crangen-Alkan-2-ones1 Cmax Crane -Alkan-10-ones Cmax CraneIn-chain-alcohols Cmax Cange AldehydesSaturated Cmax Crange UnsaturatedAldehydes Cmax SageColumbia Basin -.2 ------WilsonGrassJuniper/SageJuniper Ranch Litter Soil n.a.3-25-35 -27n.a. -n.a.29-3 1 n.a.29- -27-29n.a. -27n.a. -n.a. -n.a. -34n.a.28-32 -34n.a.30 Umatilla National Forest - - 29 29 29 - - - - Em"GreenDouglas Waxy Fir Bush" n.a.-n.a. n.a.-n.a. n.a. n.a.31 n.a.29-30 n.a. n.a.- n.a.- n.a.- n.a.- FernMapleLaurelAlder n.a.n.a.- n.a.n.a.- n.a.27-3317-29 n.a.29 n.a.25-2929 n.a.29 n.a.- n.a.- n.a.- n.a.- PonderosaPacificDouglasWhite Fir SilverFir PineFir n.a.- n.a.- n.a.17-29 n.a.29 n.a.29- n.a.29- n.a.n.a.- n.a.- n.a.n.a.28-3028-32 n.a.30 2: : NotDetennined analyzed.Not by detected.GCIMS. 53 1 al

543.3 71

292 i 323 L -

3.3

1.7

108.3 b

59.3

U L.L 211 so 1)43 2438 250 3439 is.o: 188.0 1

352365 4543

358 408 458 5438 558 608

108.3 r e.ax c 153 63 37 59.3 1g7

I iii

tj 1L T Ij1J. r.11F?° !.. 50 108 1543 23) 2543 3438 33.

1.7 M-t8-Z8 378

j t

359 4843 458 598 550 698

Figure IV.1. Examples of homolog mass spectra: (a) C27-a1kan-2-one; (b) C31 -aIkan-1O-one; (c) C in-chain alcohol. 61 distributions are bimodal withCmatC19or C21, andC29, C31,orC33(Simoneit, 1985; 1986b; Simoneit et al., 1988; 1991a; Kawamura and Gagosian, 1987) and they have been ascribed to anthropogenic activity or to atmospheric oxidative processes (Chapter II, Standley, 1987). However, in the case of the Harmattan samples from western Africa they appear to have a dual origin, both from anthropogenic sources and directly from vegetation waxes (Simoneit et al., 1988). These compounds have also been detected in sediments (e.g. Volkman et al., 1981; Simoneit, 1978a, b; Simoneit and Mazurek, 1979) where they generally match the-a1kane distributions. In the present study, the -a1kan-2-ones are not present in the transect aerosols. This may be due to the lack of input from anthropogenic activity, and limited vegetation sources (grass), or to insufficient atmospheric oxidative processes. The occurrence of -a1kan- 10-ones in epicuticular waxes of higher plants (Gymnosperms and fruits) has been reported (Tulloch, 1976). The -a1kan-10-ones are common in vegetation species from a number of families in the transect areas, and have Cmmainly atC29(cf. Table IV.2; Fig. IV.lb). The patterns of -a1kan-10-ones in the transect aerosols (C atC29)directly reflect the regional vegetation input (Table IV. 1). The -a1kan-10-one concentrations of the transect aerosols range from 2.0 to 253.4 pg!m3

In-Chain-Alcohols

In-chain-alcohols are biologically related to in-chain-ketones and hydroxyketones (Tulloch, 1976). They are always free and have an odd number of carbons. In-chain- alcohols have been detected from many species of source vegetation in the transect regions with carbon number ranges fromC27toC37andCmatC29and C31 (Table IV.2; Fig. P1.lc). They are not found in the transect aerosols (Table P1.1). This is probably due their instability in the atmospheric environment.

Saturated Aldehydes

Saturated aldehydes (-a1kana1s), which are genetically related to the free alcohols with an even carbon number predominance and usually with thesame chain lengths as the free alcohols, occur in only minor quantities in epicuticularwaxes (Tulloch, 1976). Aldehydes are present at small amounts in red alder leafwax with a carbon number range fromC17toC26andCmatC24(Table P1.2; Fig. IV.2a). In 62

57 20.8)

188.81 I a3

7132 se.a- 1

287 LI I. 225 222 L16I38 i5 a it ji I 4!II I1k 14

58 188 288 258 358

5.8 -!

2.5 M-I8 M-L3-28 418 398 362 434M I J !II 4e3 458 see 28. 188.8 b

58.8 83 I

69 1 313

345 LI II111125 222 28 279 18S 334 149157 is IlL ,

I 58 188 158 280 258 389 358 5.8

2.5-1 48

363 377 388 'I 480 450 500 550 60

Figure IV.2. Examples of homolog mass speca: (a) .-triacontana1; (b)-octacos-6-ena1. 63

sword fern only C30 is detected (Table IV.2). These compounds have been detected in the smoke aerosols from the prescribed burns in the Oregon Coastal Region at concentrations up to 1 ng/m3. There these compounds have aCmat C22 and an even carbon number predominance which indicates they are derived by oxidation from -alkano1s in plant wax (Standley, 1987). Aldehydes were not detected in the transect

aerosols, which may be due to a lack of input or preferential oxidation of aldehydes ton- alkanoic acids in the environment (Simoneit et al., 1988).

Unsaturated Aldehydes

Mono-unsaturated aldehydes are found as major components in many waxes of vegetation along the transect (Table IV.2; Fig. IV.2b). They range from C28 to C34 with an even carbon number predominance andCmat C28 or C30 (Table P1.2). They are not present in the transect aerosols and their conspicuous absence is probably due to their instability and rapid oxidation in the environment.

Unknown Homologs

Unknown homologs are found as major components in some waxes of conifers from these study areas (Fig. IV.2c). They are present in white fir of Umatilla National Forest 11 ranging from C27 to C33 with aCmaxof C31, and in Douglas fir of Umatilla National Forest I and II from C27 to C31 with aCmaxof C3l(27) and from C27 to C37 with aCmof C35, respectively.

ji-Alkanol Acetates

n-Alkanol acetates have been detected in wax from red alder before (Prahi and Pinto, 1987). They are not found in either the transect aerosols or the source vegetation.

Wax Esters

Wax esters (n-alkyl--a1kanoates) are a major component (0.4% to 79.3% of total lipid, cf. Table 11.3; Fig. IV.3b) of the epicuticular waxes of the vegetation samples analyzed. Wax esters of higher plants ranging in chain length from C32 to Chave been described, although the range is narrower for many waxes (Tulloch, 1976) and Table IV.3. Ketone molecular marker concentrations in the transect aerosols. Compound1 Concentration(pg/m3) Name Molecularweight2 Compositioncompoundof parent I Coast II III WillametteI II ColumbiaI Basin II UmatillaI II I (e.g.BicycicSesguiterpenoids sesquiterpenone XXVII)3(I)4 220 C15H240 - - - n.a. n.a. - - - 3.4 45 UnknownDiterpenoids IV.1 290346 C21H3004 9.12.4 11.4 0.3 0.41.7 n.a. n.a. 1.3 5.2 - 3.3 786 UnknownPimaricEpi-manoylManoyloxide*(XXX)(L) acid(XXXII)(S) IV.2 oxide* (XXXI)(L) 362316290 C20H3002C20HO 14.8 5.2 - 6.91.4- 0.20.7- n.a.n.a. n.a. 21.762.4 4.8- 40.4 3.96.0- 12.0 2.21.7- 19.718.0 8.8- 2 2,5-cyclohexadiene-2,5-Bis(lAnthropogenic ,1-dimethylpropyl)- 1 ,4-dione - 3 Phenanthrene(XXVIII)(S) (XXIX)(S) 248178 C18H12C14H10C16H2402 0.61.0 7.0- 0.8 - n.a. n.a. 2.4- 6.3 - - 3.02.1 9 Chrysene (XXXIH)(S) 228 - 2.3 - - n.a. n.a. - - 4.4 1110 NorlupeolTnterpenoids (XXXI V)3(S)4 426412 C29H480 - - - n.a. n.a. - - - 1312 UnknownaAmyrin* IV.3 (XVI)(S)Amyrin* (XIV)(S) 426?424 ?C30H500C30H480 - - - n.a. n.a. - - - 161514 Friedelin*UnknownUnknown IV.5(XX)(S) IV.4 426440 C30H500C30H4802 - - - n.a.n.a. n.a. - - - - Table IV.3. continued Compound1 Conceniraiion(pg/m3) Name Molecularweight2 Compositioncompoundof parent I CoastII III I Willamette II I Columbia Basin II I Umatilla II 17 -Amyrone (XXXV)(I) 424 C30H480 - - n.a. n.a. - 1918 3:4-seco-3--nor-olean-a-Amyrone12-en-2-oic (XXXVI)(I) acid (XXXVII)(I) 444424 C29H5002CH48O - - - n.a. n.a. 2120 Dihydmcanaric(XXXVIII)(I)3 :4-seco-olean- 1acid 2-en-3-oic acid 456 C30H5002 - - - n.a. n.a. 22 Unknown(XXXIX)(I) IV.7 456 C30H5002 - - - n.a. n.a. - - 252423 FriedelinolTaraxerone*Dihydroburic (XLII)(I) (XIII)(I) acid (XL)(I) 428424456 C30H520C30H480 - n.a. n.a. - - - 21: AcidsCompounds are given are aslisted methyl in the ester order derivatives. that they elute on a DB-5 (J & W Scientific) 0.25mm x 30m capillary column. -tr.*: = Compounds= not trace. detected.: Refer also to found chemicalI =Interpreted, in alcohol structures fractions. L = cited Literature in Appendix reference V. and S = Standard compound retention and mass spectrum. n.a. = not analyzed. LJ 55 180.8 aH 63a3

58.8 111

II125 139 239 Ll$ 157 185 213 269 285237 323 341 I I 58 100 158 288 258 388 350 188.0,

so. a

450 588 558 608 658

b cd 3638

TINE-F

Figure P1.3. Example of: (a) mass spectrum of the cluster of C32wax esters with acid/alcohol moieties ofC14118, C1616, C18114,and Cj10 in laurel wax; (b) GC trace of the ketone fraction of alder wax showing the C34 to C wax esters, with a, b, andc indicating the C27, C29 and C31 -alkanes, d and e indicating the C31 and C33 -a1kan- 10-ones. 67

marine wax esters generally range from C26 to C42 (Sargent, 1976; Sargent et aL, 1976; Boon and de Leeuw, 1979). Wax esters in the source vegetation and soil from the transect regions are given in Table P/.4, and Figs. IV.4 to P1.7, respectively. The mass spectra of saturated wax esters give the molecular ion [RFCOORA]+, a fragment ion corresponding to the fatty acid moiety [RFCOO + 2H] and a fragment ion corresponding to the alcohol moiety[RA+ H](Fig. IV.3a; Aassen et al., 1971). The assignments of the individual wax esters of a cluster (wax esters with same molecular weights eluting from the GC column as a single peak) was determined from the [RFCOO + 2lIjions of the mass spectra (Fig. IV.3a). Wax esters in the source vegetation samples of this study range from C28 to C and have exclusively saturated fatty acid and alcohol moieties. The major homologs of the esters are C38, C40 and C42. Acid moieties range from C14 to C36 and alcohols from C6 to C30, respectively, with combinations of acid and alcohol moieties of C14 to C74, C16 to C22 and C26; C8 to C10 and C30; C6 to C32 predominating. The compositions of the acid and alcohol moieties vary considerably from plant species to species (Table P/.4) and are useful for characterizing the source vegetation. Wax esters with Cmat C40 have been detected in smoke samples from the Oregon Coastal area (Standley, 1987) and in rural aerosols from the western United States (Simoneit and Mazurek, 1982a). Only trace amounts of wax esters are present in the transect aerosols with Cm at C40, indicating an origin from plant waxes. This low aerosol concentration is probably due to the low vapor pressure of wax esters, to decomposition of wax esters before they are emitted to the air, and/or to photochemical reactions. Therefore, the trace amounts of wax esters present in the aerosols may be due to injection of wax esters associated with the soil particulate matter (plowed soil, Table 11.3) rather than by gas phase or direct emissions. For comparison, wax esters found in aerosols off the coast of Peru, an area marked by high sand cliffs with winds blowing strongly from the southeast most of the year and transporting aerosol material originating on land into the marine atmosphere, have higher concentrations ranging from 17-332 pg/m3 (C40-C60) with Cmat C(Schneider and Gagosian, 1985). This is 2-20 times higher than other remote marine areas (Peltzer and Gagosian, 1984; Gagosian et aL, 1982). This result strongly supports that wax esters are injectedintothe atmosphere associated with soil particles, which is not an important injection process in the case studied here. Therefore, the emission mechanisms involved do not include any significant gas to particle partitioning. Table IV.4. Analytical data for wax esters in vegetation waxes from the transect regions. (Region)Sample Cmax Wax Esters Acid Alcohol Coast Range Crange' CPI(C28.50) 00 Crange Cmax Crange Cmax AlderSalmonberryMoss Bark 34-3836-44 4238 23.029.4 - 14-2216-22 -16 - 16-2612-22 -2622 SwordWoodAlder Leaves FernFern .234-3832-44 3836 - 87.200 - - - - - Norway Spruce Sap 34-38n.d.329-50 3642n.d. n.d. 2.6 n.d.- 12-26 n.d.- 16 n.d.- 12-30 n.d.-26 WillametteDouglasBrewer Spruce Fir National Sap Forest n.d.36-38 38n.d. 20.415.8n.d. n.d.- n.d.- n.d.- n.d.- BrewerBig-coneMountainRhododendronMoss/Lichen Spruce DouglasHemlock Fir 30-4234-41-34-44 3840 - 107.743.013.2 - 22-36-- 30,32- 6-8- -8,6 Table IV.4. continued Sample(Region) Cmax Wax Esters CPI(C28..50) Crange Acid Cmax Crange Alcohol Cmax Columbia Basin 34-38cange' 36 - - - - WilsonGrassJuniper/SageJuniperSage Ranch Litter Soil -34-3828-46 -38 21.912.4 4.6- -12-34 -32 -6-18 - 6 Douglas Fir matilla National For 32-42 40 105.9 - 14-32 30- 6-20- 10 - Elm"Green Waxy Bush" 34-4234-44 4038 13.5 8.0 - - - - FernAlder 34-3834-46 38 45.8 2.3 -14-18 - 14 - 16-26 24 - PonderosaMapleLaurel Pine 36-42-30-44 42- 17.700 - - 14-22 - 16 -8-16 26 - PacificDouglasWhite Fir Silver Fir Fir 28-42-34-40 38- 83.0 8.3- - 16-32 30- 6-16- - 8 3:2: 1:Not Determined detecteddetermined. by GC/MS. 70

100 38 100Coøst Range 42 00 38 00 Coast Rang.

Soimonb.try 1 I Aid., t_ioyii Coast Rang. Coast Rang. Aids, 6a,lt .,.

50 50

IIJJ1 03Ii, '-i 0-f-i H i'i'ii 0f 30 30 C40 50 30 C40 50 00 38 Coast Rang. Coast Rang. 42 too - Coast Rang. OO Coast Rang. ad Fits Naay Ots.., Spnacs Douglas Fit Spruc. % ,.

30 50 So So

0 ..fl 50

FigureJ1f4Histogram (carbon number versus concentration) distributions ofwax esters in the source vegetation wax collected from the Coast Range. 71

100 38 WIIto,n.Iis Rhododendron

,.

50

100 40WUlomittu 100 WIllomsile Bb -cone Brewer Spruce Douqloi Fir

II . 1 II

So-I II 50

0 !.i.I1!tttIi ° II.11rI.l,I,t.I.i.1 30 C40 50 30 C40 50

Figure P1.5. Histogram (carbon number versus concentration) distributions ofwax esters in the source vegetation wax collected from the Willamette National Forest. 72

%

50

0 30 C-40 50

38 ColumbIa tOO1 38 Columbia Biin Basin Junipir Junlpsr/ Sage Lit tsr

50 50

0 0 30 C40 50 30 C-40 50

Figure IV.6. Histogram (carbon number versus concentration) distributions of wax esters in the source vegetation wax collected from the Columbia Basin. 73

100 40 IUmatiII IOouq$ai N..dle,

1.

0-i-, -I 0 30 C40 50 30 C40 50 CO CO CO

t.

50 50 So

0 0 0 30 C40 50 30 C-40 50 30 C-40 50 100 100 U.,.iIUl 42 CO LursI

f.

50 50 50 50

o 0 0 0 30 C40 50 30 C40 50 30 C40 50 30 C40 50

Figure IV.7. Histogram (carbon number versus concentration) distributions of wax esters in the source vegetation wax collected from theUtmitillaNational Forest. 74

Molecular Markers

Ketone molecular marker concentrations in the transect aerosols and their source vegetation are given in Tables P1.3 and P1.5. Manoyl and epi-manoyl oxides, which have been reported in carboxylic acid fractions (Standley, 1987), are found in the aerosols throughout the transect. Their sole occurrence in Brewer spruce and white fir imply other source inputs. The occurrence of these compounds in this fraction of the aerosols and vegetation waxes is due to incomplete separation on silica gel by thin layer chromatography. There are two diterpenoid ketones (Unknowns P1.1 and 2) present in the transect aerosols. They are probably from the source vegetation or could be atmospheric oxidation products. Many triterpenoid ketones are found in only specific vegetation species. Four open A-ring triterpenoids, 3:4-seco-3-nor-olean-12-en-2-oic acid (Structure XXXVII), 3:4-seco-olean-12-en-3-oic acid (Structure XXXVIII), methyl dihydroburic acid (Structure XL), dihydrocanaric acid (Structure XXXIX), and Unknown IV.7, are present in moss wax as major components of the ketone fraction, and are not found in any other source vegetation. Therefore they can be used as indicators of moss, but may also be derived from other sources. Trace amounts of a- and -amyrones (Structures XXXVI and XXXV) have been detected in grass wax only. Friedelin (Structure XX) is found in Norway spruce only as a major wax component in this fraction. However, none of these triterpenoids are detectable in the aerosols from the transect. This may be due to their atmospheric instability and/or lack of significant source input. Two anthropogenic compounds have been found in the transect aerosols, namely phenanthrene (XXIX) and chrysene (XXXIII) which are combustion products. Their ubiquitousoccurrence in the transect aerosols may reflect long range transport and greater stability.

Procedural Contaminants

2,5-Bis( 1,1 -dimethylpropyl)-2,5-cyclohexadiene- 1 ,4-dione (XX VIII), which is an antioxidant product, is found in the transect aerosols and is probably a contaminant from solvents (e.g. diethyl ether). Butyl myristate, butyl palmitate and butyl stearate are present in the extracts of the aerosol filters from the entire transect. These esters are common coating materials. For example, butyl myristate and butyl stearate are used for magnetic insulation Table IV.5. Sources of molecular markers in the transect aerosols (cf. Table IV.3). No. Name1 Compositioncompoundof parent Key ions and molecular weight2 Source Comments 1 (e.g.BicyclicSesguiterpenoids sesquiterpenone XXVII)3(I)4 C15H240 ifl,192,205,220 ? 45 ManoylUnknownDiterpenoids oxide(XXX)(L) IV.1 C20H340C21H3004 25.,269,3355,177,192,257,275,290 1,346 WhiteBrewerGrassDouglas Fir Spruce Fir MajorTraceMajorSmall 76 PimaricEpi-manoyl acid(XXXII)(S) oxide(XXXI)(L) ?C20H3002C20H340 5.5,177,192,257,275,2901,133,180,241,301,316 WhiteBrewerSword Fir Spruce Fern SmallMajor 8 AnthropogenicUnknown IV.2 251,362 LaurelBrewerRedDouglas Alder Spruce Fir SmallMajor 932 Phenanthrene(XXIX)(S)2,5-cyclohexadiene-Chrysene(XXXIII)(S)(XXVIII)(S)2,5-Bis( 1,1 -dimethylpropyl)- 1 ,4-dione C18H12C14H10C16H2402 114,2163,177,191,205,221,233,248 AntioxidantCombustion Product 10 Norlupeol(XXXIV)3(S)4Triterpenoids C29H480 fl135,175,400,412 Salmonberry Small Ui Table IV.5. continued No. Name1 Compositioncompoundof parent Key ions and molecular weight2 Source Comments 1211 Unknown -Amyrin(X1V)(S)IV.3 C30H480C30H500 123,424189,203,218,393,408,426 GrassLaurelRed Alder Trace 1413 Unknowna-Amyrin(XVI)(S) IV.4 ?C30H500 189,203,218,393,408,426 LaurelRedGrass Alder Trace 18171615 a-Amyrone(XXXVI)(I)Friedelin(XX)(S)Unknownl-Amyrone(XXXV)(I) IV.5 C30H480C301T480C30H500C30H4802 189,203,218,409,424189,2Q3,2j,409,424177,189,204,425,440189,204,218,269,393,408,?5,41 1,426 GrassNorwayWilsonRed Alder Ranch Spruce Soil TraceMajorTrace 212019 Dihydrocanaricacid3:4-seco-olean-3 :4-seco-3-nor-olean- 12-en-2-oic(XXX VIII)(I) acidacid(XXXVII)(I) 12-en-3-oic C30H5002C29H5002 177,189,203,218,369,441,456177,189,203,218,369,429,444 Moss Major 25242322 Fredelinol(XLII)(I)Taraxerone(XIH)(I)DihydroburicUnknown(XXXIX)(I) IV.7 acid(XL)(I) C30H520C30H480C30H5002 95,189,205,313,409,42455,95,135,175,413,428204,245,441,45695,109,189,203,218,441,456189,203,218,369,441,456 SwordMoss Fern SmallMajorMajor 2: : IReferCompounds to chemicalAcids are arelisted structures geven in the as citedordermethylesters. in same Appendix as in TableInterpreted, V. IV.4. L = Literature reference and S = Standard compound retention and mass spectrum. 77

shielding (Mito and Senzaki, 1990), and water resistant coatings for electronics (Kitagawa et al., 1989). Butyl palmitate is used in the cosmetic industry (Buil et al., 1989) and butyl stearate and butyl palmitate are utilized as lubricants in the manufacture of cans (Sharp and Channon, 1987). Butyl palmitate has been reported in only one vegetative natural source (Berger et al., 1989). Therefore the input from natural sources is expected to be negligible and these esters are most likely contaminants derived from the sampling and analytical procedures.

CONCLUSIONS

The -alkan-2-one homologs are major components of grass wax but are not found in any other source vegetation of this study area. The absence of -alkan-2-ones in the transect aerosols indicates a lack of source input. The occurrence of -a1kan-2- ones in Harmattan aerosol samples of western Africa indicates a large source input with a dual origin from vegetation and oxidative processes (Simoneit et al., 1988). The n-alkan-10-ones, which occur in many representative vegetation waxes, are widely present in the transect aerosols, and can be correlated to the regional source vegetation. In-chain-alcohols and saturated and monounsaturated aldehydes present in the transect vegetation are not found in the aerosols of the regions. This is probably due to their instability in the atmospheric environment rather than lack of source input. Unknown oxygenated homologs are found as major components in some conifer waxes but not in the aerosols of these study areas. This is probably due to their environmental instability and lack of source input. -A1kanol acetates are not detectable in both vegetation and aerosols of this area. Wax esters, a major component of the representative vegetation waxes, are present in only trace amounts in the transect aerosols but are detectable in smoke aerosols from agricultural burning (Standley, 1987). This implies that wax esters are unstable in the atmospheric environment and are more likely injected associated with smoke and/or soil particles. Thus, gas to particle partitioning is not a significant emission mechanism here. Diterpenoid and triterpenoid ketones have more complex chemical structures and are therefore more useful in source correlation of aerosols. Friedelin is found in Norway spruce wax only. Trace amounts of a- and f3-amyronesare found in grass wax only. Four open A-ring triterpenoid ketones are found in moss wax only. However, these terpenones were not detected in the transect aerosols, partly because of their instability and/or lack of source input. 79

CHAPTER V: SUMMARY

The aerosol particles, collected along a transect across the rural State of Oregon, are dominated by plant wax components with minor components from oceanic, anthropogenic, and soil sources. These aerosols show a relatively uniform distribution of four classes of neutral lipids, such as hydrocarbons, carboxylic acids, aldehydes and ketones, and alcohols. This is in contrast to the more variable and complicated distribution of neutral lipids, including hydrocarbons, wax esters, carboxylic acids, aldehydes and ketones, and alcohols in the waxes from source vegetation. Wax esters, which comprise a major class of neutral lipids in the source vegetation and the surface soil, are detected only in trace amounts in the transect aerosols. This may partly be due to photooxidative degradation of wax esters in the atmosphere and their low volatility. The occurrence of wax esters in smoke aerosols of Oregon (Standley, 1987) and in aerosols off the coast of Peru (Schneider and Gagosian, 1985) implies that they are more likely introduced in association with smoke and/or soil particles. Thus, gas to particle partitioning does not appear to be a significant mechanism in this case. All aerosols from the four regions have a significant percentage of polar fractions containing unknown compounds and this percentage is less than that in the source vegetation. This may also be due to photochemical alteration of these polar materials once in the atmosphere. The molecular marker signatures of the plant waxes of the various vegetation species from the geographic areas were used to identify the sources of the corresponding aerosols. Plant wax components in the Oregon aerosols correlate with their source vegetation and are characterized by the homolog distributions of the -a1kanols (even carbon number predominance), and in-chain ketones (odd carbon number predominance). The n-alkan-1O-ones, which occur in many vegetation species waxes, are present in the transect aerosols and correlate with the regional source vegetation. The -a1kan-2-one homologs are a major component of grass wax but are not found in any other source vegetation waxes. The absence of the-a1kan-2-ones in the transect aerosols indicates a lack of source input, compared to their wide occurrence in Harrnattan aerosols in western Africa (Simoneit et al., 1988). This is consistent with the species dominance of the regional vegetation. An increase in Cmin the -aIkanol homologs of the transect aerosols is observed along the transect from the cooler coast to the warmer desert areas. The ACL parameters (Poynter and Eglinton, 1990) of the jj- alkanes and -alkanols in the aerosols reflect the fingerprints of the waxes from the major regional source vegetation and are typical of temperate climates. Phytosterols and triterpenoids are major components of the transect aerosols and their representative source vegetation. The phytosterols are comprised mainly of cholesterol, brassicasterol, and 3-sitosteroI, with lesser amounts of campesterol and stigmasterol. Cholesterol, which is not a major component of the plant waxes, may be derived from a marine source, e.g. algae (Patterson, 1971), from anthropogenic activities associated with cooking and processing of animal meat and fats (e.g. Rogge et al., 1991), or from soils. Triterpenoid alcohols and/or acids are common in both the aerosols and plant waxes of the region. They are more specific to the source vegetation. However, triterpenoids are not too stable, with most undergoing rapid reactions and transformations in the atmospheric environment. Only a-amyrin, 3-amyrin, oleanolic acid, and ursolic acid have been detected in these aerosols. The interpretations based on the data for the homologs and molecular markers from the alcohol and ketone fractions, which were discussed here, are analogous as the hydrocarbon and carboxylic acid fractions and confirm the conclusions discussed by Standley (1987). BIBLIOGRAPHY

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Simoneit B. R. T., Cardoso J. N. and Robinson N. 1991c. An assessment of the origin and composition of higher molecular weight organic matter in aerosols over the South Atlantic from about 3O700S. Chemosphere 23, 447-465. Standley L. J. 1987. Determination of molecular signatures of natural and thermogenic products in tropospheric aerosols - input and transport. Ph.D. thesis, Oregon State University, Corvallis, OR, 190 pp. Standley L. J. and Simoneit B. R. T. 1987. Characterization of extractable plant wax, resin, and thermally matured components in smoke particles from prescribed burns. Environ. Sci. Technol. 21, 163-169. Standley L. J. and Simoneit B. R. T. 1990. Preliminary correlation of organic molecular tracers in residential wood smoke with the source of fuel. Atmosph. Environ. 24B, 67-73 Thomas B. R. 1969. Kauri resins - modern and fossil. In: Organic Geochemistry Methods and Results (G. Eglinton and M.T.J. Murphy, eds.), Springer, Berlin, pp. 599-618. Tulloch A. P. 1976. Chemistry of waxes of higher plants. In: Chemistry and Biochemistry of Natural Waxes, Chapt. 7 (P. E. Kolattukudy, ed.), Elsevier, New York, pp. 235-287. Volkman J. K., Gillan F. T. and Johns R. B. 1981. Sources of neutral lipids in a temperate intertidal sediment. Geochim. Cosmochim. Acta 45, 18 17-1828. Volkman J. K., Everitt D. A. and Allen D. I. 1986. Some analyses of lipid classes in marine organisms, sediments and seawater using thin-layer chromatography- flame ionization detection. J. Chromatogr. 356, 147-162. Went F. W. 1955. Air pollution. Sci. Am. 192, 63-72. Went F. W. 1960. Organic matter in the atmosphere and its possible relation to petroleum formation. Proc. Nail. Acad. Sci. U.S.A. 46, 212-221. Wesley R. C. III, Joel S. L., Daniel I. S., Edward L. W., Philip J. R., James A. B. and Vincent G. A. 1988. Particulate emissions from a mid-latitude prescribed chaparral fire.J. Geoph. Research 93, 5207-52 12. Wilkinson R. C. and Hanover J. W. 1972. Geographical variation in the monoterpene composition of red spruce. Phytochem. 11, 2007-20 10. Wolff G. T., Groblicki P. J., Cadle S. H. and Countess R. J.1982. Particulate carbon at various locations in the United States. In: Particulate Carbon Atmospheric jj (Wolff and Klimisch, eds.), Plenum, New York,pp. 297-3 15. Zavarin E., Snajberk K, Reichert T. and Tsien E. 1970. On the geographic variability ofthe monoterpenes from the cortical blister oleoresinof Abies la.siocarpa. Phytochem. 9, 377-395. APPENDICES APPENDIX I: Relevant Formulas and Calculations

1 CPI (Carbon Preference Index) of n-alkanols

[Ceven] Cl2 + C14 + .. + C34 cpi= = [Cd] C13+C15++C33

'1 CPI (Carbon Preference Index) of wax esters

[Ceveni C28 + C30 + + C50 CPI= = [C] C29 + C31 + + C49

3. "Higher Plant" ACL of -a1kanes

C27 x [C27] + C29 x [C9] + C31 x [C31] n-Alkane ACL = [C27] + [C29] + [C31]

4. "Higher Plant" ACL of -a1kanols

C26 x [C26] + C28 x [C28] + C30 x [C30] n-Alkanol ACL = [C26] + [C28] + [C30] APPENDIX II:

Histograms of 11-Alkanols (-) and a-Hydroxy Alkanoic Acids (") Distributions in Aerosols and Source Vegetation Waxes Collected Along a Transect From the State of Oregon 0.14 016 0.21 Coasl flange 020 Coast flange nq /m 007 3 nq Inc nq/m 3 20 30 40 0 _.f1-1IW1Ui!f.,.111110 20 30 40 0 10 20 30 40 0 10 F Illijil II 20 44j11 .i 30 40 021 C.- 0.20 Ci 0.21 - C,- nq/m 3 3 C 018 ng /m Ir nq/m S. ng /m 'S. 0 10 20 C- 30 40 0 10 20 c-I- 30 40 0 10 20 C 30 40 0 _1.j_,)10 20I111II1It(I C.- 30 40 031 0.17 0.46 0.52 ng /m 3 ng/m ng /m 1 WiIIam Ia flg /rT 016 0.23 0.26

20 30 40 0 10 20 C- 30 40 0 frn' 10 20 30 t.Il.44t4I44ftl..1 40 0 10 20 C.- 30 '10 0.44 3 C 0.45 0.37 3 C 0.'l0 ng/m ng /rr ng/m ng 0,22 0.23 019 0.20 20 C 30 '10 0 I'T.T4't1tIDLht9I..lI.j10 20 C- 30 40 0 10 20 C.- 30 40 0 tO 20 C 30 40 0.49 0.33 0.47 ng/m052 3 rig /m' ng/rn 3 ng /m 0.26 0.25 0)7 0.24 20 30 40 0 10 20 C,- 30 40 0 10 20 C..- 30 40 0 10 20 C,- 30 40 0.12 3 C 0.23 0.16 3 0.13 rig/rn rig /n rig/rn rig /m [TII 0.12 0.06 - un 1111111111 &I Ij LIMII& M& ii,uuun,,uiiu IIIIIIIlIIIIIIi L I. [I LI fl . !rr'''1r o 20 0.14 019 0.23 rig/rn 3 rig fir rig/rn 3 rig/ni 0.07 0.12 0 10 20 30 40 0 10 20 C.- 30 40 0 10 20 30 40 0 JO 20 C.- 30 40 019 3 C 0.23 043 3 0.33 rig/rn C ng/n rig/rn rig fln 0.12 0 22 0.16 20 C 30 40 0 10 20 C-- 30 40 0 10 20 C-- 30 40 0 JO t1ItU ftI'I1II1 Il 20 C..- 30 .. 40 'I-) ot oz o o oc .1_3 ot- 1. l-jjj itt ilt i'-'1- 0 'I IIIIIIIIItIIIII3 0 ' L1 ittiii'i'I'ii o '1 Ui o oc o I Ito [Mi] 610 t,I.0 zWI vo u w,bu LW/ Z 0 ot t-'-'-'itItititttiiItitt-'I oc -'--3 oz Oi 0 ot oc D o 01 0 OL' oc -'-3 O 01 0 Ot' oc 3 0 I 600 W/I U W/ W/ c bu0 L 10 fu ct'o ItO fu t79 0 ry tOO 500/ ID 50 0/ #0 500/ I. 50 0# (0 L 20 30 40 0 10 20 C.- 30 40 0 tO r't'44'JuIl4J41.Js.f.,...r_r,., 20 30 40 0 tO 20 30 40 C rood]SI Range Fern 100] 24 CoostSword Range Fern '°°lCoasI Range INorway Spruce C 26 t0O J 24 C BrewerCoast Spruce Range 50 0I I0 50 0I 10 500/ /0 5C 0/ (0 L 20 C.- 30 '-'i 40 0 tiiI4f1ItlIl1III1I. 10 20 C,- 30 40 0 tO 20 C 30 40 0 tO 20 C 30 40 100 100 26 I I CooslDouglas Range Fir 22 RhododendronWillomette 1001 WillomelJeMountainI lemlok 28 500/ /e 500/ /0 0/ d 500 C 0 l0 20 30 40 0 10 20 30 40 0 10 20 30 40 0 10 20 30 40 100, 26C.. DouglasWilIametle FirBig-cone 221 24 C IBrewer WillomeIte Spruce 1001 22 C Columbia BasinSage 1001 26 I C I Basin 50 0/ #0 1001 500, I0 500/ 10 50 0/ /0 0 10 20 C,. frr44J+f4f4444-119+_rrr,.r..i.,30 40 0 10 20 C 30 4_r44111411411.JI1J..r.r.r.i...i 40 0 10 20 C 30 40 0 l r.U'D 1tL1ILI1I., 20 C- 30 '+- 40 'C tOO - 22 Juniper/SageColumbia LitterBasin tOO Columbia GssBasin 26 WilsonColumbia ft BasinSoil 28 Ooug(as Fir UmolilIa 28 500/ /0 50-0/ 0 50-0/ 0 50 4176 0- 0 0 ______Ito20 C.- (24 30 40 1001 0 20 241 C 30Umalillo 40 lOOi tO 20 C.-.- 2E1 2R 30 40 l00- tO 20 C 30 40 50 0//0 50 0/ /0 50 0- ,0 500/ /0 0 10 f.,.i.(.,.I.lt(IlJJI. 20 C,- 30 .'.II-' 10 0 (0 20 f$1l-tI114f. C,- 30 40 o 4.Ti.l.tIlefiI4II_ _ --tO 20 C,- 30 40 "nhIIIuI rM 0&&l . 00 167 A 22 WhileUmalilla Fir 50 0/ 'U 500/ l0 50-0/ (0 50U, /0 I 20 30 40 0 10 20 30 40 0 40 I Ii 20 30 40 I. 24 Silver FitUmatillaPacific C- 50 0/ 10 20 C 30 40 100

APPENDIX III:

Histograms of Phytostersols (-:C27.1, C281andC291; C28.2; C79:2) Distributions in Aerosols and Source Vegetation Waxes Collected Along a Transect From the State of Oregon pg/m 5.5 - pg/rn 11.8 pg/rn3 1.0 Coast Range 50.2 2.7 5.9 0.5 pg hr 25.1 II 0 25 C- 30 0 25 C 30 ot 25 C Il I i I 30 I I 0 25 C 30 28.4 1.70 0.90 3 I ColumbiaBasin U 8.4 pg/m 14.2 pg/rn0.85 pg/rn0.45 pg/m 4.2 0 25 C- 30 0 25 C 30 01- 25 C- 30 0 25 C - 30 4.0 100 100 pg/m Coast Range Moss 0/ /0 0/ /0 2.0 50 5° 50 0 0 0 100 as C - 30 1000± 25 C 30 t00 25 C 30 25 C- 30 0/ I0 0/ I0 0/ /0 0I /0 Brewer SpruceCoast Range 1!] 50 I iI I I 0 25 C 30 0 25 C- 30 0 25 C 30 25 ______I I C- I I 30 0 100 0/ 10 100 /0 1 Big-cone Douglas Fir Willamelte 100 1 Brewer SpruceWillwnelte 100 1. 50 50-1 I so-I/01 50 I III 0 25 C - 30 0+ 25 C - I 30 I 0 2S C 30 0 25 C- 30 100 Juniper/SageColumbia Litter Basin 0I 10 0/100 10 II(FT WilsonColumbo Ranch Soil Basin 0/lOG /0 50 50 I I I! I! 0+ 25 C 30 0 25 C 30 o 25 I I I C I I 30 I L C - 30 1000I 0/100 10010/ Ponderoso Pine UmatilIa 0/tOO 5010 5010 50 50/0 0 25 30 0 25 30 OJ 25 I I I II I I 30 I 0 25 30 1001 DouglaS FirUmolillo C - 100 Pacific Silver Fir Umotillo C C C 50 50 '! I! I It 'I ' I OI 25 I I C I I 30 I 0 25 I I C I I 30 105

APPENDIX IV:

Histograms of Wax Esters Distributions in Vegetation Wax Extracts Collected Along a Transect From the State of Oregon 100 100 100 tOO 50 0/ 10 50 0/ I0 500/ 10 50 0//0 0 30 40 50 0 30 40 50 30 40 50 0 30 40 50 100 C 100 C 100 36 C Brewer SpruceCoast Range 100 C 500, do 50 0l 'U 50 0/ /0 50 0/ /0 0 30 C - 40 50 0 30 C.- 40 50 0-h 30 C 40 C- 40 50 -C 100 VIllameltahododendron 100 40 DouglasWillameIte FirBig -cone 100 500I /0 50 0/ to 500I /0 50 0) /0 0-1-1 r1 0Iii.1llttttiiii.jj 0 0 100 30 C 40 50 100 30 38 Columbia Basin C - 40 50 100 30 40 C.. 40 Umalilla 50 100 30 C 40 50 OF /0 OF /0 Juniper/Sage Liller 0/ to Douglas FirNeedles 0/ 50 50 I 50 5: C 40 lI.IhI!IhIlC 40 50 0-f-, 30 C - 40 C.. 40 50 0I 100 100 100 100 500/ /0 50 0/ /0 50 0/ /0 50 0/ /0 0 0 0 0 100 30 C 40 50 100 30 C - 40 50 100 30 C 40 50 30 C 40 50 500/ /0 50 0//0 50 0I/0 C - 40 - C - 40 50 0 30 C -r 40 50 109

APPENDIX V: Chemical Structures of Diterpenoids and Triterpenoids Cited (With CAS Registry Number Listing) 110

a

OH ' COOH COOH L 1 3-IsopropyI-5apodocarpa- II. Dehydroabietic III. 7-Hydroxydehydro- 6,8,11,13-tetraen-16-oic acid acid abietic acid a a

IV. Calocedrin 1. 0 1. 0 ' COOH ' COOR V. 7-Oxodehydroabietic VI. 7-Oxo-1 3-isopropyt- acid podocarpa-5,8,11,13- tetraen-1 6-dc acid

_'%JJn I

VII. 3-Oxodehydroabietic acid HO

HO HO

X. Campesterol XI. Stigmasterol ill

HO HO O

XII. f3-Sitosterol XIII. Taraxerone (Skimmiorie) XIV. 3-Amyrin

HO 0 HO

XV. c-Taraxasterof XVI. a-Amyrin XVII. epi-Lupeol

OH

HO

XVIII. Diplopterol XIX. Erythrodiol XX. Friedelin

200K

0

XXI. Oleanonic acid XXII. Betulinic acid XXIII. Oleanolic acid 112

:ooF ..

XXIV. Ursonic acid XXV. Ursolic acid XXVI. Morolic acid

XXVIII. 2,5-Bis(1,1-dimethylpropyl)- XXVII. Sesquiterpenone XXIX. Phenanthrene 2,5-cyclohexadiene-1 ,4-dione

cgigi

XXXIII. Chrysene XXX. Manoyl oxide XXXI. epi-Manoyl oxide XXXII. Pimaric acid

I-iC

XXXIV. Norfupeol XXXV. 3-Amyrone XXXVI. a-Amyrone 113

HO HOo

XXXVII. 3:4-Seco-3-nor-Oleafl-1 2- 3:4-Seco-atean-1 2-eri-3-oic acid en-2-oic acid

HO

XXXIX. DihydrocartariC acid XL Dihydroburic acid

HO

XLI. 1-riedelinol 114

Chemical Abstract Service (CAS) numbers of some compounds in Appendix V.

Number Name CAS number

II Dehydroabietic acid 1740-19-8 Vifi Cholesterol 57-88-5 IX Brassicasterol 474-67-9 X Campesterol 474-62-4 XI Stigmasterol 8 3-48-7 XII f3-Sitosterol 83-46-5 XIII Taraxerone 514-07-8 XIV 3-Amyrin 559-70-6 XV ir-Taraxastero1 464-98-2 XVI ct-Amyrin 638-95-9 XVII j-Lupeo1 4439-99-0 XVIII Diplopterol 1721-59-1 XIX Erythrodiol 545-48-2 XX Friedelin 559-74-0 XXII Betulinic acid 472-15-1 XXIII Oleanolic acid 508-02-1 XXIV Ursonic acid 6246-46-4 XXV Ursolic acid 77-52-1 XXVI Morolic acid 559-68-2 XXIX Phenanthrene 85-01-8 XXX Manoyl oxide 596-84-9 XXXI j-Manoy1 oxide 1227-93-6 XXXII Pimaric acid 127-27-5 XXXIII Chrysene 218-01-9 XXXV 13-Amyrone 638-97-1 XXXVI a-Amyrone 638-96-0 XXXIX Canaric acid 2067-65-4 XLI Friedelinol 5085-72-3 115

APPENDIX VI: Mass Spectral Reference File of Compounds Cited in This Study 116

213

297 Unkuon 111.1. 1'L 91 111 233

LrJ, F

tee.a C21HO2 237 197 9397 312

L1 podocarpa-6,8,11,i3et;aen F4 :n ...

C21H3002 71

II. Mechyldehydroabietate 'f7i5i732891rs 2eT

r 23

271

117 239

L ¶ 'T,In Unknown III - 2 lee 22 e

49e ee gae 117

IL

227 73

ii ¶ -; 9

III. Methyl 7hydroxydehy H38O3Si droabietata triethy1 silyl 8.9 ether 492

I 373'i i

459 698 559

180.9

ze. a

283 2391 2 281 316 339 r

, 'v'..''i'' ,-' I 159 228 259 288 358

IV. Calocedrin C20H1607 a.a

459 580 559 698 659

180.0 (çL C1HO3

I 115 V. Methyl 7oxodehydro 171 I L. r abietate , 59 188 150 280 350 118

i.a

ze. a

1295 L,,L.A 311

tza

Ligna (mixture)

a 35/

Is I 68

1.a 251 C21HO3

' 149 isz I VI. Methyl 7oxo-13isopro 197 pylpodocarpa-5 .8,11,13 f tA4 JL tetraen-15oate 158 298 259 258

iee.a C21H 197 117

155 I 328 oX '128 I 213 268287 1- I t4I I 282' 313 VII. Methyl 3oxodehydro abietace ILt . 158 288 258 328 119

a. 137

i. 1r k j Unknown 111.3 (nixture) t88.

e. a

439

378

188.8

59.a

2 309 'r1 LI 59 159 208 259 388 358 Unknown 111.4 108.0

50.0

380

458 580 558 88 650 180.8 251 -

58.9

59 180 158 288 259 Unknown 111.5 180.8

58.8

580 559 120

17 j4

a C3kiOSi VIII. Cholesterol triechyl silyl ether 33 485

Ir tJ1IT! '.

480 458 588 550

188.0

.a

58 100 158 208 253 388 358 ioe.a C31HOSi

IX. Brassicasterol 388 trimethyl silyl ether

408 453 500 550 S88

100.0- 55

58.0-.

J

108.8- r nC31H%OSi

X. Campesterol trimethyl silyl ether 37 457

.j.,.I.j.I_.I.lr;.j.I'i_._j111 358 408 458 538 558 =1: 121

r 4.0 180.8 - 255 83

330 L1i 58 100 153 288 258 394 . a

484 C32H%QSi . Stiaateoj trimethyl silyl echer

350 458 559

57

LJ

U 322 ?tIE 50 158 220 250

tee. a

ThaQ C32H58OSi XII. 5Sjosteroj tethy1 silyl ether 486

47i 458

350 458 558 i.a

50.0

180.0

XIII. Taraxerone (skiimn.jorie) 50.0 c3oI48o

409424 368

480 453 588 558 122

23

273 73

tI9

C33H53OSt XIV. 8Amyr1 tr1ethyL silyL ether -

498 233

488 48 588 550

73 aa 121 5!

,;J. I1I .I. ,4, 180 158 298 259 398 28.8

XV. 4,Taraxascerol 18.3 crimechyl sily]. ether C33H53OSi 23 498 393 499 425 483

358 498 45

188.8 218

279

50.3 73

C33HOSi

XVI. ciAmyrin 498 trimechyl silyl ether

333

I 488 377 427 a

I I 1&11l1'11r I 488 459 580 580 550 123

189

199

12t 147 t7 Z79 ,LJ, lk 1 i.e- r .ax L7) C33H53OSi

XVII. 3ci-Lupeol triethy1 silyl. ether 49$

36i13 iri 'u-I . 48$ 4Z8

!.ax 191

31 149

I I 287 328 LSL 2 23 :1, 1 fT1, 1 :,

29.3

XVIII. Diploptarol trimethyl silyl ether C33HOSi 429

II 442 !89 I I' I III'II. ,..,,I 489 48 21E

73

293 .a.

113

J!J,!jJJ ;!lt IlL 188 298 2!9 388 199.3

XIX. Erythrodiol 4O trimethyl silyl ether C36HOSi2

291 2c 4C3 481 14 7 ,j ''I .iili 'jill' 409 4!2 8a 8 S88 124

L0.X C30H500

XX. Friedelin 341

315 332 35637 4jf3 4_Il 4 308 35J 400

100_a

189 262

r_Z] 1Th &1;M'1. 1

18. '3X øø.

C31H4O3 XXI.Methyl 3-.oxo-, olean-L2-et-28-oate 488 463 393 IhhII,IIli' 308 358 480 458 508 180.8 189 73

81 Ji 12L 175

I I I ii un 147 I

!111211t I4

l5.0 413 ieee ( CH58O3sL

XXII. Methyl betulinate trimethyl silyl ether 542 377

,1LL42s ¶ 500 jI 1i' 480 458 580 550 580 659 125

e. o

25 3 247 23

l 2a iee.e

XXIII. Methyl oleanolace CH58O3Si trthethyl silyl ether

483 27 L5z

480 48 133 283

2S2

3n

I : 1 208 28 133.8 r 408 c31o3 XXIV. Methyl 3oxo urs-12en-.28oace

El

rIj.I I' 'E'''''1 126

2S2 tee. a

a.a

at 147 U. i] 4 1

. Methyl ursolate CH58O3Si trimethyl silyl ether 42 482 487 1 27 I 48

iae.a

a. a

119 I 81 147 213 !J iJJL4li. lea 229 2!ø

188 3

l. Methylorolate I trimethyl si.lyl ether CH53O3Si

483 42

408 4a a0 127

177

138

121

13 132 I.Bicyclic I. sesquierpenotte 23 308

,., -

248 0 191 tZ3 91 t49 'r1r VIII.2,5-3i(1 1- k j ______i dinethy1propy1)-2,5- I cyciohecadietie-L,4-diore 88 L0 158 288 258 38

178 188.3 ?C C14H13

71 113

IX.Phenanthrene 388 83 188 158 280 250 300

180.3

C21H0O4. Unown IV.]. 119 78 139 168 195 263 3A6 1!JI 11 I 83 180 188 280 258 338 388

121 188.3

C21H3202

O4, ct7- ' II.Methyl pinarate _____4 L59 92I3 24l 3iS 128

r at C20H340 0

t77 122 sa.a 1= 137

. Manoyl oxide 1 U:

- -

a' C20H340 ° ç.

I. Epi-anoyL oxide 918

iee.a

a. a

1178 I 1.4. J 1t2 122 157 118t 219

tag L8 299 23 388 358 Uaknon IV.2

sa. a

453 528 558 8 5O

58.3 t:ji;:j 114 175 III. Chrysene 81 125 isa 22 'I 58 188 158 388 358 129

-. t 'l 4

_t 253

XXXIV. Norlupeol C29H480

4t2

4'O 553 28 tee. a

za.a - I

383

' jIi' çtø 153 289 250

XIV. 8-Amyrin 5.3 C30H5O

426

480 458 500 550 j

1813.8

74

58.3

203

L ( r iJ I11.1Lj 58 189 158 288 258 tnknown IV.3

58.8 C30H480

381 94 '-I- l..I.l.L.I.I.I_I.r.I'I?It'II' 488 458 500 558

2-. 130

ax

28

21 i j,it27

ia.a

XVI. -Aytin .a C30H500

II 48 1892O 1Q'3.3' 119 1218 L37 i3

L4

I!1liJ rY 1 23 28 known tV.4

488 1R9 .ax 188.3-

ITT 284

189

Unknown tV .5 28.0

te. a -

393

I I I I P I 489 48 89 609 68 131

218

283 a.a

ie

8-Amyrone

C30H4s0

42

i' 408 80 08 81 218 100.3

93 121

136 161

U i

180.3

VI. iAmyrone 58.3 c3cIio K

488 458 580 550 680 132

I 55 'Z03

14 257 CCCV111. MethyL 3 :4-seco- 23 di . tLJ1L iL. L i; . L IL 3-or-o1ean-12-en-2-oaca (methyl 3:4-geco- 58 tee 158 208 258 358 friedelen-3-- e) tee.a C30H52O

12M1C3 1H520I 58 3

VIII Methyl 3.4- I seco-olean-12-en-3-oace I ...... t I 480 450 588 558 S88 L8 100.3- 55

S9 283 213 50.3- 113 2.5

., I! 1.!. tee 1 228 358 388

441 C31H5202 IX. Methyl dihydrocanarace (methyl 3:4- seco-lupea-3-oate) V

480 458 soe ee 245 180.3-

284

2i8L

i.. T1 Ji V V so 108 158 288 258 388 358 unknown IV.7 180.3

C3H52O2 58.3-

441

488 458 588 558 S88 133

218 iae. a

a.a

ji .1 . ... ie a 2 28

XL. Methyl dihydroburate C31H5202 a. 8

23 456 44 I

458 588 550 688 658

iaa.a

a. a

t1It,44

108 158 208 258 388 358 iee.a

XLI. FriedelioL C30H520

423

458 588 558 689 658

In! Z-