AN ABSTRACT OF THE THESIS OF
Xiaojing Chen
Oceanography
Master of Science
for the degree of
presented on
in
November 8. 1991
Title: Oxygenated Natural Products in Tropospheric Aerosols Sources 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 in Crnax of -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.
C
Copyright 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 by
jajjng 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 THINLAYER CHROMATOGRAPHY WITH FLAME
IONIZATION DETECTION - LIPID CLASSES OF
EPICUTICULAR WAXES OF VASCULAR PLANTS
AS BIOMARKERS IN THE LOWER TROPOSPHERIC
ENVIRONMENT
INTRODUCTION
EXPERIMENTAL METhODS
Sample Locations and Descriptions
Lipid Isolation
Lipid Analysis
RESULTS AND DISCUSSION
Lipid Concentrations and Distributions of Transect Aerosols
Lipid Distributions of Epicuticular Waxes of Source Vegetation
Lipid Distribution of Surface Soil
Source Correlations of Transect Aerosols
CONCLUSIONS
CHAPTER III. CHARACTERIZATION AND CORRELATION
OF OXYGENATED COMPOUNDS IN AEROSOL
PARTICLES AND SOURCE VEGETATION: I - ALCOHOL
FRACTION
INTRODUCTION
EXPERIMENTAL METHODS
Sample Locations and Descriptions
Lipid Isolation and Separation
Lipid Analysis
RESULTS AND DISCUSSION
Homolog Distributions: Concentrations and Reproducibility
Homolog Distributions: Correlation with Source Signatures
Parameter Analysis: Sources and Transport
Molecular Markers: Sources and Transport
Diterpenoids
Phytosterols and Triterpenoids
CONCLUSIONS
CHAPTER IV. CHARACTERIZATION AND CORRELATION
OF OXYGENATED COMPOUNDS IN AEROSOL
PARTICLES AND SOURCE VEGETATION: II - KETONES
(ALDEHYDES) AND MISCELLANEOUS TERPENOIDS
INTRODUCTION
EXPERIMENTAL METhODS
Ketone Fraction Analysis
3
3
4
4
7
8
8
9
9
17
18
18
19
19
19
19
20
21
21
22
30
34
37
37
44
52
55
55
55
55
Page
RESULTS AND DISCUSSION
Homolog Distributions: Correlation with Source Signatures
Ketones
In-Chain-Alcohols
Saturated Aldehydes
Unsaturated Aldehydes
Unknown Homologs
n-Alkanol Acetates
Wax Esters
Molecular Markers
Procedure Contaminants
CONCLUSIONS
56
56
56
61
61
63
63
63
63
74
74
77
CHAPTER V. SUMMARY
79
BIBLIOGRAPHY
81
APPENDIX I.
Relevant Formulas and Calculations
89
APPENDIX II.
Histograms of -Alkano1 (-) and U-Hydroxy
Alkanoic Acid () Distributions in Aerosols and
90
Source Vegetation Wax Collected Along a Transect
From the State of Oregon
APPENDIX III.
Histograms of Phytosterols (-: C27:i, C281, C291;
--: C282; C292) Distributions in Aerosols and
Source Vegetation Wax Collected Along a Transect
From the State of Oregon
100
APPENDIX IV.
Histograms of Wax Ester Distributions in Vegetation
Wax Extracts Collected Along a Transect From
the State of Oregon
105
APPENDIX V.
Chemical Structures of Diterpenoids and Triterpenoids
Cited (With CAS Registry Number Listing)
109
APPENDIX VI.
Mass Spectral Reference File of Compounds Cited
in This Study
115
LIST OF FIGURES
Page
Figure
II. 1.
Location map of the sampling sites of the aerosol particles
in the transect across the State of Oregon.
11.2.
Examples of Iatroscan analyses for aerosols from the transect
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
11.3.
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) Wilamette National Forest; (c) Columbia Basin;
(d) Umatilla National Forest.
12
11.4.
Examples of lairoscan 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 mm in hexane-diethyl ether (96:4).
15
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.
16
111.1.
Histogram (carbon number versus concentration)
distributions of -a1kanols and tu-hydroxy alkanoic
acids (-) in the aerosols and source vegetation waxes
collected from the Coast Range.
26
6
Page
Figure
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
of -alkanols and co-hydroxy alkanoic acids (S") in the aerosols,
source vegetation waxes and soil collected from the Columbia Basin.
28
111.4.
Histogram (carbon number versus concentration) distributions
in the aerosols
of -a1kanols and co-hydroxy alkanoic acids
and source vegetation waxes collected from the Umatilla National
Forest.
29
111.5.
Examples of: (a) mass spectrum of methyl 14-hydroxytetradecanoate
trimethylsilyl ether, (b) mass spectrum of methyl 16-hydroxyhexadecanoate 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).
32
111.6.
Example of: (a) mass spectrum of methyl 3-oxohexacosanoate;
(b) fragmentogram of fl-C25 to C29 3-oxo-alkanoic acid methyl esters.
33
111.7.
Mass fragmentograms of diterpenoids (m/z 237; 239) from the
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, 8,11,13tetraen- 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).
42
111.8.
Mass fragmentograms of diterpenoids (m/z 251; 253) from the
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-isopropylpodocarpa5,8,11,1 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,
43
cf. Table 111.5).
111.9.
Histogram (carbon number versus concentration) distributions
of phytosterols (-:
C27:l, C28:l, C29:i; --: C28:2; ---: C29:2)
in the aerosols and source vegetation waxes collected from the
Coast Range.
45
Page
Figure
111.10.
Histogram (carbon number versus concentration) distributions
46
C28:2; ---: C29:2)
of phytosterols (-: C27:1, C28:1, C291;
in the aerosols and source vegetation waxes collected from the
Willamette National Forest.
111.11.
Histogram (carbon number versus concentration) distributions
C29:2)
of phytosterols (-: C27:1, C281, C291; --S: C282.
in the aerosols, source vegetation waxes and soil collected from
the Columbia Basin.
47
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
(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,
49
cf. Table 111.5).
111.14.
Ternary diagram of phytosterols (C27, C28, C29) in the aerosols
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.
50
111.15.
Ternary diagram of phytosterols (C27, C28, 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;
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.
51
111.16.
Mass fragmentograms of oleanolic and ursolic acids (ni/z 203)
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).
53
Page
Figure
IV. 1.
Examples of homolog mass spectra: (a) C27 -a1kan-2-one;
(b) C31 n-alkan-10-one; (c) C27 in-chain alcohol.
60
IV.2.
Examples of homolog mass spectra: (a) -Triacontana1;
(b) -octacos-6-enal.
62
IV.3.
Example of: (a) mass spectrum of the cluster of C32 wax esters
with acid/alcohol moieties of C14118, C16116, C18/14, and C22110
in laurel wax; (b) GC trace of the ketone fraction of alder wax
showing the C34 to C46 wax esters, with a, b, and c indicating the
C27, C29 and C31 n-alkanes, d and e indicating the C31 and C33
n-alkan- 10-ones.
66
IV.4.
Histogram (carbon number versus concentration) distributions
of wax esters in the source vegetation wax collected from
the Coast Range.
70
IV.5.
Histogram (carbon number versus concentration) distributions
of wax esters in the source vegetation wax collected from the
Willamette National Forest.
71
IV.6.
Histogram (carbon number versus concentration) distributions
of wax esters in the source vegetation wax collected from the
Columbia Basin.
72
IV.7.
Histogram (carbon number versus concentration) distributions
of wax esters in the source vegetation wax collected from the
Umatilla National Forest.
73
LIST OF TABLES
Page
Table
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
regions
13
111.1.
Analytical data for transect aerosols
23
111.2.
Analytical data for -alkanols in vegetation waxes from the transect
regions
25
111.3.
The ACL parameters of-a1kanes and -a1kanols in the transect
aerosols
35
111.4.
The ACL parameters of-a1kanes and -alkanols in vegetation
waxes from the transect
36
111.5.
Molecular marker concentrations in the transect aerosols
38
111.6.
Concentrations of molecular markers in source vegetation wax
(normalized to C
of n-alkanols)
40
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
transect regions
68
IV.5.
75
Sources of molecular markers in the transect aerosols
(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 of atmospheric
aerosols from rural areas. Thus, the study of the specific sources, compositions, and
transport of organic matter in the atmosphere are essential to understand the formation
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 chromatography with flame 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
soil sample
of the major representative vegetation from the same regions. One j.j,
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
AN APPLICATION OF IATROSCAN
CHAPTER II:
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 et al., 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
Designation
(cf. Fig. 11.1)
Location
Ambient
Temperature
Site Description
A-I
The Oregon
Coast Range
10-23
Canopy of a mixed coniferous
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
Coast Range
10-23
Canopy of an homogeneous alder
grove, and in the same
environment as A-I.
A-rn
The Oregon
Coast Range
10-23
Open range, and in the same
environment as A-I.
B-I
Willamette
20
Above tree line, near top of a ridge
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.
20
Canopy of a mixed coniferous
forest, 10 m below B-I, east of the
same populated agricultural and
industrial region as B-I.
National Forest
B-il
Wifiamette
National Forest
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
National Forest
5-13
Open range, surrounding
mountains with sites logged by
clear cutting and relatively clear or
grown over with small trees and
brush.
D-il
Umatilla
National Forest
13-28
Edge of a mixed coniferous forest,
within a few km of a four-lane
highway.
*Adapted from Standley, 1987.
Portland
Salem
A 1,11 & HI
0
OBI&ll
0D11
OCI'
CI
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-Nnitrosoguanidine (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 Distributions of Transect 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
Table 11.3. Analytical data for lipids in the transect aerosol particles.
Sample
Total extract
weight
(jig/rn3)
Lipid concentrations [%(j.tg/m3)]
Hydrocarbons
Coast Range
I.
Mixed coniferous forest
II. Alder grove
Aldehydes
and ketones
Alcohols
acids
Polar
lipids
18.2(0.4)
11.4(0.3)
15.0(0.4)
43.1(1.0)
Carboxylic1
2.4
3.2
2.0
12.3(0.3)
12.4(0.3)
14.0(0.3)
11.9(0.2)
27.4(0.6)
34.2(0.7)
4.6
4.3
7.9(0.4)
13.0(0.6)
7.4(0.3)
22.8(1.0)
5.9(0.3)
9.7(0.4)
13.8(0.6)
17.1(0.7)
64.9(3.0)
37.4(1.6)
Columbia Basin
I. Rowe Creek
II. Wilson Ranch
2.1
3.6
10.4(0.2)
41.4(1.5)
7.0(0.1)
10.2(0.4)
7.5(0.2)
5.1(0.2)
17.7(0.4)
9.4(0.3)
57.4(1.2)
33.9(1.2)
Umatilla National Forest
I. Open range
II. Edge of mixed
coniferous forest
3.6
4.2
16.5(0.6)
12.5(0.5)
15.7(0.6)
9.5(0.4)
7.5(0.3)
6.3(0.3)
20.8(0.7)
15.1(0.6)
39.5(1.4)
56.5(2.4)
ifi. Open range
-
-
-
-
Willamette National Forest
I.
II.
Abovetreeline
Mixedconiferousforest
1: As methyl esters.
2: Not detected.
C
11
F
F
F
C
F
Elution
Figure 11.2. Examples of Jatroscan analyses for aerosols from the transect 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 Willamette 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).
12
100
100
C'nnii
p
o
a
b
Wjlhqmctie I
CntI III
71
W,IImcite II
75
50
¶0
g
U
0
U
LI
a
25
U
U
A
Ii
C
1)
E
A
P
B
I 00
1)
E
P
100
Cnlnmhiiu I
Umiil1
p
CnItumI,i II
75
.g
C
Lipid Class
Lipid Class
so
d
I
UmtjIla II
75
50
g
U
U
g
LI
25
U
0
A
B
C
D
Lipid Class
E
P
A
B
C
I)
E
P
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.
Table 11.4. Analytical data of wax lipids in vegetation from the transect regions.
Sample (Region)
Lipid concentrations (%)
Hydrocarbons
Wax esters
Carboxylic1
acids
Aldehydes
and ketones
Alcohols
Polar
lipids
Coast Range
Moss
Salmonberry
AlderBark
AlderLeaves
Wood Fern
Sword Fern
Norway Spruce
Brewer Spruce
Douglas Fir
0.5
6.4
0.4
1.0
3.3
7.2
0.9
0.1
0.1
0.5
38.8
1.8
1.7
0.6
2.4
79.3
30.6
0.6
0.8
0.8
8.4
-
-
1.7
0.9
0.9
1.1
4.5
0.4
5.7
7.3
2.5
2.3
4.3
8.3
1.7
91.0
38.5
10.2
5.5
14.2
82.5
83.0
10.5
40.1
94.7
88.6
88.2
6.1
11.2
2.1
4.4
1.4
Willamette National Forest
Moss/Lichen
Rhododendron
Mountain Hemlock
Big-coneDouglasFir
BrewerSpruce
Plowed Soil
-
-
-
24.5
3.5
5.0
3.3
0.1
1.4
6.4
0.3
0.7
1.1
0.8
9.0
5.2
21.2
1.1
-
23.7
2.6
2.8
6.3
25.6
25.5
1.5
2.2
4.4
5.8
74.4
38.6
67.7
93.0
89.8
52.5
Table 11.4. continued
Sample (Region)
Lipid concentrations (%)
Hydrocarbons
Wax esters
Carboxylic1
acids
Aldehydes
and ketones
Alcohols
Polar
lipids
Columbia Basin
Sage
Juniper
Juniper/Sage Litter
Grass
5.7
0.1
0.8
18.0
0.4
0.2
0.1
0.1
0.3
6.8
0.4
1.0
10.2
5.2
0.2
0.6
5.4
2.9
2.5
0.5
18.0
0.8
0.1
0.7
0.2
0.5
1.1
5.6
2.0
20.7
92.4
93.6
95.5
39.1
Umatilla National Forest
Douglas Fir
"Green WaxyBush"
Elm
Alder
Fern
Laurel
2.1
Maple
38.8
PonderosaPine
White Fir
Douglas Fir
Pacific SilverFir
: As methyl esters.
2:
Not detected.
-
1.5
-
0.1
0.1
1.4
1.7
-
11.2
3.3
-
0.4
0.3
-
0.8
0.2
0.3
-
-
-
11.3
2.9
0.4
4.2
1.2
0.1
1.5
0.8
0.6
2.6
5.6
9.6
2.8
3.6
-
22.3
4.7
7.2
5.4
5.8
93.2
93.2
66.2
92.7
92.3
-
16.4
83.4
92.3
91.4
92.4
-
15
b
a
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 mm in hexane-diethyl ether (96:4).
16
100
-....-...--*
75
Moss
Salznorsbeny
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
a---
Mountain Hemlock
Rhododersfron
so
Big-enne Douglas Fir
I
25
BrewerSpnsce
a---
Plowed Sod
a----
Sage
0
100
Columbia Basin
-'
75
0
5°
1)
0
p
Juniper
a-
Juniper/S age Litter
#
Grass
25
0
100
--a-
Douglas Fir
75
-+--
Elm
50
a---
Green Waxy Bush
-'
Fan
0
U
U
0
25
Maple
j.
Ponderosa Pine
J.
\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 provide a 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), and one 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 plant waxes and in aerosol
particles exhibit pronounced even carbon number preferences (generally expressed as
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-today; 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
-AlkanoIs1
Coast Range
I. Mixed coniferous forest
a.
b.
c.
d.
II. Alder grove
a.
b.
C.
a.
HI. Open range
b.
c.
Regional average
Wiflgmette National Forest
I. Above tree line
a.
b.
c.
d.
e.
f.
II. Mixed coniferous forest a.
b.
C.
d.
Regional average
Total yield
(ng/m3)
(ng/m3)
0.66
0.69
0.14
0.16
1.27
1.30
0.21
0.45
0.74
1.16
0.21
1.05
0.81
0.72
0.89
Cge2
0.20
0.20
0.21
0.18
0.31
0.17
0.20
2.20
2.29
0.56
0.73
0.52
0.53
0.46
0.52
0.44
0.45
0.37
1.81
i.52
0.49
0.33
0.47
0.45
2.20
2.24
3.03
1.61
Q.40
co-Hydroxy Alkanoic
C1
14-32
14-32
14-30
14-32
12-34
12-34
12-34
12-34
12-34
12-34
12-34
22
20
26
26
32
32
26
20
24
24
14-36
14-36
14-36
14-36
14-36
14-36
14-34
14-34
14-34
14-34
14-36
26
26
26
26
26
26
26
26
26
22
25.2
25.6
Acids1
CPI
C14
C16
(C1632)
(pg/rn3)
(pg/rn3)
11.2
4.7
7.9
11.8
11.7
6.2
4.4
5.2
10.2
8.1
8.1
4.6
5.5
19.2
7.3
14.1
16.7
6.5
7.5
4.8
4.5
9.1
3
-
-
-
-
-
-
-
2.81
7.22
9.14
139.46
50.25
115.67
54.09
21.16
18.72
0.13
1.98
0.96
1.76
19.24
130.05
64.09
147.53
40.56
6.47
16.62
21.04
123.89
44.61
102.73
52.56
48.53
42.95
0.26
4.59
2.18
4.08
52.68
356.13
175.49
404.11
10.91
Table 111.1. continued
Sample
-A1kanols1
Columbia Basin
I. Rowe Creek
a.
b.
C.
d.
II. Wilson Ranch
a.
b.
C.
d.
e.
f.
Regional average
Umatilla National Forest
(ng/m3)
(ng/m3)
0.49
0.73
0.75
0.76
0.60
0.38
0.57
0.70
0.47
0.63
0.61
a.
b.
C.
0.80
d.
e.
f.
Regional average
1.17
1.47
1.57
1.41
d.
II. Edge of mixed
coniferous forest
As trimethylsilyl ethers.
Determined by GC/MS.
: Not detected.
2:
Cmax
1.62
1.32
2.2
0.9
1.9
0.93
a.
b.
c.
I. Open range
1:
Total yield
cange2
o-Flydroxy Atkanoic Acids'
Cmax
0.12
0.23
0.16
0.13
0.20
0.14
0.19
0.23
0.19
0.23
0.18
14-32
14-32
14-32
14-32
14-34
14-34
14-34
14-34
14-34
14-34
14-34
30
30
28
28
28
28
28
28
28
28
0.43
0.33
0.64
0.21
0.43
0.17
0.27
0.38
0.40
0.42
0.37
12-34
12-34
12-34
12-34
12-34
12-34
12-34
12-34
12-34
12-34
12-34
26
26
26
26
26
26
28
28
26
26
28.4
26.4
CPI
C14
C16
(C1&32)
(pg/rn3)
(pg/rn3)
13.3
8.5
7.4
6.0
9.6
12.2
12.2
13.7
16.6
15.2
11.5
6.26
5.57
8.74
8.84
2.38
0.84
3.04
4.37
1.65
2.78
4.45
9.11
8.10
12.70
12.84
5.02
1.79
6.46
9.27
3.50
5.91
7.47
12.5
12.8
14.0
15.3
12.6
10.2
14.7
7.78
7.56
14.41
13.96
17.98
13.38
8.77
20.23
3.73
33.15
24.74
16.64
38.32
7.05
20.3
10.4
8.9
13.2
9.50
18.01
19.28
20.24
12.85
36.52
38.30
24.11
25
Table 111.2. Analytical data for -aIkanols in vegetation waxes from the transect regions.
Sample (Region)
n-Alkanols1
Cge2
Coast Range
Moss
Salmonberry
Alder Bark
Alder Leaves
Wood Fern
Sword Fern
Norway Spruce
Norway Spruce Sap
Brewer Spruce
Brewer Spruce Sap
DouglasFir
16-32
12-36
15-28
14-32
14-32
16-32
18-35
Cm
28
26
22
24
24
24
26
..3
CPI (Ci3
7.0
29.6
8.3
9.7
14.2
6.2
4.0
-
-
24
3.0
26
24.9
11.0
10.3
16-30
16-30
15-34
16-30
16-30
26
22
26
26
24
24.8
32.5
4.5
6.5
4.0
4.0
10.3
16-30
12-32
14-30
16-34
12-32
22
26
22
26
28
9.4
4.4
4.3
24.3
14-32
12-32
Regional Average
Willamette National For
MosfLichen
Rhododendron
Mountain Hemlock
Big-cone Douglas Fir
Brewer Spruce
Regional Average
Columbia Basin
Sage
Juniper
Juniper/Sage Litter
Grass
Wilson Ranch Soil
Regional Average
Umatilla National Forest
Douglas Fir
Elm
Alder
Fern
Laurel
Maple
Ponderosa Pine
White Fir
Douglas Fir
Pacific Silver Fir
Regional Average
1: As trimethylsilyl ethers.
24.8
16-30
14-30
16-34
16-30
14-30
14-30
12-34
16-30
14-32
12-30
28
24
24
26
26
26
24
22
26
24
25.0
2: Determined by GC/MS.
19.2
12.3
5.6
21.0
9.5
13.3
7.1
8.7
10.6
8.2
8.2
3.2
9.5
: Not detected.
cq.
°'
i
C.I l
2t
04
02?
dccc
I.
020
Ic
24
02?
Id
lb
dccc
1.
lb
22
020
q.
00
lb
4414
0:
00?
__:1
0
02
21
Co4I4.nq.
Ic
0
20
Ccc
24
O?
Cc..?
I.
00
24 d.c..? c.
II
Ic
Cc.. 4.cc
00
24
dcc
.4
.4
30
°:L11L
00
.°:t. L
C.cmc.c.
24
30
30
0 _____
0 4
0
Cc,ce 2ccc
24
'rL
COOc,
ccc.
I
00.1
20
Ccc 4..,.
20
30
00
'0
24
Cc... 4.cc
Occc b
I
I?3'
.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 and source vegetation
waxes collected from the Coast Range.
27
044
037
.i
O0i
OJIihII.
°' wui.....,
I.
is
020
Or,
023
o.J
0
ii
is
Ii
I
W4O4I.
2
023
024
040
H
2
023-
O
040
044
00*
2
su..,,s
0
...
zs
ii
'
'-4...--,
I
24
:.
I
O____ 0
s.o.
2.
is
is
I
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.
°
OI
0 Z3
I0.*
14
3
C
24
to
020
21
C104
0 ___ 0
C
20
20
CI.'I.
30
0
30
C
0031 C
2!
30
21
023
0201
007
0
Co4
I
0.001
I 4
00
0
II'[I
01
2!
0
01
22
0100
0....
2.
co1.,
9...,
I .
004
01
0
40
Id
,_'
0001
0041
o
C4401
I
I.
!434
I
IIII
24
110.
111
.qiJ
I
0,2_I
0
Lr.ijid.jii
0
20
10
C
0
40
0
I
0
30
01
C
30
011
0
40
2?
C11.
101
C..9.
Oo.
00
20
__
00._I
0.3..
0..
20
0.n.
110
0
Jh111..
6
S
110
110
0.
0
20
30
40
Figure 1111.3. Histogram (carbon number versus concentration) disthbutions ofalkanols and ci-hydroxy alkanoic acids (") in the aerosols, source vegetation waxes
and soil collected from the Columbia Basin.
29
03
033
lb
022
21
z
lb
II
I
'I,-,
IiI
027
21
0I
'a
'I,-,
027
t-.,42.
2*
0110
*
21
Id
21
1
I.
lb
'III
0
02l
0
031
OS
l4l42
032
04
o zz
01
1
0
200
.l.ItI.
C
20
24.10W
30
,o
200
25
711
20
10
110
Ik,141111
C-
30
24
(11.
0.
U
020
0,,
501
022
UJL
:'
i..n.
I(24
21
:..
10
3
00
30l4l.
7--
00 47
22
1242.
230
lk1Wl.
-
a..111
24
7-.
711
I
50
50
50
2
0
;
it;i.
20
30
.,tII
00J.
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.
40
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 average Cm (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 from C12 to C36 with homologs > C20 predominant (Table 111.2, Figs.
ifi. 1 to 111.4). The Cm of ji-alkanols in representative vegetation varies from species
to species with C26 and C28 predominating. The average Cm of the transect vegetation
vary from 24.9 to 25.0. There is no significant increase in Cm
from 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. In order 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 examples are obscured
by geographical and environmental factors. For example, Douglas fir from the Coast
Range (C26) and from Umatilla National Forest (area I) (C) does show an 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. Brewer spruce
from the Coast Range and Willamette National Forest exhibits the same Cm
(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 the nalkanols is from C12 to C36 with the regional Cm averages ranging from 25.2 to 28.4
(Table 111.1, Figs. 111.1 to 111.4), which directly reflects the source vegetation. The
homologs <C20 appear to be derived from microbial sources, since they are not major
constituents of plant waxes (Figs. 111.1 to 111.4; Simoneit, 1977a; Simoneit and
Mazurek, 1982a, b). A general trend of increasing Cm can be observed from the
cooler coast to the northeastern desert (Table 111.1; Figs. 111.1 to 111.4). In comparison,
-alkanols of Harmattan aerosols of Nigeria have Cmax at C, C and C30, with C30
predominant, which matches the composite vegetation wax of that region (Cox et ad.,
1982; Simoneit et al., 1988). This indicates an input of source vegetation from the
desert climate of that area (Simoneit et ad., 1988). The Cm of n-alkanols in aerosols
of n-alkanols in
over the eastern Atlantic Ocean is at C28 (Simoneit, 1977a). The
aerosols from 30 -70°S in the South Atlantic is bimodal at C16 and C26, with C16
indicating marine source input and C26 indicating terrestrial source input (Simoneit et al.,
1991c). The interpretation of the -a1kanol homolog distributions over the Atlantic in
terms of climate indicates a temperate to arctic range (Simoneit et ad., 1991c; Simoneit,
1977a). The
of the n-alkanols in aerosols from the Australian Blue Mountains is
C26
which matches the
of composited vegetation of the region (Simoneit et ad.,
1991b) and indicates temperate to desert climates. The ACL parameters of -aIkanes and
-a1kanols discussed later also support the conclusions above.
Free üi-hydroxy C14 and C16 alkanoic acids have been found in the waxes of the
Gymnosperms and also the Angiosperms of the source vegetation (Figs. 111.1 to
111.5) and these compounds are present in the corresponding aerosols ranging from 0.13
to 404.11 pg/rn3 (Table 111.1). w-Hydroxy C12, C14, and C16 alkanoic acids from the
estolide fraction of cuticular waxes of the Cupressaceae and Pinaceae have been studied
(Herbin and Robins, 1968; Herbin and Sharma, 1969). These estolides, neutral
polyesters of 4-6 molecules of 0-hydroxy C12, C14, C16, and C18 alkanoic 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 from C25 to C29 with a Cm
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
50.375
103
-L5
89
II
99
131
58
188
315
185
257
280
158
299
lF'IF r'1r
250
1FIl
358
388
311
tee. a
b
58.3
73
103
55
343
122
IL
50
P11r
180
)
175 192 289
231
1F
i
F
280
158
327k
25:
388
250
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
[00
58
ies
227
35
258
200
150
243
28.1
489424
10.8
4O
8
nil z+
C7
1 Jc3I
C29
tii/ Z
25
'
LJ (i
C28
C
A
1933
I 9:32
1.33!
2878
2047
Ri
1933
1831
1
18')8
rtA_
1260 1891
I-r
'50
1
1OO
1361
1950
2812;Li
2038
2)58
SCAN-+
Figure 1116. Example of: (a) mass specnum of methyl 3-oxohexacosanoate;
(b) fragmentogram of-C to C29 3-oxo-alkanoic acid methyl esters.
210
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 plant nalkane 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 the area
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 Forest are
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, which are
35
Table 111.3. The ACL parameters of-alkanes and -a1kanols in the transect aerosols.
-A1kane ACL*
Sample
Coast Range
I.
Mixed coniferous forest a.
b.
c.
d.
11.
Alder grove
a.
b.
c.
a.
III. Open range
b.
c.
Regional average
Willamette National Forest
I. Above tree line
a.
b.
c.
d.
11. Mixed coniferous forest
e.
f.
a.
b.
c.
d.
Regional average
Columbia Basin
I. Rowe Creek
a.
b.
c.
d.
H. Wilson Ranch
a.
b.
c.
d.
e.
f.
Regional average
Umatilla National Forest
I. Open range
a.
b.
c.
d.
11. Edge of mixed
coniferous forest
a.
b.
c.
d.
e.
f.
Regional average
ta of Standley, 1987.
-A1kanol ACL
28.7
28.9
28.8
28.5
28.7
28.7
28.7
29.0
29.0
29.1
28.8
26.6
26.8
27.0
27.3
28.2
27.7
27.2
27.8
27.8
27.3
27.4
28.6
28.6
29.8
29.6
29.3
29.9
28.7
28.6
28.4
28.6
29.0
27.4
27.2
26.3
26.4
26.4
26.4
27.4
27.3
27.6
27.6
27.0
29.0
29.1
28.7
28.6
28.8
28.8
28.7
28.7
28.8
28.9
28.8
28.3
28.8
27.8
27.7
28.0
28.0
27.7
27.7
27.7
27.5
27.9
29.3
29.0
29.3
29.1
29.0
29.2
28.9
28.8
29.2
29.0
29.1
27.7
27.6
27.6
27.5
27.4
27.5
27.5
27.4
27.2
27.3
27.5
Table 111.4.
The ACL parameters of-a1kanes and -a1kanols in vegetation waxes
from the transect.
Sample (Region)
Coast Range
Moss
Salmonberry
AlderBark
Alder Leaves
Wood Fern
Sword Fern
Norway Spruce
Norway Spruce Sap
Brewer Spruce
Brewer Spruce Sap
Douglas Fir
Regional Average
Willamette National Forest
Moss/Lichen
Rhododendron
Mountain Hemlock
Big-cone Douglas Fir
Brewer Spruce
Regional Average
Columbia Basin
Sage
Juniper
Juniper/Sage Litter
Grass
Wilson Ranch Soil
Regional Average
Umatilla National Forest
Douglas Fir
"Green Waxy Bush"
Elm
Alder
Fern
Laurel
Maple
Ponderosa Pine
White Fir
Douglas Fir
Pacific Silver Fir
Regional Average
-A1kane ACL*
-A1kanol ACL
27.4
28.2
30.1
30.5
27.9
26.7
27.7
27.1
26.9
26.7
27.3
28.6
28.2
28.1
29.5
-
-
28.7
28.9
27.6
27.3
27.5
30.5
29.8
28.5
28.1
28.9
26.1
28.3
28.0
27.0
27.5
27.4
29.2
28.7
29.6
27.4
27.0
26.7
26.2
27.9
27.0
28.9
29.1
28.4
28.9
29.0
30.0
29.2
29.0
27.4
28.2
28.5
28.6
27.9
28.7
-: Not detected.
*: Calculated from data of Standley, 1987.
28.4
-
27.8
27.2
27.7
26.9
27.2
27.8
27.8
26.7
27.1
27.5
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-5apodocarpa-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, Hawthorne et
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'
Name
Concentration(pg/m3)
Molecular
weight2
Composition
of parent
compound
Diterpenoids
Unknown 111.1
1 3-Isopropyl-5a-podocarpa-
6,8,1L13-tetraen-16-oic acid (I)3(L)4
1 3-Isopropyl-5a-podocarpa-
6,8,11,13tetraen16oicacid*(I)
Dehydroabietic acid (H)(S)
Dehydroabieticacid*(II)
Unknown 111.2
7-Hydroxydehydroabieticacid(llI)(L)
Calocedrin(IV)(I)
7-Oxodehydroabieticacid(V)(S)
Lignan (mixture)
3-Oxodehydroabietic acid(VII)(I)
Unknown 111.3 (Mixture)
Unknown 111.4
Unknown 111.5
Phytosterols
1
Cholesterol(VH1)3(S)4
2 Brassicasterol (LX)(I)
3 Campesterol (X)(S)
4 Stigmasterol (X1)(S)
6
-Sitosterol (XII)(S)
H
I
II
I
-
-
-
-
-
?
3.6
312
C20H2602
4.7
9.9
0.9
2.3
312
314
314
358
402
368
328
386
C20H2602
C20H2802
C20H2802
4.7
5.8
48.8
9.9
11.3
11.3
34.4
55.1
1.5
3.7
0.1
4.1
8.9
0.2
0.9
3.4
43.4
0.3
0.1
326
328
C2oHO3
?
C20H2803
C20H,607
C20H260-3
C22H2606
C20112603
?
380
398
?
458
470
472
484
486
C27H460
?
C2811460
C28H480
C29H480
C29H500
-
-
1.8
12.2
-
3.2
0.9
0.2
0.8
0.1
4.4
5.5
3.5
11.8
1.2
1.2
3.6
-
6.6
-
1.8
-
-
4.9
4.9
-
137.1
15.3
11.7
15.3
11.7
40.8 71.4
390.8 551.4
1.4
1.6
1.3
8.4
0.2
9.7
0.9
2.9
0.1
2.2
0.9
18.7
14.7
17.2
27.1
3.0
1.3
0.3
0.3
tr.
0.2
1.1
3.2
6.5
0.7
3.3
0.1
tr.
0.8
1.0
0.5
0.1
0.7
Umatilla
I
322
7-Oxo- 1 3-isopropylpodocarpa-
5,8,1l,13-teiraen-15-oicacid(V1)(I)
III
II
I
Columbia
Basin
Willamette
Coast
1.4
0.2
0.5
0.2
1.7
11.6
364.6 159.7
9.0
7.7
4409.0 66.7
1.5
1.2
3.4
0.2
0.6
0.3
18.6
14.2
12.3
-
1.0
0.4
2.1
1.3
0.5
28.4
1.7
16.8
14.0
0.8
-
-
3.4
9.7
2.4
0.3
27.5
10.8
18.4
50.2
2.6
-
0.8
II
12.1
0.4
484.2
0.8
1.4
0.4
14.4
-
0.4
7.3
0.4
3.9
0.9
0.5
2.8
0.5
3.0
0.7
0.7
4.6
0.8
0.9
0.5
8.4
0.8
0.3
4.0
0.4
0.3
-
0.5
-
1.2
0.1
0.3
Table 111.5. continued
Compound1
Name
Concentration(pg/m3)
Molecular
weight2
5
Triterrenoids
Taraxerone (XIII)(L)
7
-AmyrinUV)(S)
8
9
10
11
12
13
14
15
16
17
18
19
y-Taraxasterol (XV)(S)
a-Amyrin(XVI)(S)
3ct-Lupeol (XVH)(S)
Diplopterol (XVHI)(S)
Erythrodiol (XIX)(S)
Friedelin (XX)(S)
Oleanonic acid (XXI)(L)
Betulinic acid (XXII)(S)
Oleanolicacid(XXIII)(S)
Ursonic acid (XXIV)(I)
Ursolic acid (XXV)(S)
Morolic acid (XXVI)(S)
424
498
498
498
498
500
586
426
468
542
542
468
542
542
Composition
of parent
compound
C30H480
C30H500
C30H500
C30H500
C30H500
I
II
III
0.3
1.9
-
H
0.3
2:
I
II
8.4
0.9
0.9
0.7
0.5
0.3
0.2
6.0
0.5
0.9
0.6
0.5
0.3
-
0.1
1.2
-
-
-
0.8
-
-
-
-
-
0.5
2.1
0.3
2.6
1.7
0.6
1.6
0.4
0.7
1.5
0.6
-
0.9
3.7
1.2
3.0
2.1
-
Compounds are listed in the order that they elute on a DB-5 (J & W Scientific) 0.25mm x 30m capillary column
Acids are given as methyl or trimethylsilyl ester derivatives and alcohols as trimethylsilyl ethers.
: Refer to chemical structures cited in Appendix V.
: I =Interpreted, L = Literature reference and S = Standard compound retention and mass spectrum.
*: Total amount from both acid (cf. Table V.5, Standley, 1987) and alcohol fractions.
tr. trace.
- = not detected.
1:
Umatilla
H
I
C30114603
C30H4803
C30H4803
Columbia
Basin
-
C3011520
C30H5002
C30H500
C30H4603
C30H4803
C30H4803
Willamette
Coast
Table 111.6. Concentrations of molecular markers in source vegetation wax (normalized to
Cmax of n-alkanols)
Sample (Region)
Molecular markers (cf. Table 111.5)
Phytosterols
Triterpenoids
1
2
3
4
6
5
-'
0.3
-
-
-
-
-
-
0.01 0.03 0.4 -
-
-
9
7
8
1.3
0.9 0.4
10
11
12
13
-
14
16
15
17
18
19
-
Coast Range
Moss
Salmonberry
Alder Bark
Alder Leaves
Wood Fern
Sword Fern
Norway Spruce
Brewer Spruce
Douglas Fir
-
-
-
-
-
-
-
-
0.6 0.3 0.6 0.2
-
-
0.5-0.4
1.0
2.28.89.3-
-
1.5
-
-
-
-
-
-
6.0
-
0.02-
0.2
0.3
0.5
0.6 -
-
0.1-
-
-
-
9.1
4.9
-
-
-
1.62 -
-
-
-
-
-
6.2 -
tr.
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
1.4
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
0.30.10.20.20.4
-
-
-
-
1.7 -
-
-
-
-
-
-
-
-
-
-
-
illamette National For
Moss/Lichen
Rhododendron
Mountain Hemlock
Big-cone Douglas Fir
Brewer Spruce
-
0.6
3.0 -
-
-
-
-
19.38.2 29.9 25.0 40.5-
-
10.4-
-
-
-
0.2
-
Table ffl.6. continued
Sample (Region)
Molecular markers (cf. Table 111.5)
Phytosterols
Triterpenoids
1
2
3
4
6
.1
-
-
-
-
9.8
3.2
12.5-
5
7
8
-
0.5
-
9
10
11
1.12
-
-
12
13
14
15
16
17
18
19
Columbia Basin
Sage
Juniper
Juniper/Sage Litter
Grass
WilsonRanchSoil
10.0
6.7
0.02 0.01 0.060.2 0.2 0.8 0.4 3.2
-
0.7
-
-
-
-
0.03
-
tr.
0.01
-
-
-
-
-
0.01
0.01
-
Umatilla National Forest
Douglas Fir
"Green Waxy Bush"
-
-
Elm
Alder
Ponderosa Pine
White Fir
Douglas Fir
Pacific SilverFir
0.6 0.1
0.4 0.1
0.1
0.01
0.7-
1.1
3.1
2.2
-
0.2
1.5
2.4 3.1
-
0.21.4-
-
0.1-
0.2
-
-
-
0.2
0.1
-
-
-
0.04
-
-
11.2-
0.1
12.5 0.2 22.3-
-
-
0.2
-
1.4
-
-
1.1
0.1
0.4 5.9 0.8
-
-
1.0
-
1: Not detectable.
Bold numbers designate highest concentration.
2:
-
-
0.5
Fern
Laurel
Maple
7.9
-
-
-
-
-
-
-
-
-
42
it!
a
mit
.1:
(t,
ii
mit
235
I
ti!
b
mit
.1:
mit
*
ii
iW
?S
%
urns
SCAM
uie
255
I2
1
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-tetraen16-oic acid methyl ester, 1*: isomer of 13-isopropyl-5a-podocarpa-6,8,l 1,13tetraen-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
LW
2/2
Vt,
IlI
VNN
t2
it'
13S
L
b
2/2
1285
tINS
1355
Vt
it
d
I
.12
3
I
'V
'V
.1:
.1:
J
teas
ties
1215
1355
SCAN.
Vt'
I
'
l55
liNe
1285
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-isopropylpodocarpa5,8,1 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 from C27 to
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) indicates an
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 of meats
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 show a general decrease
from the coast to the northeastern desert (Table 111.5). This may 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 soil are 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 National Forest
are quite different from the others of the transect. This may be indicate an additional
45
55
1.0
11.8
isi Rooq. i
pg/rn3
pg/rn
pg/rn
0
0
25
30
C-
III
0
C
25
00
Aldei 8oA
I
25
001
i
0
I
I
30
C00
Coasl Ronq.
Wood Fein
50
50
I
0-j-
0-f-
25
100
C.-
00
Co
25
i
I
C
I
30
Range
81.,Iu Spucs
50
I
30
C-
S,.od Fun
50
25
25
30
C-
CoccI Ronq.
6
01
I
30
Coosl Rang.
Mou
50
l
C-
25
30
00
00 CooReie.
3
0.5
5.9
2.7
CoccI Rang.
I
I
30
I
50
01
25
I
I
C
I
I
i
30
01
25
I
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
100
%
25
C100
WiHomelts
C-
WIllamells
Bq.cons Douqlas Fir
Rhododandron
1
50-i
01
25
V
C
I
i
30
1
Willamette
Brewer Spruce
6
50
50
I
I00
30
01
25
i
C
I
i
I
30
C
It
25
I
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.
0.90
1.70
Columbia
Basin I
pg/iTs
pg/rn3
0.85
0.45
01-
0
25
C
00
Co4urnbla Bairn
Columbia Basin
l0(
0J
25
30
Columbia Bairn
01
C
I
30
ColumbIa Basin
Wilson Ranch Soil
50
5<
g
001
Grass
JurA,ev/Soqs Lillar
50-I
C
25
i
C
0
I
30
I;
25
C
lI
O
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
30
25
C-
C
100
L)noIIIIo
Daqlon Fir
I.
50
00
100
f.
1.
50
50
0-j25
C-
30
C
25
00
100
30
C
25
I00
thnotIIIo
Pnsdsro,a Pins
.
Douqias Fir
50
0J
25
I
C
't
30
i
30
Umoillia
PocIlic Sllsr Fir
1
50
01
25
It
i
C
I
i
30
i
01
25
i
C
I
I
30
1
01
25
Ii
i
C
I
i
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
:
IS
I4I
t
b
I9S
I4
II
'XXX
IX
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
40
60
Re1ativ
20
C29
C27
Figure ifi. 14. Ternary diagram of phytosterols (C27, C, C) in the aerosols collected
from a ansect 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
40
60
Retau
20
C29
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 were also detected in
surface soil of the Columbia Basin. Triterpenoids (primarily amyrins) are
the j
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 et al., 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 in Cm in the -a1kanol homologs of the aerosols is observed along
the transect from the cooler coast to the warmer desert areas. The regional average 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
C1
2831
LXV
LXIII
R
d
z
283
LXIII
e
283
I
152a
1548
IL
158
I
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-hydroxy C14 and C16 alkanoic
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 GCMS 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 Cm as 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 with Cm 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
with Cm of 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-10-ones
-Alkan-2-ones1
Cmax
Cmax
C(pg/m3)
In-chain-alcohols
Saturated
Aldehydes
Unsaturated
Aldehydes
Cmax
Cmax
Cmax
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
Coast Range
Mixed coniferous forest
II. Alder grove
III. Open range
29
29
29
I.
8.7
253.4
35.2
Willamette National Forest
Abovetreeline
II. Mixedconiferousforest
I.
na3
n.a.
n.a.
n.a.
n.a.
n.a.
29
29
6.5
10.6
29
29
2.0
9.7
Columbia Basin
Rowe Creek
II. Wilson Ranch
I.
Umatilla National Forest
Open range
II. Edge of mixed coniferous forest
I.
: Determined by GCIMS.
Not detected.
: Not analyzed.
2:
Table IV.2. Sources of the homologous compounds from the transect regions
Sample (Region)
-AIkan-2-ones1
n-Alkan-10-ones
Saturated
Aldehydes
In-chain-alcohols
Unsaturated
Aldehydes
Coast Range
Moss
Salmonbeny
Alder Bark
Alder Leaves
Wood Fern
Sword Fern
Norway Spruce
Norway Spruce Sap
Brewer Spruce
Brewer Spruce Sap
Douglas Fir
25-29
28(30)
-
-
n.a.
n.a.
n.a.
n.a.
31
17-26
24
-
-
n.a.
n.a.
n.a.
n.a.
na.
n.a.
29
30
30
29
29-31
27-37
28-30
28-29
28
28
29
n.a.
n.a.
n.a.
27-31
29
30-31
n.a.
29
-
n.a.3
n.a.
n.a.
n.a.
n.a.
n.a.
-
-
-
-
28-30
-
-
27-29
-
-
29
-
-
-
31
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
29
29
29
29
30-34
30
Wilbmette National Forest
Moss/Lichen
Rhododendron
Mountain Hemlock
Big-cone Douglas Fir
Brewer Spruce
-
Table IV.2. continued
Sample (Region)
-Alkan-10-ones
n-Alkan-2-ones1
Crange
Cmax
Crane
.2
-
-
-
n.a.3
Unsaturated
Aldehydes
Saturated
Aldehydes
In-chain-alcohols
Cmax
Crane
Cmax
Cange
Cmax
Crange
Cmax
-
-
-
-
-
-
-
-
29-3 1
29
-
-
-
-
28-32
30
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
25-35
27
-
-
27-29
27
-
34
-
-
-
34
-
-
-
-
-
-
-
-
-
29
29
29-30
29
-
-
-
-
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
Alder
-
-
27-33
31
29
29
-
-
-
-
Fern
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
Laurel
Maple
-
-
17-29
29
25-29
29
-
-
-
-
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
-
-
29
29
-
-
-
-
17-29
17-29
-
-
29
29
-
-
28-32
28-30
30
30
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
Columbia Basin
Sage
Juniper
Juniper/Sage Litter
Grass
Wilson Ranch Soil
Umatilla National Forest
Douglas Fir
"Green Waxy Bush"
Em
Ponderosa Pine
White Fir
Douglas Fir
Pacific SilverFir
: Detennined by GCIMS.
Not detected.
: Not analyzed.
2:
1
53
al
71
543.3
292
323
i
L
3.3
1.7
108.3
b
59.3
U
L.
so
188.0
211
L
250
2438
1)43
3439
is.o:
1
352365
4543
408
358
458
608
558
5438
r e.ax
108.3
153
c
63
37
59.3
1g7
iii
I
1L T
tj
108
50
Ij1 J.
r.11F?° !..
23)
1543
3438
2543
33.
1.7
M-t8-Z8
378
j
359
t
4843
458
598
550
Figure IV.1. Examples of homolog mass spectra: (a) C27
(b) C31 -aIkan-1O-one; (c) C in-chain alcohol.
698
-a1kan-2-one;
61
distributions are bimodal with Cm at C19 or C21, and C29, C31, or C33 (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
Cm mainly at C29 (cf. Table IV.2; Fig. IV.lb). The patterns of -a1kan-10-ones in the
transect aerosols (C
at
C29)
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-chainalcohols have been detected from many species of source vegetation in the transect
regions with carbon number ranges from C27 to C37 and Cm at C29 and 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 the same chain
lengths as the free alcohols, occur in only minor quantities in epicuticular waxes
(Tulloch, 1976). Aldehydes are present at small amounts in red alder leaf wax with a
carbon number range from C17 to C26 and Cm at C24 (Table P1.2; Fig. IV.2a). In
62
20.8)
57
188.81
I
a3
7132
se.a-
1
287
LI I.
L16I38 i5
a it
j
I
I1k 14
4! II
358
258
288
188
58
222
225
i
5.8 -!
2.5
M-I8
M-L3-28 418
398
362
J
I
434M
!II
4e3
see
458
28.
188.8
b
58.8
83
69
I
313
1
345
II111 125
LI
149
IlL
,
157
is
222
28
279
18S
334
I
58
188
158
280
258
450
500
550
389
358
5.8
2.5-1
48
363
377 388
'I
480
Figure IV.2. Examples of homolog mass speca: (a) .-triacontana1;
(b) -octacos-6-ena1.
60
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 a Cm at 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 to nalkanoic 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 and Cm at 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 a Cmax of C31, and in Douglas fir of Umatilla
National Forest I and II from C27 to C31 with a Cmax of C3l(27) and from C27 to C37
with a Cm of 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 C have
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
Molecular
weight2
Composition
of parent
compound
Coast
I
Sesguiterpenoids
Bicycic sesquiterpenone
(e.g. XXVII)3(I)4
4
Diterpenoids
Unknown IV.1
5
Manoyloxide*(XXX)(L)
6
7
Epi-manoyl oxide* (XXXI)(L)
Pimaric acid(XXXII)(S)
Unknown IV.2
8
2
3
9
10
11
12
13
14
15
16
Anthropogenic
2,5-Bis(l ,1-dimethylpropyl)2,5-cyclohexadiene- 1 ,4-dione
(XXVIII)(S)
Phenanthrene (XXIX)(S)
Chrysene (XXXIH)(S)
Tnterpenoids
Norlupeol (XXXI V)3(S)4
Amyrin* (XIV)(S)
Unknown IV.3
aAmyrin* (XVI)(S)
Unknown IV.4
Unknown IV.5
Friedelin* (XX)(S)
220
C15H240
346
290
290
316
362
C21H3004
248
C16H2402
C14H10
C18H12
178
228
412
426
424
426
?
440
426
C20HO
C20HO
-
-
-
0.4
0.3
11.4
6.9
2.4
9.1
14.8
-
C20H3002
III
II
I
1.7
0.7
-
-
5.2
1.4
0.2
1.0
7.0
0.8
0.6
2.3
Columbia
Basin
Willamette
-
-
-
-
C29H480
-
-
-
C30H500
C30H480
-
-
-
-
-
-
C30H500
-
-
-
?
-
-
-
C30H4802
C30H500
-
-
-
-
-
-
I
II
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
Umatilla
II
I
-
-
5.2
6.0
3.9
1.3
62.4
4.8
-
-
21.7
40.4
2.4
6.3
-
3.4
-
3.3
18.0
19.7
2.2
1.7
-
12.0
-
-
-
-
-
-
-
-
II
I
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
8.8
2.1
3.0
4.4
Table IV.3. continued
Compound1
Name
Conceniraiion(pg/m3)
Molecular
weight2
Composition
of parent
compound
I
17
18
19
20
21
22
23
24
25
II
III
I
II
-Amyrone (XXXV)(I)
a-Amyrone (XXXVI)(I)
424
424
C30H480
-
CH48O
-
-
n.a.
n.a.
n.a.
n.a.
3:4-seco-3--nor-olean12-en-2-oic acid (XXXVII)(I)
3 :4-seco-olean- 1 2-en-3-oic acid
444
C29H5002
-
-
-
n.a.
n.a.
456
C30H5002
-
-
-
n.a.
n.a.
456
456
456
424
428
C30H5002
C30H5002
C30H5002
C30H480
C30H520
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
n.a.
(XXXVIII)(I)
Dihydmcanaric acid
(XXXIX)(I)
Unknown IV.7
Dihydroburic acid (XL)(I)
Taraxerone* (XIII)(I)
Friedelinol (XLII)(I)
-
-
Columbia
Basin
Willamette
Coast
-
I
II
Umatilla
I
II
-
-
-
-
Compounds are listed in the order that they elute on a DB-5 (J & W Scientific) 0.25mm x 30m capillary column.
Acids are given as methyl ester derivatives.
: Refer to chemical structures cited in Appendix V.
: I =Interpreted, L = Literature reference and S = Standard compound retention and mass spectrum.
*: Compounds also found in alcohol fractions.
tr. = trace.
- = not detected.
n.a. = not analyzed.
1:
2
LJ
180.8
55
aH 63a3
58.8
111
II
125
139
Ll$
I
58
100
157
213
185
239
269 285237
323 341
I
158
288
258
388
350
450
588
558
608
658
188.0,
so. a
b cd
3638
TINE-F
Figure P1.3. Example of: (a) mass spectrum of the cluster of C32 wax esters with
acid/alcohol moieties of C14118, 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, and c
indicating the C27, C29 and C31 -alkanes, d and e indicating the C31 and C33 -a1kan10-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
+ 2lIj ions 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 Cm at
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 Cm at 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 injected into the 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.
Wax Esters
Sample
(Region)
Crange'
Cmax
34-38
36-44
34-38
32-44
34-38
.2
29-50
n.d.3
34-38
38
42
n.d.
Acid
CPI(C28.50)
Alcohol
Crange
Cmax
Crange
Cmax
16-22
14-22
16
16
12-22
16-26
22
26
-
-
-
-
-
-
-
-
00
-
-
-
-
-
-
-
-
-
-
42
n.d.
2.6
n.d.
20.4
n.d.
36-38
38
34-44
38
Coast Range
Moss
Salmonberry
Alder Bark
Alder Leaves
Wood Fern
Sword Fern
Norway Spruce
Norway Spruce Sap
Brewer Spruce
Brewer Spruce Sap
Douglas Fir
38
36
38
00
29.4
23.0
87.2
12-26
16
12-30
26
n.d.
n.d.
n.d.
n.d.
-
-
-
-
n.d.
n.d.
n.d.
n.d.
15.8
-
-
-
-
13.2
-
-
-
-
40
43.0
-
-
-
-
38
107.7
22-36
30,32
6-8
8,6
n.d.
36
Willamette National Forest
Moss/Lichen
Rhododendron
Mountain Hemlock
Big-cone Douglas Fir
Brewer Spruce
-
34-41
30-42
-
-
Table IV.4. continued
Wax Esters
Sample
(Region)
Acid
CPI(C28..50)
Alcohol
Crange
Cmax
Crange
-
-
-
12-34
32
6-18
6
-
-
-
-
-
14-32
30
6-20
-
-
-
-
-
-
-
cange'
Cmax
34-38
28-46
34-38
36
38
38
-
-
32-42
34-44
34-42
34-46
34-38
30-44
36-42
40
105.9
38
8.0
40
13.5
-
38
38
45.8
2.3
42
42
17.7
00
-
-
-
34-40
28-42
38
38
-
-
Cmax
Columbia Basin
Sage
Juniper
Juniper/Sage Litter
Grass
Wilson Ranch Soil
4.6
21.9
12.4
-
-
-
-
matilla National For
Douglas Fir
"Green Waxy Bush"
Elm
Alder
Fern
Laurel
Maple
Ponderosa Pine
White Fir
Douglas Fir
Pacific Silver Fir
1: Determined by GC/MS.
2: Not determined.
3: Not detected
8.3
83.0
-
10
24
14-18
14
16-26
-
-
-
14-22
16
8-16
-
-
-
-
-
-
-
-
-
-
-
-
16-32
30
6-16
-
-
-
-
26
8
-
70
100
100
38
Coøst Range
00
42
00
38
Soimonb.try
Coast Rang.
Coast Rang.
1
Coast Rang.
I
Aid., t_ioyii
Aids, 6a,lt
.,.
50
50
IIJJ1
00
38
03Ii,
Coast Rang.
Coast Rang.
'-i
30
42
0-f-i
H
C
too -
Coast Rang.
Naay
ad Fits
0f
i'i'ii
40
30
50
30
OO
Ots.., Spnacs
C
40
50
Coast Rang.
Douglas Fit
Spruc.
30
0
50
%
,.
So
So
..fl
50
Figure J1f4 Histogram (carbon number versus concentration) distributions of wax
esters in the source vegetation wax collected from the Coast Range.
71
100
WIIto,n.Iis
38
Rhododendron
,.
50
100
So-I
100
WUlomittu
Bb -cone
Douqloi Fir
40
II
.
II
50
0 !.i.I1!tttIi
30
C
40
WIllomsile
Brewer Spruce
50
1
II
° II.11rI.l,I,t.I.i.1
30
40
50
C
Figure P1.5. Histogram (carbon number versus concentration) distributions of wax
esters in the source vegetation wax collected from the Willamette National Forest.
72
%
50
0
40
30
38
50
CtOO
ColumbIa
Basin Junipir
1
38 Columbia Biin
Junlpsr/ Sage
Lit tsr
50
50
0
30
C
40
0
50
30
40
C-
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 I UmatiII
I
Oouq$ai
N..dle,
1.
0-i-,
30
C
40
0
-I
50
C
40
30
CO
CO
CO
50
t.
30
C
42
CO
0
U.,.iIUl
So
50
50
0
0
40
30
50
40
C-
40
30
50
50
C100
100
LursI
f.
50
50
o
30
C
40
50
0
50
30
C
40
50
0
50
30
C
40
0
50
30
C
40
Figure IV.7. Histogram (carbon number versus concentration) distributions of wax
esters in the source vegetation wax collected from the Utmitilla National Forest.
50
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
ubiquitous occurrence 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
1
Sesguiterpenoids
Bicyclic sesquiterpenone
(e.g. XXVII)3(I)4
C15H240
ifl,192,205,220
4
Diterpenoids
Unknown IV.1
C21H3004
25.,269,33 1,346
5
Manoyl oxide(XXX)(L)
C20H340
55,177,192,257,275,290
6
Epi-manoyl oxide(XXXI)(L)
C20H340
5.5,177,192,257,275,290
7
8
Pimaric acid(XXXII)(S)
Unknown IV.2
C20H3002
1,133,180,241,301,316
251,362
Composition
of parent
compound
?
Key ions and molecular
weight2
Source
?
Douglas Fir
Grass
Brewer Spruce
White Fir
Brewer Spruce
White Fir
Sword Fern
Douglas Fir
Red Alder
Brewer Spruce
Laurel
2
3
9
Anthropogenic
2,5-Bis( 1,1 -dimethylpropyl)2,5-cyclohexadiene- 1 ,4-dione
(XXVIII)(S)
Phenanthrene(XXIX)(S)
Chrysene(XXXIII)(S)
163,177,191,205,221,233,248
Comments
C16H2402
C14H10
C18H12
fl
114,2
Antioxidant Product
Combustion
Combustion
C29H480
135,175,400,412
Salmonberry
Small
Trace
Major
Major
Major
Major
Small
Major
Small
Small
Small
Triterpenoids
10
Norlupeol(XXXIV)3(S)4
Small
Ui
Table IV.5. continued
No.
Name1
Composition
of parent
compound
Key ions and molecular
weight2
Source
Comments
11
-Amyrin(X1V)(S)
C30H500
189,203,218,393,408,426
12
13
Unknown IV.3
a-Amyrin(XVI)(S)
C30H480
C30H500
123,424
Laurel
Laurel
189,203,218,393,408,426
Grass
C30H4802
C30H500
189,204,218,269,393,408,?
177,189,204,425,440
5,41 1,426
Red Alder
Laurel
Red Alder
Wilson Ranch Soil
Norway Spruce
C301T480
189,2Q3,2j,409,424
C30H480
189,203,218,409,424
Grass
Grass
Trace
Trace
Trace
Trace
Trace
Trace
Trace
Trace
Major
Major
Trace
Trace
C29H5002
177,189,203,218,369,429,444
177,189,203,218,369,441,456
Moss
Moss
Major
Major
14
15
16
17
18
19
20
21
Unknown IV.4
Unknown IV.5
Friedelin(XX)(S)
l-Amyrone(XXXV)(I)
a-Amyrone(XXXVI)(I)
3 :4-seco-3-nor-olean12-en-2-oic acid(XXXVII)(I)
3:4-seco-olean- 12-en-3-oic
acid (XXX VIII)(I)
Dihydrocanaric acid
?
Grass
Red Alder
C30H5002
(XXXIX)(I)
Moss
95,109,189,203,218,441,456
C30H5002
Unknown IV.7
Moss
204,245,441,456
C30H5002
23
Dihydroburic acid(XL)(I)
Moss
189,203,218,369,441,456
C30H5002
24
Taraxerone(XIH)(I)
Sword Fern
95,189,205,313,409,424
C30H480
25
Fredelinol(XLII)(I)
Sword Fern
55,95,135,175,413,428
C30H520
: Compounds are listed in the order same as in Table IV.4.
2: Acids are geven as methylesters.
: Refer to chemical structures cited in Appendix V.
: I Interpreted, L = Literature reference and S = Standard compound retention and mass
spectrum.
22
Major
Major
Major
Small
Small
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-2ones 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-amyrones are 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 Cm in 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).
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APPENDICES
APPENDIX I:
Relevant Formulas and Calculations
1
CPI (Carbon Preference Index) of n-alkanols
Cl2 + C14 + .. + C34
[Ceven]
cpi=
=
C13+C15++C33
[Cd]
'1
CPI (Carbon Preference Index) of wax esters
[Ceveni
CPI=
3.
[C]
C28 + C30 +
+ C50
C29 + C31 +
+ C49
=
"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
nq Inc
nq/m
Coasl flange
Coast flange
020
3
nq /m
3
007
0
20
C.-
30
40
021
_.f1-1IW1Ui!f.,.1111
10
20
Ci
30
0
40
10
C
20
30
40
0 F
10
0.20
0.21
ng /m
nq/m
ng /m
Ir
S.
'S.
-
Illijil II
20
44j11 .i
C,-
30
40
018
3
nq/m
0
3
0
10
20
C-
30
40
0
10
20
30
c-I-
40
10
20
C
0
30
40
_1.j_,)
10
I111II1It(I
20
C.-
30
40
031
0.17
0.46
ng/m
ng /m
0.52
1 WiIIam
Ia
3
ng /m
016
flg /rT
0.23
20
C
0
30
40
0.44
0.26
0
10
20
C-
30
frn'
40
10
0.45
0.37
ng/m
ng /rr
ng/m
0,22
0.23
019
3
20
C
0
t.Il.44t4I44ftl..1
30
40
10
20
30
'10
C.0.'l0
3
20
C
30
'10
0 I'T.T4't1tIDLht9I..lI.j
10
20
30
40
C-
ng
0.20
0
0
10
30
20
C.-
40
tO
20
C
30
40
052
0.49
0.33
rig /m'
ng/rn
ng /m
0)7
0.24
3
0.47
3
ng/m
0.26
0.25
20
C
0
30
40
0
10
20
30
40
0
10
C,-
20
30
40
10
0.12
0.23
0.16
0.13
3
rig/rn
rig /n
3
rig/rn
rig /m
[TII
L
0.12
&I Ij LIMII&
[I
30
0.06
- un 1111111111 fl
I.
20
C,-
C..-
LI
!rr'''1r
ii,uuun,,uiiu
M&
.
IIIIIIIlIIIIIIi
40
o 20
0.14
019
rig fir
rig/rn
3
0.23
3
rig/rn
rig/ni
0.07
0
10
20
C
0.12
0
30
40
0
10
20
30
40
10
20
C.-
019
3
rig/rn
0.23
043
ng/n
rig/rn
0.12
0 22
C
0
30
40
JO
20
30
40
C.0.33
3
20
C
0
30
40
rig fln
0.16
0
10
20
30
C--
40
0
10
20
30
C--
40
t1ItU ftI'I1II1 Il
JO
20
30
C..-
..
40
'I-)
l-jjj itt ilt
1.
oz
ot
o
'I
i'-'1- 0
o
3
IIIIIIIIItIIIII
Ito
WI
-'--3
oc
oz
0
.1_3
o
oc
Ui
'
L1 ittiii'i'I'ii
'1
[Mi]
u
ot-
oc
o
o
610
oc
ot
D
o
W/
-'-3
OL'
01
0
I
t,I.0
w,bu
z vo
ot
Oi
t-'-'-'itItititttiiItitt-'I
oc
O
Ot'
01
0
600
oc
3
L Z 0
0
0
I
fu
I
c
W/ fu
W/ U
L 10
0
W/ bu
ItO
ct'o
t79
0
tOO
ry
0/
ID
0/
#0
0/
I.
0#
(0
50
50
50
50
L
20
C
0
0
30
40
]SI Range
rood Fern
0I
10
100]
20
C.-
24
30
40
Coost Range
Sword Fern
tO
r't'44'JuIl4J41.Js.f.,...r_r,.,
20
30
40
C
'°°lCoasI Range
0
tO
t0O
26
INorway Spruce
0I
10
0/
/0
0/
(0
50
50
50
5C
20
C.-
30
'-'i
40
0
0 tiiI4f1ItlIl1III1I.
10
20
30
C,-
40
C
24
30
40
Coast Range
Brewer Spruce
J
I0
L
20
0
tO
20
30
C
40
tO
20
30
C
40
26 I Coosl Range
100
I
100
22
Douglas Fir
Willomette
1001
Rhododendron
0/
/e
0/
50
50
/0
28
WillomelJe
Mountain
I lemlok
0
0/
C
50
d
0
0
l0
20
100,
C..
26
30
40
10
20
C
24
WilIametle
Big-cone
Douglas Fir
0
30
40
10
20
22
WillomeIte
IBrewer
1001
1001
Spruce
221
C
0
30
40
10
0/
10
0/
50
50
50
50
0
frr44J+f4f4444-119+_rrr,.r..i.,
20
30
C,.
40
10
20
C
0
40
I
/0
4_r44111411411.JI1J..r.r.r.i...i
30
40
Basin
1001
Sage
0,
I0
10
30
26 I
Columbia
Basin
0/
#0
0
C
20
10
20
C
0 l r.U'D 1tL1ILI1I., '+-
30
40
20
C-
30
40
'C
tOO -
22
tOO
Columbia
Basin
Juniper/Sage
26
Columbia
Columbia Basin
Basin
Gss
Litter
0/
/0
0/0
50
50-
Ito
C.-
30
50-
(24
1001
20
C
241
/0
50
f.,.i.(.,.I.lt(IlJJI. .'.II-'
10
20
30
C,-
10
50
0
30
40
0
tO
20
C.-.-
lOOi
Umalillo
0/
0/
0
0
40
30
40
tO
0,0
0/
50
50
50
f$1l-tI114f.
(0
20
C,-
30
C
______
30
/0
o 4.Ti.l.tIlefiI4II_ _ --
40
20
l00-
2E1 2R
/0
0
28
4176
0/0
0-
20
UmolilIa
Ooug(as Fir
28
Wilson ft Soil
tO
20
C,-
30
40
"nhIIIuI
0&&l
rM
.
40
00
167
A
22
Umalilla
While Fir
0/
'U
0/
l0
0/
(0
U,
/0
50
50
50-
50
0
I
20
I.
30
24
40
Umatilla
Pacific
Silver Fit
0/
10
50
20
30
C
40
0
10
20
30
40
I
40
Ii
20
C- 30
40
100
APPENDIX III:
Histograms of Phytostersols (-:
C27.1, C281 and C291;
C28.2;
Distributions in Aerosols and Source Vegetation Waxes Collected
Along a Transect From the State of Oregon
C79:2)
-
5.5
11.8
pg/m
pg/rn
2.7
5.9
1.0
50.2
Coast Range
pg/rn3
pg hr
0.5
25.1
II
0
0
25
C-
30
30
25
ot
25
C
28.4
Il
I
0.90
pg/m
pg/rn
pg/rn
14.2
0.85
0.45
0
C-
30
30
25
C
I
0
25
30
C
I
25
I
30
C
1.70
0
i
I
Columbia
Basin U
8.4
3
pg/m
4.2
0125
0
C-
30
25
C-
30
4.0
Coast Range
100
100
0/
/0
0/
/0
5°
50
Moss
pg/m
50
2.0
0±
0
as
C -
30
0
25
30
0
C
100
30
25
25
100
30
C-
C
t00
Coast Range
Brewer Spruce
0/
I0
0/
I0
0/
/0
0I
/0
50
1!]
I
I
0
0
______
0
I
25
30
C
25
C-
30
25
30
C
25
I
i
I
C-
I
I
I
30
0
100
100
0/
10
/01
50
Willamelte
Big-cone Douglas Fir
I
50-1
100
Brewer Spruce
1
/01
1.
50
so-I
I
0
25
100
C-
0+
30
25
I
C-
I
II(FT
0
I
30
II
100
Columbo Basin
Wilson Ranch Soil
Juniper/Sage Litter
0I
10
0/
10
50
50
0
30
C
C-
30
C-
30
lOG
I
I
30
C
25
0/
/0
o
25
0
30
2S
C
Columbia Basin
0+
25
100
Willwnelte
I
I
I!
I!
I
I
I
25
I
30
C
L
100
100
1001
0I
10
0/
50
0
10
0/
0/
/0
50
50
50
0
25
1001
30
C-
25
30
C
100
Umolillo
DouglaS Fir
50
Umotillo
Pacific Silver Fir
'!
I!
I
'I
I
It
I
I
25
I
I
30
C
0
'
I
I
I
I
25
I
30
C
OJ
I
I
II
I
I
25
I
I
30
C
50
OI
tOO
UmatilIa
Ponderoso Pine
0
25
30
C
105
APPENDIX IV:
Histograms of Wax Esters Distributions in Vegetation
Wax Extracts Collected Along a Transect From
the State of Oregon
100
100
0/
10
0/
I0
50
100
0/
50
0
tOO
10
0/
/0
50
50
0
30
40
0
50
30
C
40
C
100
0,
do
100
0l
'U
50
50
0
0
40
C-
50
50
30
C
100
30
40
30
50
36
40
50
40
50
C
Coast Range
Brewer Spruce
100
0/
/0
0/
50
50
/0
0-h
30
40
C.-
50
30
40
C
C-
-C
100
100
VIllamelta
40
hododendron
0I
/0
100
WillameIte
Big -cone
Douglas Fir
0/
to
50
50
0-1-1
40
30
r1
50
0Iii.1llttttiiii.jj
40
30
100
100
0)
50
50
38 Columbia Basin
/0
0
50
C-
C
0I
/0
0
30
100
40
C..
40
Juniper/Sage
Umalilla
Douglas Fir
Liller
OF
/0
OF
/0
50
50
40
C
I
lI.IhI!IhIl
40
50
C
50
40
30
50
C
100
Needles
0/
to
0/
50
5:
0-f-,
30
40
C-
40
C..
50
0
I
100
100
100
100
0/
/0
0/
/0
0/
/0
0/
/0
50
50
50
50
0
0
30
40
50
0
30
C
100
40
C 100
0/
0
30
50
/0
0/
50
50
40
C
50
40
C -r
50
0I
/0
50
0
40
C -
-
40
C -
50
30
40
C
100
/0
30
50
109
APPENDIX V:
Chemical Structures of Diterpenoids and Triterpenoids Cited
(With CAS Registry Number Listing)
110
a
OH
' COOH
L 1 3-IsopropyI-5apodocarpa6,8,11,13-tetraen-16-oic acid
COOH
II. Dehydroabietic
III. 7-Hydroxydehydro-
acid
abietic acid
a
a
IV. Calocedrin
1.
' COOH
0
V. 7-Oxodehydroabietic
acid
1.
' COOR
VI. 7-Oxo-1 3-isopropytpodocarpa-5,8,11,13tetraen-1 6-dc acid
_'%JJn I
VII. 3-Oxodehydroabietic
acid
HO
HO
HO
X. Campesterol
0
XI. Stigmasterol
ill
HO
HO
O
XII. f3-Sitosterol
XIV. 3-Amyrin
XIII. Taraxerone (Skimmiorie)
0
HO
HO
XVI. a-Amyrin
XV. c-Taraxasterof
XVII. epi-Lupeol
OH
HO
XVIII. Diplopterol
XIX. Erythrodiol
XX. Friedelin
200K
0
XXI. Oleanonic acid
XXII. Betulinic acid
XXIII. Oleanolic acid
112
:ooF
..
XXV. Ursolic acid
XXIV. Ursonic acid
XXVI. Morolic acid
XXVIII. 2,5-Bis(1,1-dimethylpropyl)-
XXVII. Sesquiterpenone
2,5-cyclohexadiene-1 ,4-dione
XXIX. Phenanthrene
cgigi
XXX. Manoyl oxide
XXXI. epi-Manoyl oxide
XXXII. Pimaric acid
XXXIII. Chrysene
I-iC
XXXIV. Norfupeol
XXXV. 3-Amyrone
XXXVI. a-Amyrone
113
HO
HO
XXXVII. 3:4-Seco-3-nor-Oleafl-1 2-
o
3:4-Seco-atean-1 2-eri-3-oic acid
en-2-oic acid
HO
XXXIX. DihydrocartariC acid
HO
XLI. 1-riedelinol
XL Dihydroburic acid
114
Chemical Abstract Service (CAS) numbers of some compounds in Appendix V.
Number
Name
CAS number
II
Dehydroabietic acid
Cholesterol
Brassicasterol
Campesterol
Stigmasterol
f3-Sitosterol
Taraxerone
3-Amyrin
ir-Taraxastero1
ct-Amyrin
1740-19-8
57-88-5
474-67-9
474-62-4
Vifi
IX
X
XI
XII
XIII
XIV
XV
XVI
XVII
XVIII
XIX
XX
XXII
XXIII
XXIV
XXV
XXVI
XXIX
XXX
XXXI
XXXII
XXXIII
XXXV
XXXVI
XXXIX
XLI
j-Lupeo1
Diplopterol
Erythrodiol
Friedelin
Betulinic acid
Oleanolic acid
Ursonic acid
Ursolic acid
Morolic acid
Phenanthrene
Manoyl oxide
j-Manoy1 oxide
Pimaric acid
Chrysene
13-Amyrone
a-Amyrone
Canaric acid
Friedelinol
8 3-48-7
83-46-5
514-07-8
559-70-6
464-98-2
638-95-9
4439-99-0
1721-59-1
545-48-2
559-74-0
472-15-1
508-02-1
6246-46-4
77-52-1
559-68-2
85-01-8
596-84-9
1227-93-6
127-27-5
218-01-9
638-97-1
638-96-0
2067-65-4
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
233
111
LrJ,
F
tee.a
C21HO2
237
197
9397
312
L1
podocarpa-6,8,11,i3et;aen
:n
F4
...
C21H3002
71
II.
'f7i5i732891rs 2eT
Mechyldehydroabietate
23
r
271
117
239
L ¶
Unknown III - 2
lee
49e
'T,In
22
ee
e
gae
117
IL
227
73
¶
ii
-;
9
III.
Methyl 7hydroxydehy
droabietata triethy1 silyl
H38O3Si
8.9
ether
492
373'i
I
i
698
459
559
180.9
ze. a
283
2391 2
'v'..''
i''
316 339 r
,-'
281
,
I
159
228
259
288
358
459
580
559
698
659
Calocedrin
IV.
C20H1607
a.a
180.0
(çL
C1HO3
I
V.
115
Methyl 7oxodehydro
171
L.
abietate
59
188
I
r
,
150
280
350
118
i.a
ze. a
1295
L,,L.
311
A
tza
Ligna
(mixture)
a
35/
Is
I
68
251
1.a
C21HO3
'
VI.
149
Methyl 7oxo-13isopro
isz
pylpodocarpa-5 .8,11,13
tA4
f
tetraen-15oate
158
JL
I
197
298
258
259
iee.a
C21H
197
117
155
oX
'128
I
VII.
I
I
313
282'
Methyl 3oxodehydro
ILt
abietace
158
288
328
268287
213
I
t4I
258
.
328
1-
119
a.
137
i. 1r
j
k
Unknown 111.3 (nixture) t88.
e. a
439
378
188.8
59. a
'r1
59
Unknown 111.4
LI
2
309
159
208
259
388
358
458
580
558
88
650
108.0
50.0
380
251
180.8
58.9
59
Unknown 111.5
180
158
288
259
580
559
180.8
58.8
-
120
17
j4
.
a C3kiOSi
VIII. Cholesterol
triechyl silyl ether
33
485
tJ1IT!
Ir
458
480
188.0
.a
100
58
ioe.a
208
158
'.
588
253
388
C31HOSi
388
IX.
Brassicasterol
trimethyl silyl ether
408
100.0-
500
453
550
55
58.0-
J
r
108.8-
X.
Campesterol
trimethyl silyl ether
37
358
n
C31H%OSi
457
.j.,.I.j.I_.I.lr;.j.I'i_._j
408
458
111
538
=1:
558
S88
550
358
121
180.8
4.0
r
-
255
83
330
L1i
153
100
58
258
288
394
. a
484
Stiaateoj
.
C32H%QSi
trimethyl silyl echer
458
350
559
57
LJ
322
U
?tIE
50
220
158
250
tee. a
ThaQ
C32H58OSi
XII.
5Sjosteroj
tethy1 silyl ether
486
47i
458
350
558
458
i.a
50.0
180.0
XIII.
Taraxerone
(skiimn.jorie)
50.0
c3oI48o
368
409 424
480
453
588
558
122
23
273
73
tI9
8Amyr1
tr1ethyL silyL ether
XIV.
C33H53OSt
498
233
48
488
588
550
73
aa
121
5!
I1I
.I.
,;J.
,4,
180
158
298
259
398
28.8
4,Taraxascerol
XV.
crimechyl sily]. ether
18.3
C33H53OSi
23
498
393
499
425
358
483
498
45
218
188.8
279
50.3
73
C33HOSi
XVI. ciAmyrin
trimechyl silyl ether
498
333
I
488
427
377
1&11l1'11r
a
I
I
488
459
580
580
I
550
123
189
199
12t
147
XVII.
Z79
1
.ax
i.e- r
L7)
t7
lk
,LJ,
C33H53OSi
3ci-Lupeol
triethy1 silyl. ether
49$
36i13
'u- .
iri
48$
I
4Z8
!.ax
191
31
149
I
I
1
328
287
LSL
23
fT1,
:,
1
2
:1,
29.3
XVIII. Diploptarol
trimethyl silyl ether
C33HOSi
429
I
I
!89
442
II
III'II.
,..,,I
I'
48
489
21E
73
293
.a.
113
J!J ,!jJJ
;!lt IlL
188
2!9
298
388
199.3
XIX. Erythrodiol
trimethyl silyl ether
4O
C36HOSi2
291
2c
4C3
''I
409
4!2
.iili
481
7 ,j
14
8a
8
'jill'
S88
124
L0.X
C30H500
XX.
Friedelin
341
315
332
35637
4jf3
4_Il
4
400
35J
308
100_a
262
189
1
18. '3X
øø.
XXI.
&1;M'1.
1Th
r_Z]
C31H4O3
Methyl 3-.oxo-,
488
olean-L2-et-28-oate
463
393
IhhII,II li'
480
358
308
458
508
189
180.8
73
Ji
81
I
I
I
175
12L
ii
un
147
I
I4
!111211t
ieee
(
l5.0
413
CH58O3sL
Methyl betulinate
trimethyl silyl ether
XXII.
542
377
,1LL42s
1i'
jI
480
458
¶
500
580
550
580
659
125
e. o
25
23
3 247
l
2a
iee.e
XXIII. Methyl oleanolace
trthethyl silyl ether
CH58O3Si
483
27
L5z
480
133
48
283
2S2
3n
I
:
1
208
133.8
XXIV.
r
28
408
c31o3
Methyl 3oxo
urs-12en-.28oace
El
rIj.I I'
'E'''''1
126
2S2
tee. a
a.a
at
U. i]
147
1
4
CH58O3Si
Methyl ursolate
.
trimethyl silyl ether
482
42
487
27
1
I
48
iae.a
a. a
I
119
81
147
!J
213
iJJL4li.
2!ø
229
lea
188 3
l.
Methyl
orolate
I
CH53O3Si
trimethyl si.lyl ether
483
408
4a
42
a0
127
177
138
121
13
132
I. Bicyclic
I.
sesquierpenotte
23
308
,.,
248
191
0
-
t Z3
91
t49
VIII. 2,5-3i(1 1dinethy1propy1)-2,5cyciohecadietie-L,4-diore
1r
'r
k
I
j
L0
88
_________________________
i
?C
188.3
38
258
288
158
178
C14H13
71
113
IX.
Phenanthrene
280
158
188
83
388
300
250
180.3
C21H0O4.
Unown IV.].
119
78
139
11
1!JI
83
ct7Methyl pinarate
O4,
263
195
3A6
I
188
180
280
258
388
338
121
188.3
II.
168
_____
C21H3202
'
4
L59
92I3
24l
3iS
128
r
C20H340
at
0
t77 122
1= 137
sa.a
.
U
oxide
Manoyl
:
1
-
-
C20H340
a'
°
ç.
I.
Epi-anoyL
918
oxide
iee.a
a. a
1178
I
1t2 122
1.4. J
tag
157 118t
219
L8
299
23
388
358
453
528
558
8
5O
388
358
Uaknon IV.2
sa. a
58.3
t:ji;:j
114
III.
Chrysene
125
81
isa
175
22
'I
58
188
158
129
-.
4
'l
t
_t
XXXIV.
253
Norlupeol
C29H480
4t2
553
4'O
28
tee. a
za.a
-
I
383
'
153
çtø
XIV.
jIi'
289
250
500
550
8-Amyrin
5.3
C30H5O
426
458
480
1813.8
74
58.3
203
L
58
(
r
iJ
I11.1Lj
158
189
288
258
tnknown IV.3
58.8
C30H480
94
381
'-I- l..I.l.L.I.I.I_I.r.I'I?It'II'
488
458
500
2-.
558
j
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
28
23
known tV.4
488
.ax
1R9
188.3ITT
284
189
Unknown tV .5
28.0
te. a -
393
I
I
489
I
P
48
89
I
I
609
68
131
218
283
a.a
ie
8-Amyrone
C30H4s0
42
i'
100.3
08
80
408
218
81
93
121
136
161
U
i
180.3
VI.
iAmyrone
58.3
c3cIio
K
488
458
580
550
680
132
55
I
'Z03
14
CCCV111.
MethyL 3 :4-secodi
3-or-o1ean-12-en-2-oaca
(methyl 3:4-gecofriedelen-3--
e)
tee
58
257
L i;
tLJ1L iL.
.
208
158
23
L IL
.
358
258
tee.a
C30H52O
12M1 C3 1H520I
58 3
VIII
Methyl 3.4seco-olean-12-en-3-oace
I
t
I
I ..........
450
480
588
S88
558
L8
100.3-
55
283
S9
213
50.3-
113
2.5
.,
1.!.
I!
tee
228
1
441
388
358
C31H5202
Methyl
dihydrocanarace
(methyl 3:4seco-lupea-3-oate)
IX.
V
480
458
ee
soe
245
180.3-
284
2i8L
T1
so
unknown IV.7
Ji
i..
108
158
V
V
288
258
388
588
558
S88
180.3
C3H52O2
58.3-
441
488
458
358
133
218
iae. a
a.a
ji
.1
ie
XL.
a
Methyl dihydroburate
.
...
2
28
588
550
688
658
208
258
388
358
588
558
689
658
C31H5202
a. 8
456
23
44
I
458
iaa.a
a. a
t1It,44
158
108
iee.a
XLI.
FriedelioL
C30H520
423
458
In! Z-