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Final Report: Organic Tracers of Plant Classes in Biomass Combustion and Smoke in Aerosols
EPA Grant Number: R823990Title: Organic Tracers of Plant Classes in Biomass Combustion and Smoke in Aerosols
Investigators: Simoneit, Bernd R.T.
Institution: Oregon State University
EPA Project Officer: Shapiro, Paul
Project Period: October 1, 1995 through September 30, 1997
Project Amount: $196,244
RFA: Exploratory Research - Chemistry and Physics of Air (1995)
Research Category: Engineering and Environmental Chemistry
Description:
Objective:The main objective of this study was to characterize and define organic tracers attributable to biomass burning in atmospheric particles and smoke from specific fuels (e.g., wood, coal, etc.) and natural fires. The acquired information has contributed to the existing database of molecular tracer compositions that are necessary for identifying source input from biomass burning and fuel combustion emissions to the atmosphere. The identification of single and multiple plant species and fuel combustion contributions can be determined from the source-specific "chemical fingerprint." These data will be invaluable for regional source correlation and apportionment studies on contributions of organic smoke components to atmospheric particle chemistry. Summary/Accomplishments (Outputs/Outcomes):
Smoke particulate matter from multiple species of vegetation (e.g., angiosperm, gymnosperm and graminae) from arctic, temperate, and tropical climate zones and coal (e.g., ranks from lignite through bituminous) subjected to controlled burning, both under smoldering (<300 C) and flaming (>300 C) conditions, was sampled by high volume air filtration on precleaned (550 C for 3 hours) quartz fiber filters (see Table 1). The filtered particles were extracted with dichloromethane, and aliquots of the crude extracts were methylated for separation by thin layer chromatography (TLC) into hydrocarbon, carbonyl, carboxylic acid ester and polar fractions. This procedure allows for the determination of chemical information on single molecular groups or functional group series, which may not be detected due to coelution in the total extract mixture. The total extracts and all fractions were analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Compounds were identified by comparison with authentic standards, by correlation with the literature, or by interpretation of the mass spectrometric fragmentation pattern. Quantitation was conducted on molecular biomarkers, elemental, volatile, and total organic carbon.
The samples analyzed for this project are listed in Table 1 and the molecular
data are to be reported in the scientific literature.
Table 1. Biomass burning smoke sources analyzed for organic components.
| Sample | Scientific Name | Source Location |
| Temperate and Arctic Climate Zones | ||
| Gymnosperms (Softwoods) | ||
| Apache Pine | Pinus engelmannii | Sierra Madre, Mexico |
| California Redwood | Sequoia sempervirens | Eureka, CA |
| Douglas Fir | Pseudotsuga menziesii | McDonald Forest, Corvallis, OR |
| Eastern White Pine | Pinus strobus | McDonald Forest, Corvallis, OR |
| Florida Pine | Pinus elliottii | Florida, USA |
| Lodgepole Pine | Pinus contorta | North Tumalo Creek Trail, OR |
| Montezuma Pine | Pinus montezumae | Sierra Madre, Mexico |
| Mountain Hemlock | Tsuga mertensiana | Crater Lake, OR |
| Noble Fir | Abies procera | Philomath, OR |
| Pacific Silver Fir | Abies concolor | Mary's Peak, Philomath, OR |
| Ponderosa Pine | Pinus ponderosa | McDonald Forest, Corvallis, OR |
| Port Orford Cedar | Chamaecyprislawsonia | McDonald Forest, Corvallis, OR |
| Sitka Spruce | Picea sitchensis | Arcata, CA |
| Western White Pine | Pinus monticola | North Tumalo Creek Trail, OR |
| Angiosperms (Hardwoods) | ||
| Dwarf Birch | Betula glandulosa | Shingle Point, Yukon Territory |
| Birch | Poa glauca | Shingle Point, Yukon Territory |
| Birch | Betula alba | Corvallis, OR |
| Eucalyptus | Eucalyptus dalrympleana | Arcata, CA |
| Oregon Maple | Acer macrophyllum | Gold Beach, OR |
| Red Alder | Alnus Rubra | Mary's Peak, Philomath, OR |
| Silver Birch | Betula pendula | Corvallis, OR |
| Graminae (Grasses) | ||
| Aquatic Grass | Arctophila fulva | Shingle Point, Yukon Territory |
| Cotton Grass | Eripohorum vaginatum | Shingle Point, Yukon Territory |
| Rye Grass | Lolium perenne | Philomath, OR |
| Tropical Climate Zone | ||
| Angiosperms (Hardwoods) | ||
| Andiroba | Carapa guineensis | Amazonia |
| Mangrove | Avicennia sp. | Amazonia |
| Castanha-do-Para | Bertholettia excelsa | Amazonia |
| Clusia | Clusia sp. | Amazonia |
| Cumaru | Dipterix osorata | Amazonia |
| Marupa | Simaruba amara | Amazonia |
| Mangrove | Rhizophaor sp. | Amazonia |
| Vismia | Visma guineensis | Amazonia |
| Keruing Tree | Dipterocarpus cornutus | Malaysia |
| Graminae (Grasses) | ||
| Bamboo | Dendrocalamus giganteus | Malaysia |
| Sugercane | Saccharum officinarum | Malaysia |
| Miscellaneous | ||
| Tobacco | Nicotiana tobacum | Chile |
| Latex | Hevea brasiliensis | Malaysia |
| Geological Sources | ||
| Coal | ||
| Lignite | Fortuna mine | Aachen, Germany |
| Brown Coal | Leuna | Thuringen, Germany |
| Sub-bituminous Coal | Wepo Formation, Mesa Verde Group | Black Mesa, AZ |
| Bituminous Coal | Wales | Great Britain |
Biomass Smoke. The major, directly emitted organic
components identified in smoke particles from species-specific biomass burns
were straight chain aliphatic compounds from vegetation wax, diterpenoid acids
(biomarkers) from resins, and triterpenoids from gums. The major natural
products altered by combustion included derivatives from phenolic (lignin) and
monosaccharide (cellulose) biopolymers and oxygenated and aromatic products from
diterpenoids, triterpenoids, and steroids. Biomarkers are present as minor
components and include derivatives of diterpenoids, triterpenoids and
phytosterols, as well as unaltered high molecular weight wax esters. Polycyclic
aromatic hydrocarbons (PAHs) also were identified in all samples, but as minor
constituents. In general, each individual plant species emits a "chemical
fingerprint" of natural and thermally altered organic constituents upon burning,
which is source-specific and unique in composition. The incomplete combustion of
organic natural products results in derivatives that still retain structural
characteristics of the precursor compounds. From these products it is possible
to determine precursor/product relationships and reaction pathways. This
application further strengthens the use of biomarkers as source-specific tracers
in biomass burning studies.
Coal Smoke. The abundances and
distributions of organic constituents in coal smoke also are dependent on
thermal combustion temperature, aeration and duration, and coal rank. The major
organic components identified in coal smoke were homologous series of n-alkanes,
n-alkenes, n-alkanoic acids, and n-alkanols, which are derived from the higher
plant origins of the coals. Lignite (immature coal rank) retains a strong
"chemical fingerprint" of its source plant material; thus, the major tracers in
lignite smoke were the natural products (e.g., diterpenoids from resin acids)
and their thermally altered derivatives (aromatic biomarkers). The major tracers
for lignite were identified as 6,7-dehydroferruginol and ferruginol. The major
aromatic biomarkers in smoke samples of higher rank coals were picene, C1 and C2
substituted picenes, and the thermally-derived hydropicene series. Picene was
identified as the major tracer for bituminous coal smoke, while the C1 and C2
substituted picenes and the hydropicene series were identified as major tracers
for lower rank sub-bituminous coal smoke. Thus, picene, substituted picenes, and
the hydropicenes are strong indicators of coal maturity, which in turn can be
used to assess the maturity of the coal that was burned. PAHs also were present
in all samples of coal smoke, but only at intermediate abundances.
Although the concentrations of organic compounds in smoke aerosols
are highly variable and dependent on combustion temperature and conditions, the
biomarkers and their altered products are source-specific. The primary biomarker
sources from biomass burning are the thermal degradation products of the
structural polymers cellulose and lignin, the diterpenoid acids from bleed
resins, the triterpenoids from gums, and the epicuticular waxes. The
distributions and abundances of these components are generally unique for each
individual plant species. The burning of coals (fossil biomass fuel) also
releases organic compounds indicative of the inherited vegetation origin of the
sample, but reflecting the results of geological alteration. Coal smoke
emissions can be distinguished from contemporary biomass smoke compositions.
Release of these natural components and their thermally altered derivatives from
burning permits the tracing of fuel type (generally angiosperm, gymnosperm,
graminae) and the determination of source contributions to atmospheric aerosols.
The major molecular components identified in both biomass and coal smoke
include: (1) fatty acids (n-alkanoic acids), (2) monosaccharide derivatives from
cellulose (biomass only), (3) phenolic derivatives from lignin, and
(4)
terpenoids and combustion derivatives. The minor molecular components include:
straight-chain aliphatics (n-alkanes and n-alkenes), PAHs, steroids and
combustion derivatives, and wax esters. Smoke from coals is distinguishable from
contemporary vegetation smoke. This compound composition information is
important for modeling chemical mass emission (reaction, kinetics) and physical
(radiative heat transfer) behavior of organic aerosols in the atmosphere and is
necessary for determining the contributions of burning and combustion processes to global climate change.
Journal Articles on this Report: 13 Displayed | Download in RIS Format
| Other project views: | All 30 publications | 15 publications in selected types | All 13 journal articles |
| Type | Citation | ||
|---|---|---|---|
|
|
Elias VO, Simoneit BRT, Pereira AS, Cardoso JN. Mass spectra of triterpenyl alkanoates, novel natural products. Journal of Mass Spectrometry 1997;32(12):1356-1361. |
R823990 (Final) |
not available |
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Elias VO, Simoneit BRT, Pereira AS, Cardoso JN. High temperature gas chromatography with a glass capillary column for the analysis of high molecular weight tracers in smoke samples from biomass burning. Journal of High Resolution Chromatography 1998;21(2):87-93. |
R823990 (Final) |
not available |
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Elias VO, Simoneit BRT, Pereira AS, Cabral JA, Cardoso JN. Very high molecular weight organic marker (>C40) emissions from biomass burning in Amazonia. Revista Latino-Americana de Geoquimica Organica 1998;4:65-71. |
R823990 (Final) |
not available |
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Elias VO, Simoneit BRT, Pereira AS, Cabral JA, Cardoso JN. Detection of high molecular weight organic tracers in vegetation smoke samples by high-temperature gas chromatography-mass spectrometry. Environmental Science & Technology 1999;33(14):2369-2376. |
R823990 (Final) |
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Oros DR, Simoneit BRT. Identification of molecular tracers in organic aerosols from temperate climate vegetation subjected to biomass burning. Aerosol Science and Technology 1999;31(6):433-445. |
R823990 (Final) |
not available |
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Oros DR, Standley LJ, Chen X, Simoneit BRT. Epicuticular wax compositions of predominant conifers of western North America. Zeitschrift fur Naturforschung 1999;54C:17-24. |
R823990 (Final) |
not available |
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Oros DR, Simoneit BRT. Identification and emission rates of molecular tracers in coal smoke particulate matter. Fuel, April 2000;79(5):515-536. |
R823990 (Final) |
not available |
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Oros DR, Simoneit BRT. Identification and emission factors of molecular tracers in organic aerosols from biomass burning Part 1. Temperate climate conifers. Applied Geochemistry 2001;16(13):1513-1544. |
R823990 (Final) |
not available |
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Oros DR, Simoneit BRT. Identification and emission factors of molecular tracers in organic aerosols from biomass burning Part 2. Deciduous trees. Applied Geochemistry 2001;16(13):1545-1565. |
R823990 (Final) |
not available |
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Simoneit BRT, Rogge WF, Lang Q-Y, Jaffe R. Molecular characterization of smoke from campfire burning of pine wood (Pinus elliottii). Chemosphere - Global Change Science, January 2000;2(1):107-122. |
R823990 (Final) |
not available |
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Simoneit BRT. A review of biomarker compounds as source indicators and tracers for air pollution. Environmental Science and Pollution Research 1999;6(3):159-169. |
R823990 (Final) |
not available |
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Simoneit BRT, Schauer JJ, Nolte CG, Oros DR, Elias VO, Fraser MP, Rogge WF, Cass GR. Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles. Atmospheric Environment, January 1999;33(2):173-182. |
R823990 (Final) |
not available |
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Simoneit BRT, Oros DR, Elias VO. Molecular tracers for smoke from charring/burning of chitin biopolymer. Chemosphere - Global Change Science, January 2000;2(1):101-105. |
R823990 (Final) |
not available |
air, atmosphere, chemicals, toxics, particulates, polycyclic aromatic hydrcarbons, PAH, organics, PNS, indicators, environmental chemistry, analytical survey, northwest. , Toxics, Air, Geographic Area, Scientific Discipline, RFA, HAPS, Physics, air toxics, Chemistry, EPA Region, particulate matter, Environmental Chemistry, State, International, incineration, California (CA), exposure and effects, Volatile Organic Compounds (VOCs), chemical speciation sampling, hydrocarbon, smoke aerosols, monitoring, biomass combustion, particulates, Oregon, molecular markers, point source correlations, Brazil, atmospheric chemistry, OR, Region 10, organic tracers of plant classes, California, ambient aerosol, tropical rain forests
Progress and Final Reports:
Original Abstract