Milestone Identification of biomass burning...

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AIRUSE

LIFE11 ENV/ES/584

Milestone

Identification of biomass

burning tracers

Action B4

Coordinated by:

Action B4 - Milestone - Identification of biomass burning tracers

AIRUSE LIFE 11 ENV/ES/584 December / 13

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The Milestone “Identification of biomass burning tracers” is complete. The chemical

analysis of the numerous particulate matter samples from the combustion experiments

already carried out at UAVR have shown, in accordance with literature, that levoglucosan

is an unequivocal biomass burning tracer. Their stereoisomers, galactosan and mannosan,

are also abundant compounds in smoke. Although the three anhydrosugars are always

emitted by biomass burning sources, the proportions between them depend on what biofuel

is being burnt. Thus, the simultaneous determination of the three stereoisomers is

recommended in order to apportion the contribution from different biomass burning

emissions (e.g. softwood versus hardwood).

The relative proportions of levoglucosan to mannosan (L/M) have been used for source

reconstruction of combustion derived byproducts in atmospheric aerosols. For example,

inputs from very specific poor-quality brown coals gave L/M ratios greater than 50 in

atmospheric aerosols (Fabbri et al., 2009). Differences in the L/M ratio (Table 1) in smoke

from softwood and hardwood/grass combustion (~5 versus ~10-20, respectively) can

further support discrimination between inputs from these combustion sources to the

atmosphere (Louchouarn et al., 2009; and references therein). Herbaceous tissues can

produce relatively high L/M ratios, in the range from 25 to 50 (Engling et al., 2009). In the

present study, lower ratios than those reported for soft-and hardwood smoke were obtained

(Tables 2 and 3). In addition to differences in the cellulosic content of the different

biofuels, the emission of saccharidic compounds may strongly depend on combustion

characteristics that are not well-understood. Under controlled combustion conditions (150-

1050 ºC), Kuo et al. (2008) determined the levoglucosan content in samples from 3 wood

species. The anhydrosugar was only detectable in low temperature samples (150-350 ºC),

with maximum yield obtained from samples produced at 250 ºC, regardless of plant

species. A laboratory emission study of wood and pellet boilers gave 0.3% w/w to 22%

w/w levoglucosan to particle mass, indicating that the levoglucosan fraction may be highly

dependent on combustion parameters, making it uncertain to use it as a quantitative tracer

under real-world burning conditions (Hedberg et al., 2006). Another variable that has a

strong influence on the yield of levoglucosan from cellulose is the presence of inorganic

ions (Dobele et al., 2005). It has been observed that the presence of mineral matter in wood

decreases the temperature of cellulose pyrolysis (Williams and Horne, 1994). Thus,

quantitative estimates of wood burning inputs to atmospheric particles will be very

doubtful using exclusively levoglucosan as a tracer.



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Table 1. Ratios of anhydrosugars in emissions from biomass burning (L –levoglucosan, M –mannosan, G –galactosan).

Table 2. Anhydrosugars in wood smoke (% w/w PM10) from an eco-labelled woodstove.



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Table 3. Organic carbon-normalised concentrations of sugars (mg g-1OC) in the emissions from the combustion of

various biomass fuels in a traditional woodstove and in a fireplace.



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In the particulate matter emitted from residential appliances tested at the combustion

facility of UAVR, levoglucosan was detected at concentrations between two and three

hundred mg per g of organic carbon (OC), which are similar to the values reported for the

stove combustion of typical American wood species (Fig. 1). The L/M ratios were

generally lower than 3 in particles from the combustion of softwood, whereas the same

ratio for hardwood can reach values greater than 20 (Fig. 2).

Figure 1. Levoglucosan-OC normalised concentrations. Comparison between different residential combustion

appliances.

Figure 2. Levoglucosan-to-mannosan ratio found in smoke particles from different residential combustion appliances.

Combustion of wood and other biomass fuels produces other source-specific organic

compounds arising from pyrolysis of lignin, including substantial amounts of 4substituted

methoxylated phenolic compounds, which, as it occurs with anhydrosugars or resin acids

(in the case of coniferous), can be used as atmospheric markers to determine the

contribution of wood smoke to ambient atmospheric fine particulate matter. Gymnosperm

smoke is made up almost solely from 4-hydroxy-3-methoxy phenyl (guaiacyl or vanillyl)



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compounds. Angiosperms generate both vanillyl and 4hydroxy-3,5-dimethoxyphenyl

(syringyl) constituents. Non-woody tissue of both gymnosperms and angiosperms can be

distinguished from woody tissue by their lower yields of vanillyl and syringyl phenols and by

the characteristic production of phenylallyl (cinnamyl) phenols. Grasses give rise essentially to

4-hydroxyphenyl (coumaryl) products. Some sterols can also be pointed out as biomass

burning tracers.

Differences in emission rates of resin acids can be used to distinguish between the smoke

produced when burning hardwood or softwood. Resin acids, such as those listed in Table 4,

are significant components of softwood emissions, but are not found, or are detected at

relatively minor levels, in the emissions from hardwoods.

Table 4. Average OC-normalised concentrations of resin acids (mg/g OC).

Methoxyphenols have been identified in all smoke types, but differences between soft-and

hardwood were observed. Particles from softwood combustion contain higher proportion of

vanillyl compounds, such as vanillic acid, with one methoxy group, whilst syringyl

compounds, with two methoxy groups, dominate in particles from hardwood burning

(Table 5). Stigmasterol is a phytosterol that can be used as a potential tracer to separate

softwood and hardwood smoke, since it was never detected in the coniferous samples.

Retene was the dominant aromatic hydrocarbon found in the softwood smoke. Very low

concentrations were observed in particulates emitted from hardwood combustion.



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Table 5. Average OC-normalized concentrations of some biomass burning tracerss (mg/g OC).

Table 6 compiles a list with the most important biomass burning organic tracers. The

composition of smoke particles suggests that differences in the source profiles of organic

compounds between wood types and combustion appliances merit consideration in receptor

modeling techniques, such as CMB, to apportion the contribution of biomass burning to

ambient aerosol concentrations.



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Table 6. Biomass burning tracers and characteristic fragments when they are detected by mass spectrometry (MS).



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REFERENCES

Alves, C., Gonçalves, C., Evtyugina, M., Pio, C., Mirante, F., Puxbaum, H., 2010. Particulate organic

compounds emitted from experimental wildland fires in a Mediterranean ecosystem. Atmospheric

Environment 44, 2750-2759.

Dobele, G., Rossinskaja, G., Diazbite, T., Telysheva, G., Meier, D., Faix, O., 2005. Application of catalysts

for obtaining 1,6-anhydrosaccharides from cellulose and wood by fast pyrolysis. Journal of

Analytical and Applied Pyrolysis 74, 401-405.

Engling, G., Carrico, C., Kreidenweis, S., Collett Jr, J., Day, D., Malm, W., Lincoln, E., Min Hao, W.,

Iinuma, Y., Herrmann, H., 2006. Determination of levoglucosan in biomass combustion aerosol by

high-performance anion-exchange chromatography with pulsed amperometric detection.

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Engling, G., Lee, J., Tsai, Y.-W., Lung, S.-C.C., Chou, C.C.-K., Chan, C.-Y., 2009. Size resolved

anhydrosugar composition in smoke aerosol from controlled field burning of rice straw. Aerosol

Science and Technology 43, 662–672.

Fabbri, D., Torri, C., Simoneit, B., Marynowski, L., Rushdi, A., Fabianska, M., 2009. Levoglucosan and

other cellulose and lignin markers in emissions from burning of Miocene lignites. Atmospheric

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Hedberg, E., Johansson, C., Johansson, L., Swietlicki, E., Brorström-Lundén, E., 2006. Is levoglucosan a

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in Lycksele, Sweden. Journal of the Air & Waste Management Association 56, 1669-1678.

Kuo L., Herbert B.E., Louchouarin P., 2008. Can levoglucosan be used to characterize and quantify

char/charcoal black carbon in environmental media? Organic Geochemistry 39, 1466-1478.

Louchouarn, P., Kuo, L., Wade, T.L. and Schantz, M., 2009. Determination of levoglucosan and its isomers

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Wang, Z., Bi, X., Sheng, G.,Fu, J. 2009. Characterization of organic compounds and molecular tracers from

biomass burning smoke in South China I: Broad-leaf trees and shrubs. Atmospheric Environment 43,

3096-3102.

Williams, P.T., Horne, P.A., 1994. The role of metal salts in the pyrolysis of biomass. Renewable Energy 4,

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