Biomass Burning Markers Research Articles

Molecular characterization of free tropospheric aerosol collected at the Pico Mountain Observatory: a case study with a long-range transported biomass burning plume

Abstract. Free tropospheric aerosol was sampled at the Pico Mountain Observatory located at 2225 m above mean sea level on Pico Island of the Azores archipelago in the North Atlantic. The observatory is located ~ 3900 km east and downwind of North America, which enables studies of free tropospheric air transported over long distances. Aerosol samples collected on filters from June to October 2012 were analyzed to characterize organic carbon, elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 ± 0.7 μg m−3. On average, organic aerosol components represent the largest mass fraction of the total measured aerosol (60 ± 51%), followed by sulfate (23 ± 28%), nitrate (13 ± 10%), chloride (2 ± 3%), and elemental carbon (2 ± 2%). Water-soluble organic matter (WSOM) extracted from two aerosol samples (9/24 and 9/25) collected consecutively during a pollution event were analyzed using ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Approximately 4000 molecular formulas were assigned to each of the mass spectra in the range of m/z 100–1000. The majority of the assigned molecular formulas had unsaturated structures with CHO and CHNO elemental compositions. FLEXPART retroplume analyses showed the sampled air masses were very aged (average plume age > 12 days). These aged aerosol WSOM compounds had an average O/C ratio of ~ 0.45, which is relatively low compared to O/C ratios of other aged aerosol. The increase in aerosol loading during the measurement period of 9/24 was linked to biomass burning emissions from North America by FLEXPART retroplume analysis and Moderate Resolution Imaging Spectroradiometer (MODIS) fire counts. This was confirmed with biomass burning markers detected in the WSOM and with the morphology and mixing state of particles as determined by scanning electron microscopy. The presence of markers characteristic of aqueous-phase reactions of phenolic species suggests that the aerosol collected at the Pico Mountain Observatory had undergone cloud processing before reaching the site. Finally, the air masses of 9/25 were more aged and influenced by marine emissions, as indicated by the presence of organosulfates and other species characteristic of marine aerosol. The change in the air masses for the two samples was corroborated by the changes in ethane, propane, and ozone, morphology of particles, as well as by the FLEXPART retroplume simulations. This paper presents the first detailed molecular characterization of free tropospheric aged aerosol intercepted at a lower free troposphere remote location and provides evidence of low oxygenation after long-range transport. We hypothesize this is a result of the selective removal of highly aged and polar species during long-range transport, because the aerosol underwent a combination of atmospheric processes during transport facilitating aqueous-phase removal (e.g., clouds processing) and fragmentation (e.g., photolysis) of components.

Fossil vs. non-fossil sources of fine carbonaceous aerosols in four Chinese cities during the extreme winter haze episode of 2013

Abstract. During winter 2013, extremely high concentrations (i.e., 4–20 times higher than the World Health Organization guideline) of PM2.5 (particulate matter with an aerodynamic diameter < 2.5 μm) mass concentrations (24 h samples) were found in four major cities in China including Xi'an, Beijing, Shanghai and Guangzhou. Statistical analysis of a combined data set from elemental carbon (EC), organic carbon (OC), 14C and biomass-burning marker measurements using Latin hypercube sampling allowed a quantitative source apportionment of carbonaceous aerosols. Based on 14C measurements of EC fractions (six samples each city), we found that fossil emissions from coal combustion and vehicle exhaust dominated EC with a mean contribution of 75 ± 8% across all sites. The remaining 25 ± 8% was exclusively attributed to biomass combustion, consistent with the measurements of biomass-burning markers such as anhydrosugars (levoglucosan and mannosan) and water-soluble potassium (K+). With a combination of the levoglucosan-to-mannosan and levoglucosan-to-K+ ratios, the major source of biomass burning in winter in China is suggested to be combustion of crop residues. The contribution of fossil sources to OC was highest in Beijing (58 ± 5%) and decreased from Shanghai (49 ± 2%) to Xi'an (38 ± 3%) and Guangzhou (35 ± 7%). Generally, a larger fraction of fossil OC was from secondary origins than primary sources for all sites. Non-fossil sources accounted on average for 55 ± 10 and 48 ± 9% of OC and total carbon (TC), respectively, which suggests that non-fossil emissions were very important contributors of urban carbonaceous aerosols in China. The primary biomass-burning emissions accounted for 40 ± 8, 48 ± 18, 53 ± 4 and 65 ± 26% of non-fossil OC for Xi'an, Beijing, Shanghai and Guangzhou, respectively. Other non-fossil sources excluding primary biomass burning were mainly attributed to formation of secondary organic carbon (SOC) from non-fossil precursors such as biomass-burning emissions. For each site, we also compared samples from moderately to heavily polluted days according to particulate matter mass. Despite a significant increase of the absolute mass concentrations of primary emissions from both fossil and non-fossil sources during the heavily polluted events, their relative contribution to TC was even decreased, whereas the portion of SOC was consistently increased at all sites. This observation indicates that SOC was an important fraction in the increment of carbonaceous aerosols during the haze episode in China.

Reactive oxygen species associated with water-soluble PM<sub>2.5</sub> in the southeastern United States: spatiotemporal trends and source apportionment

Abstract. We assess the potential of the water-soluble fraction of atmospheric fine aerosols in the southeastern United States to generate reactive oxygen species (ROS) and identify major ROS-associated emission sources. ROS-generation potential of particles was quantified by the dithiothreitol (DTT) assay and involved analysis of fine particulate matter (PM) extracted from high-volume quartz filters (23 h integrated samples) collected at various sites in different environmental settings in the southeast, including three urban-Atlanta sites, in addition to a rural site. Paired sampling was conducted with one fixed site in Atlanta (Jefferson Street), representative of the urban environment, with the others rotating among different sites, for ~250 days between June 2012 and September 2013 (N=483). A simple linear regression between the DTT activity and aerosol chemical components revealed strong associations between PM ROS-generation potential and secondary organic aerosol (WSOC – water-soluble organic carbon) in summer, and biomass burning markers in winter. Redox-active metals were also somewhat correlated with the DTT activity, but mostly at urban and roadside sites. Positive matrix factorization (PMF) was applied to apportion the relative contribution of various sources to the ROS-generation potential of water-soluble PM2.5 in urban Atlanta. PMF showed that vehicular emissions contribute uniformly throughout the year (12–25%), while secondary oxidation processes dominated the DTT activity in summer (46%) and biomass burning in winter (47%). Road dust was significant only during drier periods (~12% in summer and fall). Source apportionment by chemical mass balance (CMB) was reasonably consistent with PMF, but with higher contribution from vehicular emissions (32%). Given the spatially large data set of PM sampled over an extended period, the study reconciles the results from previous work that showed only region- or season-specific aerosol components or sources contributing to PM ROS activity, possibly due to smaller sample sizes. The ubiquitous nature of the major sources of PM-associated ROS suggests widespread population exposures to aerosol components that have the ability to catalyze the production of oxidants in vivo.

Continental heat anomalies and the extreme melting of the Greenland ice surface in 2012 and 1889

AbstractRecent decades have seen increased melting of the Greenland ice sheet. On 11 July 2012, nearly the entire surface of the ice sheet melted; such rare events last occurred in 1889 and, prior to that, during the Medieval Climate Anomaly. Studies of the 2012 event associated the presence of a thin, warm elevated liquid cloud layer with surface temperatures rising above the melting point at Summit Station, some 3212 m above sea level. Here we explore other potential factors in July 2012 associated with this unusual melting. These include (1) warm air originating from a record North American heat wave, (2) transitions in the Arctic Oscillation, (3) transport of water vapor via an Atmospheric River over the Atlantic to Greenland, and (4) the presence of warm ocean waters south of Greenland. For the 1889 episode, the Twentieth Century Reanalysis and historical records showed similar factors at work. However, markers of biomass burning were evident in ice cores from 1889 which may reflect another possible factor in these rare events. We suggest that extreme Greenland summer melt episodes, such as those recorded recently and in the late Holocene, could have involved a similar combination of slow climate processes, including prolonged North American droughts/heat waves and North Atlantic warm oceanic temperature anomalies, together with fast processes, such as excursions of the Arctic Oscillation, and transport of warm, humid air in Atmospheric Rivers to Greenland. It is the fast processes that underlie the rarity of such events and influence their predictability.

Prescribed burning of logging slash in the boreal forest of Finland: emissions and effects on meteorological quantities and soil properties

Abstract. A prescribed fire experiment was conducted on 26 June 2009 in Hyytiälä, Finland, to study aerosol and trace gas emissions from prescribed fires of slash fuels and the effects of fire on soil properties in a controlled environment. A 0.8 ha forest near the SMEAR II measurement station (Station for Measuring Ecosystem-Atmosphere Relations) was cut clear; some tree trunks, all tree tops and branches were left on the ground and burned. The amount of burned organic material was ~46.8 tons (i.e., ~60 tons ha−1). The flaming phase lasted 2 h 15 min, the smoldering phase 3 h. Measurements were conducted on the ground with both fixed and mobile instrumentation, and in the air from a research aircraft. In the middle of the burning area, CO2 concentration peaked around 2000–3000 ppm above the baseline, and peak vertical flow velocities were ~9 m s−1, as measured with a 10 Hz 3-D sonic anemometer placed within the burn area. In the mobile measurements the peak particle number concentrations were approximately 1–2 × 106 cm−3 in the plume at a distance of 100–200 m from the burn area. On the ground at the SMEAR II station the geometric mean diameter of the mode with the highest concentration was 80 ± 1 nm during the flaming phase and in the middle of the smoldering phase, but, at the end of the smoldering phase, the largest mode was 122 nm. In the volume size distributions, geometric mean diameter of the largest volume mode was 153 nm during the flaming phase and 300 nm during the smoldering phase. The lowest single-scattering albedo of the ground-level measurements was 0.7 in the flaming-phase plume and ~0.9 in the smoldering phase. Elevated concentrations of several volatile organic compounds (VOC) (including acetonitrile, a biomass burning marker) were observed in the smoke plume at ground level. Measurements at the forest floor (i.e., a richly organic layer of soil and debris, characteristic of forested land) showed that VOC fluxes were generally low and consisted mainly of monoterpenes, and VOC flux peaked after the burning. After one year, the fluxes had nearly stabilized close to the level before the burning. The clear-cutting and burning of slash increased the total long-term CO2 release from the soil, and altered the physical, chemical and biological properties of the soil, such as increased the available nitrogen contents of the soil, which in turn, affected the long-term fluxes of greenhouse gases.

Method for the determination of specific molecular markers of biomass burning in lake sediments

Fire has an influence on regional to global atmospheric chemistry and climate. Molecular markers of biomass burning archived in lake sediments are becoming increasingly important in paleoenvironmental reconstruction and may help determine the interaction between climate and fire activity. Here, we present a high performance anion exchange chromatography–mass spectrometry method to allow separation and analysis of levoglucosan, mannosan and galactosan in lake sediments, with implications for reconstructing past biomass burning events. Determining mannosan and galactosan in Lake Kirkpatrick, New Zealand (45.03°S, 168.57°E) sediment cores and comparing these isomers with the more abundant biomass burning markers levoglucosan and charcoal represents a significant advancement in our ability to analyze past fire activity. Levoglucosan, mannosan and galactosan concentrations correlated significantly with macroscopic charcoal concentration. Levoglucosan/mannosan and levoglucosan/(mannosan+galactosan) ratios may help determine not only when fires occurred, but also if changes in the primary burned vegetation occurred.

Influence of Biomass Burning on the Levels of Atmospheric Polycyclic Aromatic Hydrocarbons and Their Nitro Derivatives in Chiang Mai, Thailand

ABSTRACTChiang Mai and several other provinces in northern Thailand have been annually facing air pollution problems during the dry season. Ten polycyclic aromatic hydrocarbons (PAHs); 19 nitropolycyclic aromatic hydrocarbons (NPAHs); and levoglucosan (LG), a marker for biomass burning, were quantified in total suspended particulates (TSP) collected in Chiang Mai during the dry, transition, and wet seasons in 2010. The concentrations of PAHs and NPAHs in the dry season were significantly higher than in the wet season. The [Benzo[a]pyrene (BaP)] – [benzo[ghi]perylene (BghiPe)] ratio, as an indicator of traffic, and the correlations of PAHs and NPAHs with LG showed that biomass burning significantly contributes to air pollution in the dry season. 9-Nitroanthracene (9-NA) was the most abundant NPAH which suggests that 9-NA is generated from biomass burning. We proposed the [9-NA] – [1-nitropyrene (1-NP)] ratio as a new indicator for assessing the contribution of biomass burning. Biomass burning was a major source of PAHs and NPAHs in the dry season, whereas vehicle exhaust was the main contribution in the wet season. The high carcinogenic risks in the dry season correlate with more harmful air conditions during this season. Thus, it is important to control biomass burning to reduce air-pollution-related health risks during the dry season in northern Thailand.

PM2.5 Chemical Source Profiles of Emissions Resulting from Industrial and Domestic Burning Activities in India

A study has been performed to develop PM_(2.5) (particles with aerodynamic diameters≦2.5) chemically speciated source profiles of different industrial and domestic burning practices in India. A total of fifty-five PM_(2.5) samples have been collected in emissions resulting from (1) industrial furnaces, (2) household fuels, (3) municipal solid waste burning, and (4) welding workshop burning practices, and categorized for eleven subtypes of sources. The collected samples were subjected to chemical analysis for twenty-one elemental (AI, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, S, Sb, Se, V, Zn), nine ionic (Na^+, K^+, Mg^(2+), Ca^(2+), NH_4^+, CI^-, F, NO_3^(-), SO_4^(2-)), OC, and EC source indicator species using atomic absorption spectrometry , ion chromatography and carbon analysis (thermal/optical transmittance method), respectively. The carbonaceous fraction was most abundant in household fuel burning emissions (47.6±7.45% to 65.92±13.13%). The ionic/elemental ratios of major inorganic constituents (Ca^(2+)/Ca, Mg^(2+)/Mg and Na+/Na) have been identified to describe the PM_(2.5) emissions from combustion or re-suspension dusts during industrial activities. Brick Kiln processes (BKP) have been identified as the major emitter of the highest number oftoxic species (Cd, Co, Mo, Sb and V), followed by steel rerolling mills (Hg and Pb) and steel processing industries (As, Ni). The source marker calculations also confirmed that K^+, Mn, and As are good markers for biomass burning, metallurgical industrial emission, and coal burning, respectively, similar to the findings in previous studies.

Airborne hydrogen cyanide measurements using a chemical ionisation mass spectrometer for the plume identification of biomass burning forest fires

Abstract. A chemical ionisation mass spectrometer (CIMS) was developed for measuring hydrogen cyanide (HCN) from biomass burning events in Canada using I− reagent ions on board the FAAM BAe-146 research aircraft during the BORTAS campaign in 2011. The ionisation scheme enabled highly sensitive measurements at 1 Hz frequency through biomass burning plumes in the troposphere. A strong correlation between the HCN, carbon monoxide (CO) and acetonitrile (CH3CN) was observed, indicating the potential of HCN as a biomass burning (BB) marker. A plume was defined as being 6 standard deviations above background for the flights. This method was compared with a number of alternative plume-defining techniques employing CO and CH3CN measurements. The 6-sigma technique produced the highest R2 values for correlations with CO. A normalised excess mixing ratio (NEMR) of 3.68 ± 0.149 pptv ppbv−1 was calculated, which is within the range quoted in previous research (Hornbrook et al., 2011). The global tropospheric model STOCHEM-CRI incorporated both the observed ratio and extreme ratios derived from other studies to generate global emission totals of HCN via biomass burning. Using the ratio derived from this work, the emission total for HCN from BB was 0.92 Tg (N) yr−1.

Levoglucosan concentrations in ice-core samples from the Tibetan Plateau determined by reverse-phase high-performance liquid chromatography–mass spectrometry

AbstractLevoglucosan is a unique marker for biomass burning that can be transported in the atmosphere and preserved in archives such as ice cores. A new method to determine the concentrations of levoglucosan in Tibetan ice-core samples using high-performance liquid chromatography with electrospray ionization mass spectrometry (HPLC-ESI/MS) was developed. Levoglucosan was separated from coeluting water-soluble organic compounds using a C18column with a gradient program from 50% to 90% methanol in ultrapure water. An external standard calibration curve (R2= 0.9958) was established by plotting the ion m/z 163 [M+H]+peak area versus the amount of analyte. The repeatability ranges between 11% and 2% at a concentration around 10 and 150 ng mL−1. The limit of detection was 10 ng mL−1and the limit of quantification was 40 ng mL−1. Levoglucosan concentrations ranged from 10 to 718 ng mL−1in the Muztagh Ata ice core and from 10 to 93 ng mL−1in the Tanggula ice core. These concentrations, up to 1000 times higher than those measured in samples from Antarctic and Greenland, showed the higher vulnerability of the Tibetan Plateau glaciers to biomass burning events.

Dynamic variations of ultrafine, fine and coarse particles at the Lu-Lin background site in East Asia

The characteristics of atmospheric ultrafine particles (i.e. <100 nm, nanoparticles or PM0.1), PM2.5 and PM10 were studied at the Lulin Atmospheric Background Station (LABS, 2862 m a.s.l., Taiwan) as part of the 7SEAS/Dongsha campaign. Sampling was conducted in July and August of 2009 and September to November of 2010, during which two 96-h and four 72-h PM samples were taken. Real-time particle size distributions were measured continuously from July to August of 2009 and July to November of 2010. PM0.1, PM2.5 and PM10 were collected by using two MOUDIs (micro-orifice uniform deposit impactor, MSP 110) and a Dichotomous PM10 sampler (Andersen SA-241) while real-time size distributions of particles of 5.5–350 nm in diameter were measured by an SMPS (scanning mobility particle sizer, TSI 3936). Filter samples were analyzed for gravimetric mass and chemical compositions, including organic carbon (OC), element carbon (EC), water-soluble ions and trace elements. Meteorology parameters and gaseous O3 and CO concentrations were also monitored along with the SMPS data for studying particle nucleation, condensation, SOA (secondary organic aerosol) formation and long-range air pollutant transport at the LABS. SMPS data showed that nanoparticle concentrations at the LABS remained relatively stable at low level (∼300–500 #/cm3) during the nighttime (22:00–04:00), increased during daytime, and reached a maximum (∼2000–4000 #/cm3) in the afternoon (12:00–16:00). The NMD (number median diameter) showed an opposite trend with the peak number concentrations observed in the afternoon corresponding to the smallest NMD (20–40 nm). These results indicate the dominance of local sources rather than the transport from other atmospheric air because that the lifetime of nanoparticles was only few minutes. Chemical analysis of filter samples showed that the concentrations of trace elements K and Mn, which serve as biomass burning markers, were elevated in the fine particle fractions during November 9–12th when the air mass passed through South and Southeast Asia prior to reaching the LABS. The concentrations of K and Mn would have been low if the aerosols had local origins The biomass burning derived K was found in all fine particle samples at the LABS suggesting that the free troposphere around Taiwan is frequently impacted by the long-range transport of biomass burning plumes via the westerly winds.

Levoglucosan as a specific marker of fire events in Greenland snow

ABSTRACTWe demonstrate the use of levoglucosan (1,6-anhydro-β-d-glucopyranose) as a source-specific proxy of past fire activity in snow pits and ice cores. Levoglucosan is unambiguously a degradation product derived from cellulose burning at temperatures greater than 300 °C and is widely used as a biomass burning marker in aerosol analyses. We analyse samples collected from a 3 m snow pit at Summit, Greenland (72°20′N, 38°45′W; 3270 m a.s.l.), with a known depositional history where biomass burning aerosols were traced from their source in a Canadian smoke plume, through their eastward transport and deposition on the Greenland ice sheet, and their eventual burial by accumulating snow layers. The snow pit levoglucosan profile replicates oxalate concentrations from a known forest fire event, suggesting the applicability of levoglucosan as a marker of past fire activity in snow and by extension in ice cores. However, levoglucosan concentration peaks in the snow pit differ from those of ammonium and potassium, which are traditionally used as biomass burning proxies in snow and ice studies but which incorporate sources other than fire activity. The source specificity of levoglucosan can help determine the past relative contribution of biomass burning aerosols when used in conjunction with other proxies in snow and ice.

Characterisation of airborne particles and associated organic components produced from incense burning

Airborne particles generated from the burning of incense have been characterized in order to gain an insight into the possible implications for human respiratory health. Physical characterization performed using field-emission scanning electron microscopy showed incense particulate smoke mainly consisted of soot particles with fine and ultrafine fractions in various aggregated forms. A range of organic compounds present in incense smoke have been identified using derivatisation reactions coupled with gas chromatography-mass spectrometry analysis. A total of 19 polar organic compounds were positively identified in the samples, including the biomass burning markers levoglucosan, mannosan and galactosan, as well as a number of aromatic acids and phenols. Formaldehyde was among 12 carbonyl compounds detected and predominantly associated with the gas phase, whereas six different quinones were also identified in the incense particulate smoke. The nano-structured incense soot particles intermixed with organics (e.g. formaldehyde and quinones) could increase the oxidative capacity. When considering the worldwide prevalence of incense burning and resulting high respiratory exposures, the oxygenated organics identified in this study have significant human health implications, especially for susceptible populations.

Submicron aerosol analysis and organic source apportionment in an urban atmosphere in Pearl River Delta of China using high-resolution aerosol mass spectrometry

[1] The Pearl River Delta (PRD) region in South China is one of the most economically developed regions in China while also noted for its severe air pollution, especially in the urban environments. In order to understand in depth the aerosol chemistry and the emission sources in PRD, an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at an urban site in the Hong Kong–Shenzhen metropolitan area between 25 October and 2 December 2009. Ten minute–resolved measurement data were analyzed, and an average mass concentration of 44.5 ± 34.0 μg m−3 was calculated for the entire campaign. On average, organic matter was the most abundant PM1 component accounting for 39.7% of the total mass, followed by sulfate (24.5%), black carbon (measured by aethalometer, 14.0%), ammonium (10.2%), nitrate (10.0%), and chloride (1.6%). Moreover, organic matter comprised an increasing fraction of the PM1 loading as the PM1 loading increased, denoting its key role in particulate pollution in this region. Calculations of organic elemental composition based on the high-resolution organic mass spectra obtained indicated that C, H, O, and N on average contributed 33.8%, 55.1%, 10.2%, and 0.9%, respectively, to the total atomic numbers of organic aerosol (OA), which corresponded to an OM/OC ratio (the ratio of organic matter mass/organic carbon mass) of 1.57 ± 0.08. Positive matrix factorization analysis was then conducted on the high-resolution organic mass spectral data set. Four OA components were identified, including a hydrocarbon-like (HOA), a biomass burning (BBOA), and two oxygenated (LV-OOA and SV-OOA) components, which on average accounted for 29.5%, 24.1%, 18.8%, and 27.6%, respectively, of the total organic mass. The HOA was found to have contributions from both fossil fuel combustion and cooking emissions, while the BBOA was well correlated with acetonitrile, a known biomass burning marker. The LV-OOA and SV-OOA corresponded to more aged and fresher secondary organic aerosol, respectively. The diurnal variations of the LV-OOA and SV-OOA showed significant increase in concentration in the daytime, denoting their substantial photochemical formation. Back trajectory analysis indicated that the short-range regional transport from the northeast was the key factor leading to severe submicron aerosol pollution in this area. The HR-ToF-AMS measurement results in this campaign are completely compared with a previous paper that reports the HR-ToF-AMS measurement results at a rural site in PRD in the same season, based on which the regional pollution characteristics of submicron particle in PRD were analyzed.

The use of polar organic compounds to estimate the contribution of domestic solid fuel combustion and biogenic sources to ambient levels of organic carbon and PM 2.5 in Cork Harbour, Ireland

PM 2.5 samples collected at Cork Harbour, Ireland during summer, autumn, late autumn and winter, 2008–2009 were analyzed for polar organic compounds that are useful markers for aerosol source characterization. The determined compounds include tracers for biomass burning primary particles, fungal spores, markers for secondary organic aerosol (SOA) from isoprene, α-/ β-pinene, and d-limonene. Seasonal and temporal variations and other characteristic features of the detected tracers are discussed in terms of aerosol sources and processes. The biogenic species were detected only during the summer period where the contributions of isoprene SOA and fungal spores to the PM 2.5 organic carbon (OC) were estimated to be 1.6% and 1% respectively. The biomass burning markers, and in particular levoglucosan, were present in all samples and attributed to the combustion of cellulose-containing fuels including wood, peat, bituminous and smokeless coal. The contribution of domestic solid fuel (DSF) burning to the measured OC mass concentration was estimated at 10.8, 50, 66.4 and 74.9% for summer, autumn, late autumn and winter periods, respectively, based on factors derived from a series of burning experiments on locally available fuels. Application of an alternative approach, namely principal component analysis–multiple linear regression (PCA–MLR), to the measured concentrations of the polar organic marker compounds used in conjunction with real-time air quality data provided similar trends and estimates for DSF combustion during all seasons except summer. This study clearly demonstrates that, despite the ban on the sale of bituminous coal in Cork and other large urban areas in Ireland, DSF combustion is still the major source of OC during autumn and winter periods and also makes a significant contribution to PM 2.5 levels. The developed marker approach for estimating the contribution of DSF combustion to ambient OC concentrations can, in principle, also be applied to other locations.

Polar organic and inorganic markers in PM 10 aerosols from an inland city of China — Seasonal trends and sources

Polar organic compounds and elements were quantified in PM 10 aerosols collected in urban and rural areas of Baoji, an inland city of China, during winter and spring 2008. Concentrations of biomass burning markers and high molecular weight n-alkanoic acids (HMW, > C 22:0) were heavily increased in winter. In contrast, sugars presented in higher levels in the spring, among which sucrose was the most abundant with an average of 219 ng m −3 in winter and 473 ng m −3 in spring respectively. This suggests enhanced biotic activity in the warm season, whereas no obvious trend was observed for sugar alcohols, concentrations of the three sugar alcohols in spring were only 0.94–2.3 times as those in winter, indicating a second pathway of their formation other than fungal spores in cold season. Major crustal elements (i.e., Fe, K, Mn and Ti) in PM 10 aerosols were also observed in larger concentrations in spring samples than those in winter due to an enhancement of coarse particles from soil minerals. By using principal component analysis (PCA) and positive matrix factorization (PMF), sources and their contributions to the PM components were also investigated in this study. Four factors were extracted with both models, and the sources represented by different factors were based on the highest loaded marker species as follows: factor 1, soil and road dust (Fe, Sr and Ti); factor 2, biomass burning (levoglucosan, galactosan and syringic acid); factor 3, microbial emissions (fructose and sucrose); and factor 4, fossil fuel combustion and fungal spores influence (Pb, Zn, arabitol and mannitol). The high correlation between PM 10 and factor 1 suggested that PM 10 pollution in Baoji was dominated by soil and dust re-suspension.

Anhydrosugar and sugar alcohol organic markers associated with carboxylic acids in particulate matter from incense burning

Aerosol from the burning two types of sandalwood-based incense, Hsing Shan and Lao Shan, was analyzed to characterize the chemical profile of total particulate matter emitted. The total particulate matter (PM) mass emission factors were 46.3 ± 2.68 mg g −1 of Hsing Shan incense and 43.7 ± 1.08 mg g −1 of Lao Shan incense. Chemical analysis of emissions from the two types of incense revealed that of the 25 components in four groups characterized, anhydrosugars formed the major group, at 46.7–52.2% w/w of the identified particulate and 1078.3–1169.8 μg g −1 of incense, followed by inorganic salts at 30.4–31.8% w/w of identified particulate and 681.6–734.0 μg g −1 of incense, carboxylic acids at 12.0–17.1% w/w of the identified particulate and 268.6–392.8 μg g −1 of incense, and sugar alcohols at 4.44–5.38% w/w of the identified particulate and 102.3–120.6 μg g −1 of incense. More anhydrosugars and sugar alcohols were emitted from Lao Shan incense than from Hsing Shan incense whereas more carboxylic acids and organic salts were emitted from Hsing Shan than from Lao Shan. These differences were due to structural and functional differences in the young sandalwood used to make Hsing Shan and the aged sandalwood used to make Lao Shan. The anhydrosugar levoglucosan, used as a marker of biomass burning, was always the most abundant species in emitted PM for both incenses ( Lao Shan 21.7 mg g −1 of PM and Hsing Shan 18.7 mg g −1). K + and Cl − were the second most abundant components (K + and Cl − were summed), accounting for 10.6 mg g −1 of Hsing Shan PM and 9.85 mg g −1 of Lao Shan PM. The most abundant carboxylic acids in the emissions were formic, acetic, succinic, glutaric and phthalic acid. The latter is a fragrance ingredient and a potential health hazard and was twice as prevalent in Lao Shan emissions. Xylitol was the most prevalent of the sugar alcohols at 35.7–36.6% w/w of total identified sugar alcohols. These abundant species are potential markers for incense burning. K +, levoglucosan, mannosan and xylitol are already reported in discriminator ratios for wood burning and it is proposed here that these can and should also apply to incense burning. The calculated discriminator ratios for two types of incense burning reported here are 0.229–0.288 for K/Levo, 12.5–13.5 for Levo/Manno, and 21.5–23.7 for the novel discriminator ratio Levo/Xylitol.

Fire and climate: Biomass burning recorded in ice and lake cores

Human activities including fossil fuel burning are currently altering the global climate system at rates faster than ever recorded in geologic time. Biomass burning causes carbon dioxide emissions equal to 50% of those from fossil-fuel combustion and so are highly likely to influence future climate change. However, aerosols continue to be one of the least understood aspects of the modern climate system and even less is known about their past influence. Ice and lake core proxy records provide quantifiable data on past fire regimes across most spatial and temporal scales. Some monosaccharide anhydrides such as levoglucosan, mannosan and galactosan are used as specific molecular markers for biomass burning as they can only be produced by combustion processes at temperatures greater than 300 °C and are present in both ice and lake cores. Other paleofire tracers such as microcharcoal, polycyclic aromatic hydrocarbons, and pollen records augment the fire history derived at single sites or across regions. As both pyrochemical and climate parameters are determined from the same depth and time within the ice or sediment matrix, the multi-proxy nature of ice and lake cores presents an ideal material to investigate the links between fires and climate change.

Atmospheric Stability of Levoglucosan: A Detailed Laboratory and Modeling Study

Levoglucosan, an important molecular marker for biomass burning, represents an important fraction of the water-soluble organic carbon in atmospheric particles influenced by residential wood burning and wildfires. However, particle phase oxidation processes of levoglucosan by free radicals are not well-known. Hence, detailed kinetic studies on the reactivity of levoglucosan with OH, NO(3), and SO(4)(-) radicals in aqueous solutions were performed to better understand the levoglucosan oxidation in the deliquescent particles. The data obtained were implemented into a parcel model with detailed microphysics and complex multiphase chemistry to investigate the degradation fluxes of levoglucosan in cloud droplets and in deliquescent particles. The model calculations show that levoglucosan can be oxidized readily by OH radicals during daytime with mean degradation fluxes of about 7.2 ng m(-3) h(-1) in summer and 4.7 ng m(-3) h(-1) in winter for a polluted continental plume. This indicates that the oxidation of levoglucosan in atmospheric deliquescent particles is at least as fast as that of other atmospherically relevant organic compounds and levoglucosan may not be as stable as previously thought in the atmosphere, especially under high relative humidity conditions.

Seasonal variations of elemental carbon in urban aerosols as measured by two common thermal-optical carbon methods

Two commonly employed laboratory-based elemental carbon (EC) and organic carbon (OC) thermal/optical methods for the analysis of ambient particulate matter were used to analyze 709 twenty-four hour integrated PM 2.5 samples along with 76 field blanks from the St. Louis-Midwest Supersite in East St. Louis, Illinois. The two laboratory ECOC methods were the Aerosol Characterization Experiment—Asia (ACE-Asia) method based on National Institute of Occupational Safety and Health (NIOSH 5040) method and the Interagency Monitoring of Protected Visual Environments (IMPROVE) protocol. As in previous intercomparisons between these two methods, there was excellent agreement for total carbon (i.e. sum of EC and OC), but significant differences were observed in the split between the measured EC and OC. The 709 daily PM 2.5 samples spanned a time series of two years that allowed an assessment of seasonal relationships between the EC reported by the two methods. Seasonal average ACE-Asia and IMPROVE EC concentration values were highest in the fall and lowest in the spring. Differences between the seasonal average IMPROVE and ACE-Asia EC concentration values were about 40% greater in summer compared to winter. While IMPROVE EC values were always larger than ACE-Asia EC, the EC difference between these methods exhibited a strong seasonal variation with largest differences occurring in the spring and especially summer with the smallest differences in the fall and winter. Seasonal average EC differences (IMPROVE − ACE-Asia) were anti-correlated with molecular markers for biomass burning and mobile source emissions that had wintertime maximum concentrations. The EC difference between methods did have a moderate positive correlation with indicators of secondary organic aerosol and sulfate suggesting that oxidized organic aerosol associated with atmospheric processing or other secondary components of ambient aerosol could be associated with the seasonal differences between these EC measurements.