Quantification of monosaccharide anhydrides by liquid chromatography combined with mass spectrometry: application to aerosol samples from an urban and a suburban site influenced by small-scale wood burning

Levels of the monosaccharide anhydride (MA) levoglucosan and its isomeric compounds galactosan and mannosan were quantified in the PM10 fraction (particulate matter < or = 10 microm in aerodynamic diameter) of ambient aerosols from an urban (Oslo) and a suburban (Elverum) site in Norway, both influenced by small-scale wood burning. MAs are degradation products of cellulose and hemicellulose, and levoglucosan is especially emitted in high concentrations during pyrolysis and combustion of wood, making it a potential tracer of primary particles emitted from biomass burning. MAs were quantified using a novel high-performance liquid chromatography/ high-resolution mass spectrometry-time of flight method. This approach distinguishes between the isomeric compounds of MAs and benefits from the limited sample preparation required before analysis, and no extensive derivatization step is needed. The highest concentrations of levogucosan, galactosan, and mannosan (sigmaMA) were recorded in winter because of wood burning for residential heating (sigmaMA(MAX) = 1,240 ng m(-3)). This finding was substantiated by a relatively high correlation (R2 = 0.64) between the levoglucosan concentration and decreasing ambient temperature. At the suburban site, sigmaMA accounted for 3.1% of PM10, whereas the corresponding level at the urban site was 0.6%. The mass size distribution of MAs associated with atmospheric aerosols was measured using a Berner cascade impactor. The size distribution was characterized with a single mode at 561 nm. Ninety-five percent of the mass concentration of the MAs was found to be associated with particles < 2 micro.m. A preliminary attempt to estimate the contribution of wood burning to the mass concentration of PM10 in Oslo using levoglucosan as a tracer indicates that 24% comes from wood burning. This is approximately a factor of 2 lower than estimated by the AirQUIS dispersion model.     

Seasonal variations of monosaccharide anhydrides in PM1 and PM2.5 aerosol in urban areas

The concentrations of monosaccharide anhydrides (levoglucosan, mannosan, galactosan) in PM1 and PM2.5 aerosol samples were measured in Brno and ?lapanice in the Czech Republic in winter and summer 2009. 56 aerosol samples were collected together at both sites to investigate the different sources that contribute to aerosol composition in studied localities. Daily PM1 and PM2.5 aerosol samples were collected on pre-fired quartz fibre filters.The sum of average atmospheric concentration of levoglucosan, mannosan and galactosan in PM1 aerosol in ?lapanice and Brno during winter was 513 and 273 ng m^?3, while in summer the sum of average atmospheric concentration of monosaccharide anhydrides (MAs) was 42 and 38 ng m^?3, respectively. The sum of average atmospheric concentration of MAs in PM1 aerosol formed 71 and 63% of the sum of MA concentration in PM2.5 aerosol collected in winter in ?lapanice and Brno, whereas in summer the sum of average atmospheric concentration of MAs in PM1 aerosol formed 45 and 43% of the sum of MA concentration in PM2.5 aerosol in ?lapanice and Brno, respectively.In winter, the sum of MAs contributed significantly to PM1 mass ranging between 1.37% and 2.67% of PM1 mass (Brno – ?lapanice), while in summer the contribution of the sum of MAs was smaller (0.28–0.32%). Contribution of the sum of MAs to PM2.5 mass is similar both in winter (1.37–2.71%) and summer (0.44–0.55%).The higher concentrations of monosaccharide anhydrides in aerosols in ?lapanice indicate higher biomass combustion in this location than in Brno during winter season. The comparison of levoglucosan concentration in PM1 and PM2.5 aerosol shows prevailing presence of levoglucosan in PM1 aerosol both in winter (72% on average) and summer (60% on average).The aerosol samples collected in ?lapanice and Brno in winter and summer show comparable contributions of levoglucosan, mannosan and galactosan to the total amount of monosaccharide anhydrides in both aerosol size fractions. Levoglucosan was the most abundant monosaccharide anhydride with a relative average contribution to the total amount of MAs in the range of 71–82% for PM1 aerosols and 52–79% for PM2.5 aerosols.     

Wood burning impact on PM10 in three Austrian regions

Anhydrosugars (levoglucosan, mannosan and galactosan) were investigated during one year in three Austrian regions at three types of sites (city-heavy traffic-impacted, city-residential and background) in order to assess the magnitude of the contribution of wood smoke to the particulate matter load and its organic fraction. The annually averaged concentrations of levoglucosan ranged from 0.12 to 0.48 μg m^?3. The levoglucosan concentration exhibited a strong annual cycle with higher concentrations in the cold season. The minor anhydrosugars had a similar annual trend, but their concentrations were lower by a factor of about 5 and about 25 in the cold season for mannosan and galactosan, respectively. Levoglucosan concentrations were higher at the inner-urban as compared to rural sites. The contribution of wood smoke to organic carbon and PM₁₀ levels was calculated using a constant ratio of levoglucosan and OC, respectively PM₁₀ as derived for fire wood typical for Alpine European regions [Schmidl, C., Marr, I.L., Caseiro, A.e, Kotianová, P., Berner, A., Bauer, H., Kasper-Giebl, A., Puxbaum, H., 2008a. Chemical characterisation of fine particle emissions from wood stove combustion of common woods growing in mid-European Alpine regions. Atmospheric Environment 42, 126–141]. The estimated contribution of wood smoke-OC to the OC of PM₁₀ ranged from one third to more than half in the cold season with higher contributions up to 70% in winter (December, January and February) in the smaller cities and the rural background. This indicates, that wood smoke is the predominant source of organic material at rural and small urban sites in central Europe. Consistently, wood smoke was an important contributor to PM₁₀ during the cold season, with contributions of around 10% in the Vienna larger region and around 20% at rural sites in the densely forested regions of Salzburg and Styria during the winter months. In those regions residential sites exhibited highest relative wood smoke contents in PM₁₀ during autumn (September till November), indicating the use of wood stoves for auxiliary heating in the transition of warm to cold season. Using the relationships between the different anhydrosugars the combustion of softwood was found to be dominant for the wood smoke occurrence in ambient air at the investigated sites. Potassium, a commonly used tracer for biomass burning, correlated well to levoglucosan, with a mass ratio of around 0.80 in the cold season.     

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

Levoglucosan (L), mannosan (M), galactosan (G) and other cellulose and lignin markers from burn tests of Miocene lignites of Poland were determined by gas chromatography–mass spectrometry (GC–MS) to assess their distributions and concentrations in the smoke. Their distributions were compared to those in the pyrolysis products of the lignites. Levoglucosan and other anhydrosaccharides are products from the thermal degradation of cellulose and hemicellulose and are commonly used as tracers for wood smoke in the atmosphere. Here we report emission factors of levoglucosan in smoke particulate matter from burning of lignite varying from 713 to 2154 mg kg^?1, which are similar to those from burning of extant plant biomass. Solvent extracts of the lignites revealed trace concentrations of native levoglucosan (0.52–3.7 mg kg^?1), while pyrolysis yielded much higher levels (1.6–3.5 × 10⁴ mg kg^?1), indicating that essentially all levoglucosan in particulate matter of lignite smoke is derived from cellulose degradation. The results demonstrate that burning of lignites is an additional input of levoglucosan to the atmosphere in regions where brown coal is utilized as a domestic fuel. Interestingly, galactosan, another tracer from biomass burning, is not emitted in lignite smoke and mannosan is emitted at relatively low concentrations, ranging from 7.8 to 70.5 mg kg^?1. Thus, we propose L/M and L/(M + G) ratios as discriminators between products from combustion of lignites and extant biomass. In addition, other compounds, such as shonanin, belonging to lignans, and some saccharides, e.g., α- and β-glucose and cellobiose, are reported for the first time in extracts of bulk lignites and of smoke particulate matter from burning these lignites.     

Wood smoke as a source of particle-phase organic compounds in residential areas

The objective of this study was to investigate the organic composition of wood smoke emissions and ambient air samples in order to determine the wood smoke contribution to the ambient air pollution in the residential areas. From November 2005 to March 2006 particle-phase PM₁₀ samples were collected in the residential town Dettenhausen surrounded by forests near Stuttgart in southern Germany. Samples collected on pre-baked glass fibre filters were extracted using toluene with ultrasonic bath and analysed by gas chromatography mass spectrometry (GC-MS). 21 polycyclic aromatic hydrocarbons (PAH) including 16 USEPA priority pollutants, different organic wood smoke tracers, primarily 21 species of syringol and guaiacol derivatives, levoglucosan and its isomers mannosan, galactosan and dehydroabietic acid were detected and quantified in this study. The concentrations of these compounds were compared with the fingerprints of emissions from hardwood and softwood combustion carried out in test facilities at Universitaet Stuttgart and field investigations at a wood stove during real operation in Dettenhausen. It was observed that the combustion derived PAH was detected in higher concentrations than other PAH in the ambient air PM₁₀ samples. Syringol and its derivatives were found in large amounts in hardwood burning but were not detected in softwood burning emissions. On the other hand, guaiacol and its derivatives were found in both softwood and hardwood burning emissions, but the concentrations were higher in the softwood smoke compared to hardwood smoke. So, these compounds can be used as typical tracer compounds for the different types of wood burning emissions. In ambient air samples both syringol and guaiacol derivatives were found which indicates the wood combustion contribution to the PM load in such residential areas. Levoglucosan was detected in high concentrations in all ambient PM₁₀ samples. A source apportionment modelling, Positive Matrix Factorization (PMF) was implemented to quantify the wood smoke contribution to the ambient PM₁₀ bound organic compounds in the residential area.     

Temporal variation and impact of wood smoke pollution on a residential area in southern Germany

This paper is a continuation of our previous publication (Bari, M.A., Baumbach, G., Kuch, B., Scheffknecht, G., 2009. Wood smoke as a source of particle-phase organic compounds in residential areas. Atmospheric Environment 43, 4722–4732) and describes a detailed characterisation of different particle-phase wood smoke tracer compounds in order to find out the impact of wood-fired heating on ambient PM₁₀ pollution in a residential area near Stuttgart in southern Germany. The results from previous flue gas measurements help distinguishing different tracer compounds in ambient PM₁₀ samples. In the residential area, significant amounts of hardwood markers (syringaldehyde, acetosyringone, propionylsyringol, sinapylaldehyde) and low concentrations of softwood markers (vanillin, acetovanillone, coniferyldehyde, dehydroabietic acid, retene) were found in the ambient air. The general wood combustion markers Levoglucosan, mannosan and galactosan were detected in high concentrations in all particle-phase PM₁₀ samples. To find out the size distribution of ambient particles, cascade impactor measurements were carried out. It was found that more than 70% of particulate matter was in the particle diameter of less than 1 μm. Using emission ratio of levoglucosan to PM₁₀, it can be demonstrated that during winter months 59% of ambient PM₁₀ pollution could be attributed to residential wood-fired heating.     

Chemical composition of aerosols during a major biomass burning episode over northern Europe in spring 2006: Experimental and modelling assessments

The long-range transported smokes emitted by biomass burning had a strong impact on the PM_2.5 mass concentrations in Helsinki over the 12 days period in April and May 2006. To characterize aerosols during this period, the real-time measurements were done for PM_2.5, PM_2.5–10, common ions and black carbon. Moreover, the 24-h PM₁ filter samples were analysed for organic and elemental carbon (OC and EC), water-soluble organic carbon (WSOC), ions and levoglucosan. The Finnish emergency and air quality modelling system SILAM was used for the forecast of the PM_2.5 concentration generated by biomass burning. According to the real-time PM_2.5 data, the investigated period was divided into four types of PM situations: episode 1 (EPI-1; 25–29 April), episode 2 (EPI-2; 1–5 May), episode 3 (EPI-3; 5–6 May) and a reference period (REF; 24 March–24 April). EPI-3 included a local warehouse fire and therefore it is discussed separately. The PM₁ mass concentrations of biomass burning tracers—levoglucosan, potassium and oxalate—increased during the two long-range transport episodes (EPI-1 and EPI-2). The most substantial difference between the episodes was exhibited by the sulphate concentration, which was 4.9 (±1.4) μg m⁻³ in EPI-2 but only 2.4 (±0.31) μg m⁻³ in EPI-1 being close to that of REF (1.8±0.54 μg m⁻³). The concentration of particulate organic matter in PM₁ was clearly higher during EPI-1 (11±3.3 μg m⁻³) and EPI-2 (9.7±4.0 μg m⁻³) than REF (1.3±0.45 μg m⁻³). The long-range transported smoke had only a minor impact on the WSOC-to-OC ratio. According to the model simulations, MODIS detected the fires that caused the first set of concentration peaks (EPI-1) and the local warehouse fire (EPI-3), but missed the second one (EPI-2) probably due to dense frontal clouds.     

Wood Smoke Contribution to Winter Aerosol in Fresno,CA

Abstract

In an effort to better quantify wintertime particulate matter (PM) and the contribution of wood smoke to air pollution events in Fresno, CA, a field campaign was conducted in winter 2003–2004. Coarse and fine daily PM samples were collected at five locations in Fresno, including residential, urban, and industrial areas. Measurements of collected samples included gravimetric mass determination, organic and elemental carbon analysis, and trace organic compound analysis by gas chromatograph mass spectrometry (GC/MS). The wood smoke tracer levoglucosan was also measured in aqueous aerosol extracts using high-performance anion exchange chromatography coupled with pulsed amperometric detection. Sample preparation and analysis by this technique is much simpler and less expensive than derivatized levoglucosan analysis by GC/MS, permitting analysis of daily PM samples from all five of the measurement locations. Analyses revealed low spatial variability and similar temporal patterns of PM_2.5 mass, organic carbon (OC), and levoglucosan. Daily mass concentrations appear to have been strongly influenced by meteorological conditions, including precipitation, wind, and fog events. Fine PM (PM_2.5) concentrations are uncommonly low during the study period, reflecting frequent precipitation events. During the first portion of the study, levoglucosan had a strong relationship to the concentrations of PM_2.5 and OC. In the later portion of the study, there was a significant reduction in levoglucosan relative to PM_2.5 and OC. This may indicate a change in particle removal processes, perhaps because of fog events, which were more common in the latter period. Combined, the emissions from wood smoke, meat cooking, and motor vehicles appear to contribute ~65–80% to measured OC, with wood smoke, on average, accounting for ~41% of OC and ~18% of PM_2.5 mass. Two residential sites exhibit somewhat higher contributions of wood smoke to OC than other locations.     

Chemical speciation,transport and contribution of biomass burning smoke to ambient aerosol in Guangzhou,a mega city of China

Intensive measurements of aerosol (PM₁₀) and associated water-soluble ionic and carbonaceous species were conducted in Guangzhou, a mega city of China, during summer 2006. Elevated levels of most chemical species were observed especially at nighttime during two episodes, characterized by dramatic build-up of the biomass burning tracers levoglucosan and non-sea-salt potassium, when the prevailing wind direction had changed due to two approaching tropical cyclones. High-resolution air mass back trajectories based on the MM5 model revealed that air masses with high concentrations of levoglucosan (43–473 ng m^?3) and non-sea-salt potassium (0.83–3.2 μg m^?3) had passed over rural regions of the Pearl River Delta and Guangdong Province, where agricultural activities and field burning of crop residues are common practices. The relative contributions of biomass burning smoke to organic carbon in PM₁₀ were estimated from levoglucosan data to be on average 7.0 and 14% at daytime and nighttime, respectively, with maxima of 9.7 and 32% during the episodic transport events, indicating that biomass and biofuel burning activities in the rural parts of the Pearl River Delta and neighboring regions could have a significant impact on ambient urban aerosol levels.     

Results from a pilot-scale air quality study in Addis Ababa, Ethiopia

Twenty-one samples were collected during the dry season (26 January–28 February 2004) at 12 sites in and around Addis Ababa, Ethiopia and analyzed for particulate matter with aerodynamic diameter <10 μm (PM₁₀) mass and composition. Teflon-membrane filters were analyzed for PM₁₀ mass and concentrations of 40 elements. Quartz-fiber filters were analyzed for chloride, sulfate, nitrate, and ammonium ions as well as elemental carbon (EC) and organic carbon (OC) content. Measured 24-h PM₁₀ mass concentrations were <100 and 40 μg m⁻³ at urban and suburban sites, respectively. PM₁₀ lead concentrations were <0.1 μg m⁻³ for all samples collected, an important finding because the government of Ethiopia had stopped the distribution of leaded gasoline a few months prior to this study. Mass concentrations reconstructed from chemical composition indicated that 34–66% of the PM₁₀ mass was due to geologically derived material, probably owing to the widespread presence of unpaved roads and road shoulders. At urban sites, EC and OC compounds contributed between 31% and 60% of the measured PM₁₀ while at suburban sites carbon compounds contributed between 24% and 26%. Secondary sulfate aerosols were responsible for <10% of the reconstructed mass in urban areas but as much as 15% in suburban sites, where PM₁₀ mass concentrations were lower. Non-volatile particulate nitrate, a lower limit for atmospheric nitrate, constituted <5% and 7% of PM₁₀ at the urban and suburban sites, respectively. At seven of the 12 sites, real-time PM₁₀ mass, real-time carbon monoxide (CO), and instantaneous ozone (O₃) concentrations were measured with portable nephelometers, electrochemical analyzers, and indicator test sticks, respectively. Both PM₁₀ and CO concentrations exhibited daily maxima around 7:00 and secondary peaks in the late afternoon and evening, suggesting that those pollutants were emitted during periods associated with motor-vehicle traffic, food preparation, and heating of homes. The morning concentration maxima were likely accentuated by stable atmospheric conditions associated with overnight surface temperature inversions. Ozone concentrations were measured near mid-day on filter sample collection days and were in all cases <45 parts per billion.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Evidence for a significant contribution of wood burning aerosols to PM2.5 during the winter season in Paris,France

Although particulate emissions from residential wood burning have become a subject of great scientific concern for a few years, data related to their impact on the air quality of large European urban centres are still missing. In the present study, we investigated the chemical and optical properties of fine (PM_2.5) carbonaceous aerosols in Paris during the 2005 winter season in order to track the presence of wood burning emissions in such a large city. The use of a seven wavelength Aethalometer allowed us to document shortwave light absorption by brown-carbon-containing organic aerosols of biomass burning origin. In particular, a well-marked diurnal pattern of the spectral dependence of light absorption, with maxima during the night, could be observed every day of the campaign and attributed to wood burning emissions. Relatively high absorption Ångstrom exponents and WSOC/OC ratios (respectively 1.25 and 0.35 on average for the period of study) also indicated the importance of biomass burning aerosols in the Paris atmosphere in winter. Finally, a rough estimate of the contribution of wood burning carbonaceous aerosols to PM_2.5 could be achieved. This contribution was found to be as high as 20 ± 10% on average at the Paris background site investigated here.     

Is Levoglucosan a Suitable Quantitative Tracer for Wood Burning? Comparison with Receptor Modeling on Trace Elements in Lycksele,Sweden

Abstract

Particle emissions from residential wood combustion in small communities in Northern Sweden can sometimes increase the ambient particle concentrations to levels comparable to densely trafficked streets in the center of large cities. The reason for this is the combination of increased need for domestic heating during periods of low temperatures, leading to higher emission rates, and stable meteorological conditions. In this work, the authors compare two different approaches to quantify the wood combustion contribution to fine particles in Northern Sweden: a multivariate source-receptor analysis on inorganic compounds followed by multiple linear regression (MLR) of fine particle concentrations and levoglucosan used as a tracer. From the receptor model, it can be seen that residential wood combustion corresponds with 70% of modeled particle mass. Smaller contributions are also seen from local nonexhaust traffic particles, road dust, and brake wear (each contributing 14%). Of the mass, 1.5% is explained by long-distance transported particles, and 2% derives from a regional source deriving from either oil combustion or smelter activities.

In samples collected in ambient air, a significant linear correlation was found between wood burning particles and levoglucosan. The levoglucosan fraction in the ambient fine particulate matter attributed to wood burning according to the multivariate analysis ranged from <2% to 50%. This is much higher than the fraction found in the emission from the boilers expected to be responsible for most emissions at this site (between 3% and 6%). A laboratory emission study of wood and pellet boilers gave 0.3%_wt to 22%_wt levoglucosan to particle mass, indicating that the levoglucosan fraction may be highly dependent on combustion conditions, making it uncertain to use it as a quantitative tracer under real-world burning conditions. Thus, quantitative estimates of wood burning contributions will be very uncertain using solely levoglucosan as a tracer.     

Characterization and seasonal variations of levoglucosan in fine particulate matter in Xi’an,China

PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) samples (n = 58) collected every sixth day in Xi’an, China, from 5 July 2008 to 27 June 2009 are analyzed for levoglucosan (1,6-anhydro-β-d-glucopyranose) to evaluate the impacts of biomass combustion on ambient concentrations. Twenty-four-hour levoglucosan concentrations displayed clear summer minima and winter maxima that ranged from 46 to 1889 ng m^?3, with an average of 428 ± 399 ng m^?3. Besides agricultural burning, biomass/biofuel combustion for household heating with straws and branches appears to be of regional importance during the heating season in northwestern China. Good correlations (0.70 < R < 0.91) were found between levoglucosan relative to water-soluble K⁺, Cl^?, organic carbon (OC), elemental carbon (EC), and glyoxal. The highest levoglucosan/OC ratio of 2.3% was found in winter, followed by autumn (1.5%). Biomass burning contributed to 5.1–43.8% of OC (with an average of 17.6 ± 8.4%).

Implications:?PM_2.5 levoglucosan concentrations and the correlation between levoglucosan relative to other compounds during four seasons in Xi’an showed that the influence of biomass burning is maximum during the residential heating season (winter), although some important influences may be detected in spring (field preparation burnings) and autumn (corn stalks and wheat straw burning, fallen dead leaves burning) at Xi’an and surrounding areas. Household heating with biomass during winter was quite widespread in Guanzhong Plain. Therefore, the control of biomass/biofuel combustion could be an effective method to reduce pollutant emission on a regional scale.     

Source apportionment of PM2.5 and PM10 aerosols in Brisbane (Australia) by receptor modelling

Aerosol samples for PM_2.5 and PM₁₀ (particulate matter with aerodynamic diameters less than 2.5 and 10 μm, respectively) were collected from 1993 to 1995 at five sites in Brisbane, a subtropical coastal city in Australia. This paper investigates the contributions of emission sources to PM_2.5 and PM₁₀ aerosol mass in Brisbane. Source apportionment results derived from the chemical mass balance (CMB), target transformation factor analysis (TTFA) and multiple linear regression (MLR) methods agree well with each other. The contributions from emission sources exhibit large variations in particle size with temporal and spatial differences. On average, the major contributors of PM₁₀ aerosol mass in Brisbane include: soil/road side dusts (25% by mass), motor vehicle exhausts (13%, not including the secondary products), sea salt (12%), Ca-rich and Ti-rich compounds (11%, from cement works and mineral processing industries), biomass burning (7%), and elemental carbon and secondary products contribute to around 15% of the aerosol mass on average. The major sources of PM_2.5 aerosols at the Griffith University (GU) site (a suburban site surrounded by forest area) are: elemental carbon (24% by mass), secondary organics (21%), biomass burning (15%) and secondary sulphate (14%). Most of the secondary products are related to motor vehicle exhausts, so, although motor vehicle exhausts contribute directly to only 6% of the PM_2.5 aerosol mass, their total contribution (including their secondary products) could be substantial. This pattern of source contribution is similar to the results for Rozelle (Sydney) among the major Australian studies, and is less in contributions from industrial and motor vehicular exhausts than the other cities. An attempt was made to estimate the contribution of rural dust and road side dust. The results show that road side dusts could contribute more than half of the crustal matter. More than 80% of the contribution of vehicle exhausts arises from diesel-fuelled trucks/buses. Biomass burning, large contributions of crustal matter, and/or local contributing sources under calm weather conditions, are often the cause of the high PM₁₀ episodes at the GU site in Brisbane.     

The impact of wood stove technology upgrades on indoor residential air quality

Fine particulate matter (PM_2.5) air pollution has been linked to adverse health impacts, and combustion sources including residential wood-burning may play an important role in some regions. Recent evidence suggests that indoor air quality may improve in homes where older, non-certified wood stoves are exchanged for lower emissions EPA-certified alternatives. As part of a wood stove exchange program in northern British Columbia, Canada, we sampled outdoor and indoor air at 15 homes during 6-day sampling sessions both before and after non-certified wood stoves were exchanged. During each sampling session two consecutive 3-day PM_2.5 samples were collected onto Teflon filters, which were weighed and analyzed for the wood smoke tracer levoglucosan. Residential PM_2.5 infiltration efficiencies (F_inf) were estimated from continuous light scattering measurements made with nephelometers, and estimates of F_inf were used to calculate the outdoor- and indoor-generated contributions to indoor air. There was not a consistent relationship between stove technology and outdoor or indoor concentrations of PM_2.5 or levoglucosan. Mean F_inf estimates were low and similar during pre- and post-exchange periods (0.32 ± 0.17 and 0.33 ± 0.17, respectively). Indoor sources contributed the majority (～65%) of the indoor PM_2.5 concentrations, independent of stove technology, although low indoor-outdoor levoglucosan ratios (median ≤ 0.19) and low indoor PM_2.5-levoglucosan correlations (r ≤ 0.19) suggested that wood smoke was not a major indoor PM_2.5 source in most of these homes. In summary, despite the potential for extensive wood stove exchange programs to reduce outdoor PM_2.5 concentrations in wood smoke-impacted communities, we did not find a consistent relationship between stove technology upgrades and indoor air quality improvements in homes where stoves were exchanged.     

Seasonal distribution of polar organic compounds in the urban atmosphere of two large cities from the North and South of Europe

Polar organic species, including n-alkanols, sterols, anhydrosugars, n-alkanoic acids, n-alkenoic acids and dicarboxylic acids were quantified to typify the composition of fine (PM_2.5) and coarse (PM_10–2.5) aerosols collected simultaneously at roadside and background sites in Oporto (Portugal) and Copenhagen (Denmark) during separate month-long intensive summer and winter campaigns. As a general trend, both cities exhibit roadside average concentrations higher than their correspondent urban background levels. The polar organics are more abundant in the fine fraction, exhibiting a seasonal pattern with high winter concentrations and low summer loads. Aerosols from both cities showed typical distributions of n-alkanols and n-alkanoic acids in the ranges C₁₂–C₂₈ and C₈–C₂₈, respectively. The <C₂₀ homologues, usually attributed to kitchen emissions, vehicular exhausts and microbial origins, dominated the fatty acid fraction. Linear alcohols were mainly represented by higher molecular weight homologues from vegetation waxes. Molecular tracer species for wood smoke (e.g. levoglucosan, mannosan and resinic acids) were found to contribute significantly to the urban aerosol, especially in winter. Ratios between these tracers indicated different biofuel contributions to the atmospheric particles of the two cities. Secondary constituents from both biogenic (e.g. pinonic acid) and anthropogenic precursors (e.g. phthalic and benzoic acids) were detected in both cities and seasons.     

Influence of combustion conditions on yields of solvent-extractable anhydrosugars and lignin phenols in chars: Implications for characterizations of biomass combustion residues

Anhydrosugars, such as levoglucosan and its isomers (mannosan, galactosan), as well as the solvent-extractable lignin phenols (methoxylated phenols) are thermal degradation products of cellulose/hemicellulose and lignin, respectively. These two groups of biomarkers are often used as unique tracers of combusted biomass inputs in diverse environmental media. However, detailed characterization of the relative proportion and signatures of these compounds in highly heterogeneous plant-derived chars are still scarce. Here we conducted a systematic study to investigate the yields of solvent-extractable anhydrosugars and lignin phenols in 25 lab-made chars produced from different plant materials under different combustion conditions. Solvent-extractable anhydrosugars and lignin phenols were only observed in chars formed below 350 °C and yields were variable across different combustion temperatures. The yields of mannosan (M) and galactosan (G) decreased more rapidly than those of levoglucosan (L) under increasing combustion severity (temperature and duration), resulting in variable L/M and L/(M + G) ratios, two diagnostic ratios often used for identification of combustion sources (e.g. hardwoods vs. softwoods vs. grasses). Our observations thus may provide an explanation for the wide ranges of values reported in the literature for these two ratios. On the other hand, the results of this study suggest that the ratios of the major solvent-extractable lignin phenols (vanillyls (V), syringyls (S), cinnamyls (C)) provide additional source reconstruction potential despite observed variations with combustion temperature. We thus propose using a property-property plot (L/M vs. S/V) as an improved means for source characterization of biomass combustion residues. The L/M-S/V plot has shown to be effective in environmental samples (soil organic matter, atmospheric aerosols) receiving substantial inputs of biomass combustion residues.     

Long-range transport episodes of fine particles in southern Finland during 1999–2007

The frequency, strength and sources of long-range transport (LRT) episodes of fine particles (PM_2.5) were studied in southern Finland using air quality monitoring results, backward air mass trajectories, remote sensing of fire hot spots, transport and dispersion modelling of smoke and chemical analysis of particle samples (black carbon, monosaccharide anhydrides, oxalate, succinate, malonate, SO₄^2?, NO₃^?, K⁺ and NH₄⁺). At an urban background site in Helsinki, the daily WHO guideline value (24-h PM_2.5 mean 25 μg m^?3) was exceeded during 1–7 LRT episodes per year in 1999–2007. The 24-h mean maximum concentrations varied between 25 and 49 μg m^?3 during the episodes, which was 3–6 times higher than the local mean concentration (8.7 μg m^?3) in 1999–2007. The highest particle concentrations (max. 1-h mean 163 μg m^?3) and the longest episodes (max. 9 days) were mainly caused by the emissions from open biomass burning, especially during springs and late-summers in 2002 and 2006. During the period 2001–2007, the satellite remote sensing of active fire hot spots and transport and dispersion modelling of smoke indicated that approximately half of the episodes were caused partly by the emissions from wildfires and/or agricultural waste burning in fields in Eastern Europe, especially in Russia, Belarus and Ukraine. Other episodes were mainly caused by the LRT of ordinary anthropogenic pollutants, e.g. from energy production, traffic, industry and wood combustion. During those ‘other episodes’, air masses also arrived from Eastern Europe, including Poland. The highest concentrations of biomass-burning tracers, such as monosaccharide anhydrides (levoglucosan + mannosan + galactosan) and K⁺, were observed during open biomass-burning episodes, but quite high values were also measured during some winter episodes due to wood combustion emissions. Our results indicate that open biomass burning in Eastern Europe causes high fine particle concentration peaks in large areas of Europe almost every year.     

Wintertime PM2.5 and PM10 Source Apportionment at Sacramento,California

ABSTRACT

The chemical mass balance (CMB) model was applied to winter (November through January) 1991–1996 PM2.5 and PM10 data from the Sacramento 13th and T Streets site in order to identify the contributions from major source categories to peak 24-hr ambient PM_2.5 and PM₁₀ levels. The average monthly PM₁₀ monitoring data for the nine-year period in Sacramento County indicate that elevated concentrations are typical in the winter months. Concentrations on days of highest PM₁₀ are dominated by the PM2.5 fraction. One factor contributing to increased PM_2.5 concentrations in the winter is meteorology (cool temperatures, low wind speeds, low inversion layers, and more humid conditions) that favors the formation of secondary nitrate and sulfate aerosols. Residential wood burning also elevates fine particulate concentrations in the Sacramento area.

The results of the CMB analysis highlight three key points. First, the source apportionment results indicate that primary motor vehicle exhaust and wood smoke are significant sources of both PM_2.5 and PM₁₀ in winter. Second, nitrates, secondarily formed as a result of motor-vehicle and other sources of nitrogen oxide (NO_x), are another principal cause of the high PM_2.5 and PM₁₀ levels during the winter months. Third, fugitive dust, whether it is resuspended soil and dust or agricultural tillage, is not the major contributor to peak winter PM_2.5 and PM10 levels in the Sacramento area.