Burning Markers Research Articles

Aerosol composition and microstructure in the smoky atmosphere of Moscow during the August 2010 extreme wildfires

This is a comprehensive study of the physicochemical characterization of multicomponent aerosols in the smoky atmosphere of Moscow during the extreme wildfires of August 2010 and against the background atmosphere of August 2011. Thermal–optical analysis, liquid and ion chromatography, IR spectroscopy, and electron microscopy were used to determine the organic content (OC) and elemental content (EC) of carbon, organic/inorganic and ionic compounds, and biomass burning markers (anhydrosaccharides and the potassium ion) and study the morphology and elemental composition of individual particles. It has been shown that the fires are characterized by an increased OC/EC ratio and high concentrations of ammonium, potassium, and sulfate ions in correlation with an increased content of levoglucosan as a marker of biomass burning. The organic compounds containing carbonyl groups point to the process of photochemical aging and the formation of secondary organic aerosols in the urban atmosphere when aerosols are emitted from forest fires. A cluster analysis of individual particles has indicated that when the smokiest atmosphere is characterized by prevailing soot/tar ball particles, which are smoke-emission micromarkers.

Optical properties and possible sources of brown carbon in PM2.5 over Xi'an, China

To quantify optical and chemical properties of PM2.5 brown carbon (BrC) in Xi'an, 58 high-volume ambient PM2.5 samples were collected during 2 November 2009 to 13 October 2010. Mass concentrations of chemical components were determined, including water-soluble ions, water-soluble organic carbon, levoglucosan, organic carbon (OC), and element carbon (EC). BrC, as an unidentified and wavelength-dependent organic compound, was also measured from water-soluble carbon (WSOC) at 340 nm using UV–vis spectrometer. The wavelength-dependent absorption coefficient (babs) and mass absorption coefficient (MAC) were much abundant at 340 nm, and the high Absorption Ångström coefficient (AAC) values were observed around 5.4, corresponding to the existence of BrC in ambient PM2.5, especially in winter. Good correlations (R > 0.60) between babs and biomass burning markers, such as levoglucosan and K+, in winter indicated significant amounts of primary BrC from biomass burning emissions. Secondary organic carbon BrC (SOCBrC) was more abundant in winter than in summer. SOCBrC in winter was mainly fresh SOC formed from aqueous phase reactions while in summer, aged SOC from photo-chemical formation. Source profiles of BrC optical parameters were detected, which verified sources of BrC from biomass burning and coal burning emissions in areas surrounding Xi'an. The rapidly decreasing babs-340nm values from biomass burning smoldering to straw pellet burning suggested that burning straw pellet instead of burning straw directly is an effective measure for reducing BrC emissions.

Benzo[ghi]perylene activates the AHR pathway to exert biological effects on the NL-20 human bronchial cell line.

Polycyclic aromatic hydrocarbons (PAH) are produced by incomplete combustion of organic material. In the Mexico City atmosphere, the most abundant PAH is benzo[ghi]perylene (BghiP), a gasoline combustion marker. At present, there are no reports of the effects of BghiP on human bronchial cells, so the aim of the study was to evaluate the effects in vitro of BghiP on the NL-20 cell line. Results showed that BghiP induced the formation of small vesicles throughout the cytoplasm, with absence of nuclear fragmentation. At 48h exposition, damage in cell membrane increased significantly at 1.24μg/mL of BghiP (p<0.05). Immunocytochemistry revealed that BghiP provokes nuclear translocation of AhR receptor, which indicates that this compound can induce transcription of genes via receptor binding (AhR pathway activation). BghiP induced a two-fold increase (p<0.05) in the expression of AhR and CYP4B1 (a lung-specific pathway effector). In the presence of the receptor antagonist CH-223191, the loss of viability, the nuclear translocation and the overexpression of genes decreased, though this did not prevent the formation of vesicles. BghiP induced oxidative stress and in presence of the receptor antagonist this increased significantly. In conclusion, BghiP can activate the overexpression of AhR and CYP4B1, and the effects are abated by the AhR receptor antagonist. This is the first report to prove that BghiP utilizes the AhR pathway to exert its toxic effects on the NL-20 human bronchial cell line .

Characteristics and sensitivity analysis of multiple-time-resolved source patterns of PM2.5 with real time data using Multilinear Engine 2

With real time resolved data of Particulate matter (PM) and chemical species, understanding the source patterns and chemical characteristics is critical to establish controlling of PM. In this work, PM2.5 and chemical species were measured by corresponding online instruments with 1-h time resolution in Beijing. Multilinear Engine 2 (ME2) model was applied to explore the sources, and four sources (vehicle emission, crustal dust, secondary formation and coal combustion) were identified. To investigate the sensitivity of time resolution on the source contributions and chemical characteristics, ME2 was conducted with four time resolution runs (1-h, 2-h, 4-h, and 8-h). Crustal dust and coal combustion display large variation in the four time resolutions runs, with their contributions ranging from 6.7 to 10.4 μg m−3 and from 6.4 to 12.2 μg m−3, respectively. The contributions of vehicle emission and secondary formation range from 7.5 to 10.5 and from 14.7 to 16.7 μg m−3, respectively. The sensitivity analyses were conducted by principal component analysis-plot (PCA-plot), coefficient of divergence (CD), average absolute error (AAE) and correlation coefficients. For the four time resolution runs, the source contributions and profiles of crustal dust and coal combustion were more unstable than other source categories, possibly due to the lack of key markers of crustal dust and coal combustion (e.g. Si, Al). On the other hand, vehicle emission and crustal dust were more sensitive to time series of source contributions at different time resolutions. Findings in this study can improve our knowledge of source contributions and chemical characteristics at different time solutions.

Online molecular characterization of fine particulate matter in Port Angeles, WA: Evidence for a major impact from residential wood smoke

We present on-line molecular composition measurements of wintertime particulate matter (PM) during 2014 using an iodide-adduct high-resolution, time-of-flight chemical ionization mass spectrometer (HR-TOF-CIMS) coupled to a Filter Inlet for Gases and AEROsols (FIGAERO). These measurements were part of an intensive effort to characterize PM in the region with a focus on ultrafine particle sources. The technique was used to detect and quantify different classes of wood burning tracers, including levoglucosan, methoxyphenols, and nitrocatechols, among other compounds in near real-time. During the campaign, particulate mass concentrations of compounds with the same molecular composition as levoglucosan ranged from 0.002 to 19 μg/m3 with a median mass concentration of 0.9 μg/m3. Wood burning markers, in general, showed a strong diurnal pattern peaking at night and in the early morning. This diurnal profile combined with cold, stagnant conditions, wind directions from predominantly residential areas, and observations of lower combustion efficiency at night support residential wood burning as a dominant source of wintertime PM in Port Angeles. This finding has implications for improving wintertime air quality in the region by encouraging the use of high efficiency wood-burning stoves or other cleaner home heating options throughout the relevant domain.

Daily personal exposure to black carbon: A pilot study

Continuous personal monitoring is the benchmark for air pollution exposure assessment. Black carbon (BC) is a strong marker of primary combustion like vehicle and biomass emissions. There have been few studies that quantified daily personal BC exposure and the contribution that different microenvironments make to it. In this pilot study, we used a portable aethalometer to measure BC concentrations in an individual's breathing zone at 30-s intervals while he performed his usual daily activities. We used a GPS and time-activity diary to track where he spent his time. We performed twenty 24-h measurements, and observed an arithmetic mean daily exposure concentration of 603 ng/m3. We estimated that changing commute modes from bus to train reduced the 24-h mean BC exposure concentration by 29%. Switching from open windows to closed windows and recirculated air in a car led to a reduction of 32%. Living in a home without a wood-fired heater caused a reduction of 50% compared with a wood-heated home. Our preliminary findings highlight the potential utility of simple approaches to reduce a person's daily BC exposure.

Size-distribution of airborne polycyclic aromatic hydrocarbons and other organic source markers in the surroundings of a cement plant powered with alternative fuels

The distributions of polycyclic aromatic hydrocarbons (PAHs) and molecular tracer organic compounds for biomass combustion, traffic emissions, soil dust, and secondary aerosol processing have been studied in three fractions of ambient air particulate matter (PM10, 2.5, and 1) collected in the vicinity of a cement plant. PAH concentrations were used to estimate the carcinogenic risks in humans. Combustion related compounds, including PAHs, and those from secondary aerosol processing, predominated in the finest (PM<1) fraction, while saccharides related to organic soil dust predominated in the coarse fraction (2.5<PM<10). The molecular markers of biomass combustion were found in high concentrations, indicating the influence of biomass burning on PM. Most predominant PAHs were five and six rings species, related to a PAH profile characteristic of urban-industrial environments. The concentrations of benzo[a]pyrene varied between 0.2 and 1.0ng/m3, which is close but lower than the annual limit value of 1ng/m3 established by law. Exposure and inhalation carcinogenic risks from total PAHs were below the EPA threshold of acceptable risk (1·10−6).

Characterization of primary and secondary organic aerosols in Melbourne airshed: The influence of biogenic emissions, wood smoke and bushfires

Detailed chemical characterisation was performed for wintertime and summertime PM10 samples collected in Melbourne, Australia. The samples were analysed for marker compounds of biomass burning and biogenic secondary organic aerosol (SOA). The chemical analysis showed that the site was significantly influenced by the emissions from wintertime domestic wood combustion and summertime bushfires. Monosaccharide anhydrides were major primary biomass burning marker compounds found in the samples with the average concentrations of 439, 191, 57 and 3630 ngm−3 for winter 2004, winter 2005, summer 2005 and summer 2006, respectively. The highest concentration was determined during the summer 2006 bushfire season with the concentration of 15,400 ngm−3. Biomass burning originating SOA compounds detected in the samples include substituted nitrophenols, mainly 4-nitrocatechol (Mr 155), methyl-nitrocatechols (Mr 169) and dimethyl-nitrocatechols (Mr 183) with the sum concentrations as high as 115 ngm−3 for the wintertime samples and 770 ngm−3 for the bushfire influenced samples. In addition to this, elevated levels of biogenic SOA marker compounds were determined in the summertime samples influence by bushfire smoke. These marker compounds can be categorised into carboxylic acid marker compounds and heteroatomic organic acids containing nitrogen and sulfur. Carboxylic acid marker compounds can be largely attributed to oxidation products originating from 1,8-cineole, α-pinene and β-pinene that are main constituents of eucalyptus VOC emissions. Among those, diaterpenylic acid, terpenylic acid and daterebic acid were found at elevated levels in the bushfire influenced samples. Heteroatomic monoterpene SOA marker compounds (Mr 295, C10H17NO7S) were detected during both winter and summer periods. Especially high levels of these compounds were determined in the severe bushfire samples from summer 2006. Based on the results obtained from the chemical analysis and a macro tracer method, we estimated that 1,8-cineole SOA alone contributed up to 3.5% of secondary organic carbon mass during the bushfire period in 2006. It is likely that biogenic VOC oxidation can be an important source of biomass burning organic aerosol mass.

Impacts of co-firing biomass on emissions of particulate matter to the atmosphere

Gas and particle emissions from co-firing coal and two types of biomass versus coal was evaluated in a circulating fluidized bed boiler operating with a constant energy input. Compared to coal, co-firing 50% oat hulls (by weight) significantly reduced the emission of particulate matter (PM) by 90%, polycyclic aromatic hydrocarbons (PAH) by 40%, metals by 65%, and fossil carbon dioxide by 40%. In contrast, co-firing 3.8% wood chips (by weight) had a negligible impact on the emissions of PM and PAH, but caused a 6% reduction in metals. Fuel-based emission factors for PM, metals, and organic species including biomass burning markers retene and levoglucosan, were determined. Enrichment factors (EF) were computed to examine the distribution of metals across PM, fly ash, and bottom ash and demonstrated enrichment in volatile metals (e.g. Fe, Al, and Cr) in PM and fly ash. Co-firing 50% oat hulls led to a significant depletion of K in PM and its enrichment in bottom ash. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM–EDX) analysis revealed a wide heterogeneity in particle sizes and compositions across particles for all fuel types. Overall, this study demonstrates that co-firing a 50% oat hulls with coal provides several benefits to air quality and outlines important changes to PM composition when biomass is co-fired with coal.

Characterization of aerosol composition, concentrations, and sources at Baengnyeong Island, Korea using an aerosol mass spectrometer

To improve understanding of the sources and chemical properties of particulate pollutants on the western side of the Korean Peninsula, an Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) measured non-refractory fine (PM1) particles from May to November, 2011 at Baengnyeong Island, South Korea. Organic matter and sulfate were generally the most abundant species and exhibited maximum concentrations of 36 μg/m3 and 39 μg/m3, respectively. Nitrate concentrations peaked at 32 μg/m3 but were typically much lower than sulfate and organic matter concentrations. May, September, October, and November featured the highest monthly average concentrations, with lower concentrations typically observed from June through August. Potential source contribution function (PSCF) analysis and individual case studies revealed that transport from eastern China, an area with high SO2 emissions, was associated with high particulate sulfate concentrations at the measurement site. Observed sulfate aerosol sometimes was fully neutralized by ammonium but often was acidic; the average ammonium to sulfate molar ratio was 1.49. Measured species size distributions revealed a range of sulfate particle size distributions with modes between 100 and 600 nm. Organic aerosol source regions were widespread, including contributions from eastern China and South Korea. Positive matrix factorization (PMF) analysis indicated three “factors,” or types of organic aerosol, comprising one primary, hydrocarbon-like organic aerosol (HOA) and two oxidized organic aerosol (OOA) components, including a more oxidized (MO-OOA) and a less oxidized (LO-OOA) oxidized organic aerosol. On average, HOA and OOA contributed 21% and 79% of the organic mass (OM), respectively, with the MO-OOA fraction nearly three times as abundant as the LO-OOA fraction. Biomass burning contributions to observed OM were low during the late spring/early summer agricultural burning season in eastern China, since airflow into eastern China during the Asian Monsoon generally prevents transport of emissions eastward to the Korean Peninsula. Concentrations of the m/z 60 AMS biomass burning marker were more abundant in autumn, when transport patterns appeared to bring some smoke from fires in northern Asia to the island.

Emissions of PAHs derived from sugarcane burning and processing in Chiapas and Morelos México

Sugarcane burning is an agricultural practice implemented to ease farm worker duties; nevertheless, as a consequence, tons of particles are emitted to the atmosphere. Additionally, during harvesting the sugar-mills operate the whole day emitting hundreds of tons of pollutants. Therefore, health risks to neighboring population should be a major governmental concern, leading first to identification and quantification of toxic compounds, such as polycyclic aromatic hydrocarbons (PAHs). In order to establish the magnitude of the problem, four sampling campaigns of PM10 and PM2.5 were carried out in this study, during harvesting and no-harvesting seasons in two municipalities of México, with different climatic and social conditions. Concentrations of PM10, PM2.5, and organic compounds were determined daily, followed by extraction, identification and quantification of the 17 EPA-established PAHs from all samples. The results showed that during harvest, the PM10 mass increased lightly in Chiapas, but approximately twice in Morelos, whereas total PAH concentrations increased twice and six times, respectively. The most abundant PAHs, namely: indene [1,2,3cd] pyrene, benzo[b]fluoranthene, benzo[a]pyrene and dibenzo [a,h] anthracene are composed of 5 or more aromatic rings. Of the total PAHs quantified, 44% to 52% corresponded to carcinogenic compounds, consequently, the overall carcinogenic potential increased twice or three times. Principal component analysis with varimax rotation was applied to source apportionment at each site, suggesting three different sources during harvesting: the combustion process in the sugar mill, sugarcane burning and vehicular emissions. The combustion markers for sugar mill are, BAA, BBF, BKF, BAP, IND and BGP, whereas for sugarcane burning were ANT, PHE, FLT and PYR. The results obtained indicate that processing and burning sugarcane are the main sources of the PAH levels measured, proving that the health risks are boosted during harvesting due to increases of PM and PAHs.

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 &gt; 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.

Investigating types and sources of organic aerosol in Rocky Mountain National Park using aerosol mass spectrometry

Abstract. The environmental impacts of atmospheric particles are highlighted in remote areas where visibility and ecosystem health can be degraded by even relatively low particle concentrations. Submicron particle size, composition, and source apportionment were explored at Rocky Mountain National Park using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer. This summer campaign found low average, but variable, particulate mass (PM) concentrations (max = 93.1 μg m−3, avg. = 5.13 ± 2.72 μg m−3) of which 75.2 ± 11.1% is organic. Low-volatility oxidized organic aerosol (LV-OOA, 39.3% of PM1 on average) identified using Positive Matrix Factorization appears to be mixed with ammonium sulfate (3.9% and 16.6% of mass, respectively), while semi-volatile OOA (27.6%) is correlated with ammonium nitrate (nitrate: 4.3%); concentrations of these mixtures are enhanced with upslope (SE) surface winds from the densely populated Front Range area, indicating the importance of transport. A local biomass burning organic aerosol (BBOA, 8.4%) source is suggested by mass spectral cellulose combustion markers (m/z 60 and 73) limited to brief, high-concentration, polydisperse events (suggesting fresh combustion), a diurnal maximum at 22:00 local standard time when campfires were set at adjacent summer camps, and association with surface winds consistent with local campfire locations. The particle characteristics determined here represent typical summertime conditions at the Rocky Mountain site based on comparison to ~10 years of meteorological, particle composition, and fire data.

Radiocarbon analysis of elemental and organic carbon in Switzerland during winter-smog episodes from 2008 to 2012 – Part 1: Source apportionment and spatial variability

Abstract. While several studies have investigated winter-time air pollution with a wide range of concentration levels, hardly any results are available for longer time periods covering several winter-smog episodes at various locations; e.g., often only a few weeks from a single winter are investigated. Here, we present source apportionment results of winter-smog episodes from 16 air pollution monitoring stations across Switzerland from five consecutive winters. Radiocarbon (14C) analyses of the elemental (EC) and organic (OC) carbon fractions, as well as levoglucosan, major water-soluble ionic species and gas-phase pollutant measurements were used to characterize the different sources of PM10. The most important contributions to PM10 during winter-smog episodes in Switzerland were on average the secondary inorganic constituents (sum of nitrate, sulfate and ammonium = 41 ± 15%) followed by organic matter (OM) (34 ± 13%) and EC (5 ± 2%). The non-fossil fractions of OC (fNF,OC) ranged on average from 69 to 85 and 80 to 95% for stations north and south of the Alps, respectively, showing that traffic contributes on average only up to ~ 30% to OC. The non-fossil fraction of EC (fNF,EC), entirely attributable to primary wood burning, was on average 42 ± 13 and 49 ± 15% for north and south of the Alps, respectively. While a high correlation was observed between fossil EC and nitrogen oxides, both primarily emitted by traffic, these species did not significantly correlate with fossil OC (OCF), which seems to suggest that a considerable amount of OCF is secondary, from fossil precursors. Elevated fNF,EC and fNF,OC values and the high correlation of the latter with other wood burning markers, including levoglucosan and water soluble potassium (K+) indicate that residential wood burning is the major source of carbonaceous aerosols during winter-smog episodes in Switzerland. The inspection of the non-fossil OC and EC levels and the relation with levoglucosan and water-soluble K+ shows different ratios for stations north and south of the Alps (most likely because of differences in burning technologies) for these two regions in Switzerland.

Reactive oxygen species associated with water-soluble PM&amp;lt;sub&amp;gt;2.5&amp;lt;/sub&amp;gt; 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.

Spatial variations of levoglucosan in four European study areas

Relatively little is known about long term effects of wood smoke on population health. A wood combustion marker – levoglucosan – was measured using a standardized sampling and measurement method in four European study areas (Oslo, The Netherlands, Munich/Augsburg, Catalonia) to assess within and between study area spatial variation. Levoglucosan was analyzed in addition to: PM2.5, PM2.5 absorbance, PM10, polycyclic aromatic hydrocarbons (PAH), nitrogen oxides (NOx), elemental and organic carbon (EC/OC), hopanes, steranes and elemental composition. Measurements were conducted at street, urban and regional background sites. Three two-week samples were taken per site and the annual average concentrations of pollutants were calculated using continuous measurements at one background reference site. Land use regression (LUR) models were developed to explain the spatial variation of levoglucosan. Much larger within than between study area contrast in levoglucosan concentration was found. Spatial variation patterns differed from other measured pollutants: PM2.5, NOx and EC. Levoglucosan had the highest spatial correlation with ΣPAH (r=0.65) and the lowest with traffic markers — NOx, Σhopanes/steranes (r=−0.22). Levoglucosan concentrations in the cold (heating) period were between 3 and 20 times higher compared to the warm period. The contribution of wood-smoke calculated based on levoglucosan measurements and previous European emission data to OC and PM2.5 mass was 13 to 28% and 3 to 9% respectively in the full year. Larger contributions were calculated for the cold period.The median model R2 of the LUR models was 60%. The LUR models included population and natural land related variables. In conclusion, substantial spatial variability was found in levoglucosan concentrations within study areas. Wood smoke contributed substantially to especially wintertime PM2.5 OC and mass. The low to moderate correlation with PM2.5 mass and traffic markers offers the potential to assess health effects of wood smoke separate from traffic-related air pollution.

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.

Markers and influence of open biomass burning on atmospheric particulate size and composition during a major bonfire event

This study aims to characterize PM from the open burning of bonfires as well as detect a series of useful tracer species for source apportionment studies. Total suspended particulate (TSP), PM10 and PM2.5 were collected before, during, and after St. Joseph's Eve (18th of March). On this day, several bonfires are lit throughout the study area. Levoglucosan (Lvg), OC, EC, PAHs, soluble ions, and some metals (Al, Cd, Cu, Ni, and Pb) have been determined in each fraction.Results show that the contamination of the area is similar to what is generally found in suburban areas. The fine fraction makes the highest contribution to PM. This fraction is mainly related to compounds composing the PM secondarily formed, while the coarser fractions are associated with natural matrices.The bonfire event is an important source of particulate. All the combustion markers determined in PM2.5 (EC, OC, PAHs (except for Flu and Pyr), K+, Cl−, and Lvg) register a higher concentration. Lvg/OC ratio confirms higher wood smoke emissions during these days. Both the concentration and the compound profile indicate a different origin of PAHs in the atmosphere. The highest concentration of K+ and OC in TSP confirm the contribution of open fire, as well, to this fraction, which can be ascribable mainly to combustion ash. Nitrates and sulphates also show a higher concentration in the PM10-TSP fraction. Surprisingly, there is also an increase in the concentration of components not usually considered combustion markers, i.e. Pb and Al in PM2.5. This is probably ascribable to their bioaccumulation. In conclusion, Lvg, OC, PAHs, Al, and Pb can be used together as specific markers of bonfires to identify this source of particulate matter.

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.