Organic Molecular Markers Research Articles

<italic>n</italic>-Alkanes and hydrogen isotope fractionations of aquatic plants in lakes on the Changbai Mountains-Lake Baikal transect

With the advance of gas chromatography/thermal conversion isotope ration mass spectrometry (GC/TC/IRMS), compound-specific hydrogen isotope composition ( d D) of molecular organic markers is increasingly used as a palaeoclimate proxy. To explore the hydrogen isotopic fractionation relationships between the alkanes derived from aquatic plants in lakes and the lake waters, we have investigated n -alkane distributions and their d D values of the aquatic plants collected from 5 typical lakes on the Changbai Mountains-Lake Baikal transect in the northern East Asian monsoon regime. The n -C23 and/or n -C25 alkanes are the dominant compounds in submerged aquatic plants. The average chain length (ACL) and the P aq values range from 22.7-26.3 and 0.5-0.99, respectively. d D values of different n -alkanes from a single plant are similar, especially for the n -C21, n -C23 and n -C25. The mean apparent hydrogen isotope fractionation between the lacustrine aquatic plant alkanes and lake waters is -159‰ for the study area, consistent with the conclusion obtained from a European transect (-160‰). We suggest that n -alkanes from aquatic plants can be used to trace the hydrogen isotope composition of the environmental water. On a global scaled basis, the average d D values of n -C23 and n -C25 alkanes might be an optimized proxy with great potential in paleoenvironmental study.

Organic tracer-based source analysis of PM2.5 organic and elemental carbon: A case study at Dongguan in the Pearl River Delta, China

Organic carbon (OC) and elemental carbon (EC) are major constituents of PM2.5 and their source apportionment remains a challenging task due to the great diversity of their sources and lack of source-specific tracer data. In this work, sources of OC and EC are investigated using positive matrix factorization (PMF) analysis of PM2.5 chemical composition data, including major ions, OC, EC, elements, and organic molecular source markers, for a set of 156 filter samples collected over three years from 2010 to 2012 at Dongguan in the Pearl River Delta, China. The key organic tracers include levoglucosan, mannosan, hopanes, C27–C33n-alkanes, and polycyclic aromatic hydrocarbons (PAHs). Using these species as input for the PMF model, nine factors were resolved. Among them, biomass burning and coal combustion were significant sources contributing 15–17% of OC and 24–30% and 34–35% of EC, respectively. Industrial emissions and ship emissions, identified through their characteristic metal signatures, contributed 16–24% and 7–8% of OC and 8–11% and 16–17% of EC, respectively. Vehicle exhaust was a less significant source, accounting for 3–4% of OC and 5–8% of EC. Secondary OC, taken to be the sum of OC present in secondary sulfate and nitrate formation source factors, made up 27–36% of OC. Plastic burning, identified through 1,3,5-triphenylbenzene as a tracer, was a less important source for OC(≤4%) and EC (5–10%), but a significant source for PAHs at this site.The utility of organic source tracers was demonstrated by comparing PMF runs with different combinations of organic tracers removed from the input species list. Levoglucosan and mannosan were important additions to distinguish biomass burning from coal combustion by reducing collinearity among source profiles. Inclusion of hopanes and 1,3,5-triphenylbenzene was found to be necessary in resolving the less significant sources vehicle exhaust and plastic burning. Inclusion of C27–C33n-alkanes and PAHs can influence the source profiles resolved by PMF and thereby affect the source contributions to OC and EC. Considerably more OC (44% vs. 27% of OC) was apportioned to the secondary factors when only major components were considered in comparison with the PMF analysis with the full suite of organic tracers, mainly at the expense of coal combustion and industrial emissions. EC apportionment to the few major combustion sources was found more sensitive to inclusion of organic tracers than OC apportionment, with PAHs playing a prominent role. This work demonstrates the importance of having distinct organic tracers in identifying and quantifying OC and EC sources.

Multiphase Chemical Kinetics of OH Radical Uptake by Molecular Organic Markers of Biomass Burning Aerosols: Humidity and Temperature Dependence, Surface Reaction, and Bulk Diffusion

Multiphase reactions of OH radicals are among the most important pathways of chemical aging of organic aerosols in the atmosphere. Reactive uptake of OH by organic compounds has been observed in a number of studies, but the kinetics of mass transport and chemical reaction are still not fully understood. Here we apply the kinetic multilayer model of gas-particle interactions (KM-GAP) to experimental data from OH exposure studies of levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). The model accounts for gas-phase diffusion within a cylindrical coated-wall flow tube, reversible adsorption of OH, surface-bulk exchange, bulk diffusion, and chemical reactions at the surface and in the bulk of the condensed phase. The nonlinear dependence of OH uptake coefficients on reactant concentrations and time can be reproduced by KM-GAP. We find that the bulk diffusion coefficient of the organic molecules is approximately 10(-16) cm(2) s(-1), reflecting an amorphous semisolid state of the organic substrates. The OH uptake is governed by reaction at or near the surface and can be kinetically limited by surface-bulk exchange or bulk diffusion of the organic reactants. Estimates of the chemical half-life of levoglucosan in 200 nm particles in a biomass burning plume increase from 1 day at high relative humidity to 1 week under dry conditions. In BBA particles transported to the free troposphere, the chemical half-life of levoglucosan can exceed 1 month due to slow bulk diffusion in a glassy matrix at low temperature.

Chemical speciation and source apportionment of fine particulate matter in Santiago, Chile, 2013

Santiago is one of the largest cities in South America and has experienced high fine particulate matter (PM2.5) concentrations in fall and winter months for decades. To better understand the sources of fall and wintertime pollution in Santiago, PM2.5 samples were collected for 24h every weekday from March to October 2013 for chemical analysis. Samples were analyzed for mass, elemental carbon (EC), organic carbon (OC), water soluble organic carbon (WSOC), water soluble nitrogen (WSTN), secondary inorganic ions, and particle-phase organic tracers for source apportionment. Selected samples were analyzed as monthly composites for organic tracers. PM2.5 concentrations were considerably higher in the coldest months (June–July), averaging (mean±standard deviation) 62±15μg/m3 in these two months. Average fine particle mass concentration during the study period was 40±20μg/m3. Organic matter during the peak winter months was the major component of fine particles comprising around 70% of the particle mass. Source contributions to OC were calculated using organic molecular markers and a chemical mass balance (CMB) receptor model. The four combustion sources identified were wood smoke, diesel engine emission, gasoline vehicles, and natural gas. Wood smoke was the predominant source of OC, accounting for 58±42% of OC in fall and winter. Wood smoke and nitrate were the major contributors to PM2.5. In fall and winter, wood smoke accounted for 9.8±7.1μg/m3 (21±15%) and nitrate accounted for 9.1±4.8μg/m3 (20±10%) of fine PM. The sum of secondary inorganic ions (sulfate, nitrate, and ammonium) represented about 30% of PM2.5 mass. Secondary organic aerosols contributed only in warm months, accounting for about 30% of fine PM during this time.

Source apportionment of PM2.5 carbonaceous aerosol in Baghdad, Iraq

Baghdad is the second largest city in the Middle East and suffers from severe air quality degradation due to the high levels of the atmospheric particulate matter (PM). Limited information exists regarding the sources of PM in Baghdad, and the lack of information on sources inhibits the development of control strategies to reduce air pollution. To better understand the nature of fine particulate matter (PM2.5) in Baghdad and the Middle East, a one year sampling campaign to collect PM2.5 was conducted from September 2012 through September 2013, missing August 2013 samples due to the security situation. 24-hour integrated samples collected on a 1-in-6day schedule were analyzed for the major components, and monthly average samples were analyzed by gas chromatography mass spectrometry (GCMS) methods to measure particle-phase organic molecular markers. The results of organic molecular markers were used in a chemical mass balance (CMB) model to quantify the sources of PM2.5 organic carbon (OC) and PM2.5 mass. Primary sources accounted for 44% of the measured PM2.5, and secondary sources were estimated to make up 28% of the measured PM2.5. Picene, a tracer of coal combustion detected in Baghdad where there is no evidence for coal combustion, can be attributed to burning crude oil and other low quality fuels in Baghdad. Source apportionment results showed that the dominant sources of the carbonaceous aerosols in Baghdad are gasoline (37±6%) and diesel engines (17±3%) which can be attributed to the extensive use of gasoline and diesel powered generators in Baghdad. Wood burning and residual oil combustion contributed to 5±0.4 and 1±0.2% respectively of OC. The unresolved sources contributed to 42±19% of the OC which represented the secondary organic aerosol (SOA) and the unidentified sources.

Source apportionment of air pollution exposures of rural Chinese women cooking with biomass fuels

Particulate matter (PM) from different sources may differentially affect human health. Few studies have assessed the main sources of personal exposure to PM and their contributions among residents of developing countries, where pollution sources differ from those in higher-income settings. 116 daily (24-h) personal PM2.5 exposure samples were collected among 81 women cooking with biomass fuels in two villages in rural Yunnan, China. The PM samples were analyzed for mass and chemical composition, including water-soluble organic carbon (WSOC), black carbon (BC), and molecular markers. We found black carbon, n-alkanes and levoglucosan dominated the most abundant fractions of the total measured species and average personal PM2.5 exposure was higher in winter than that in summer in both villages. The composition data were then analyzed using a positive matrix factorization (PMF) receptor model to identify the main PM emission sources contributing to women's exposures and to assess their spatial (between villages) and seasonal variation in our study setting. The 6-factor solution provided reasonably stable profiles and was selected for further analysis. Our results show that rural Chinese women cooking with biomass fuels are exposed to a variety of sources. The identified factors include wood combustion (41.1%), a cooking source (35.6%), a mobile source (12.6%), plant waxes (6.7%), pyrolysis combustion (3.0%), and secondary organic aerosols (SOA; 1.0%). The mean source contributions of the mobile source, cooking source, and wood combustion factor to PM2.5 exposure were significantly different between women living in the two study villages, whereas the mean SOA, wood combustion, and plant waxes factors differed seasonally. There was no relationship between source contributions and questionnaire-based measurements of source-specific exposures, implying that the impacts of source contributions on exposure are affected by complex spatial, temporal and behavioral patterns that are difficult to quantify using questionnaire-based measurements. Epidemiologic studies, health risk assessments, and intervention programs would benefit from a better understanding of the sources impacting PM exposure among populations in developing countries.

Impact of regional transport on the anthropogenic and biogenic secondary organic aerosols in the Los Angeles Basin

This manuscript explores the role of regional transport on anthropogenic and biogenic secondary organic carbon (SOC) concentrations in ambient fine particulate (PM2.5) organic carbon (OC) in the Los Angeles (LA) Basin. Daily organic molecular markers, water soluble organic carbon (WSOC), OC, and elemental carbon (EC) measurements from May 2009 through April 2010 at a central site in downtown LA, and results from a positive matrix factorization (PMF) analysis of these data, were used to understand the role of regional transport on SOC concentrations. A backward-trajectory analysis, coupled with the measurements and estimated source contributions, were used to evaluate the origins of SOC aerosols. Anthropogenic and biogenic SOC were identified in central LA over the study period, together contributing 40% of the annual average PM2.5 OC mass. There were distinct seasonal variations, with high contributions of anthropogenic SOC in summer, and high contributions of biogenic SOC in spring. The back-trajectory analysis, coupled with daily source contributions of SOC and organic compounds as indicators, allowed us to identify potential source locations and dominant meteorological conditions contributing to elevated SOC at the measurement site. The results show that air mass movements from the Pacific Ocean are associated with higher contributions of anthropogenic SOC to the PM2.5 OC in downtown LA, suggesting that the combination of local meteorological conditions and local anthropogenic emissions led to an increase in the anthropogenic SOC. In contrast, air masses passing over the Central Valley and forested areas where there are biogenic hydrocarbon emissions are closely associated with higher contributions of biogenic SOC in the region. The study emphasizes that higher anthropogenic SOC contributions are due to the combination of local emissions with humidity air from the ocean, and that higher biogenic SOC contributions are impacted by transport of pollutants from regions outside the LA Basin.

Molecular markers in ambient aerosol in the Mahanadi Riverside Basin of eastern central India during winter.

Organic molecular markers are important atmospheric constituents. Their formation and sources are important aspects of the study of urban and rural air quality. We collected PM10 aerosol samples from the Mahanadi Riverside Basin (MRB), a rural part of eastern central India, during the winter of 2011. PM10 aerosols were characterized for molecular markers using ion chromatography. The concentration of PM10 ranged from 208.8 to 588.3 μg m(-3) with a mean concentration of 388.9 μg m(-3). Total concentration of anhydrosugars, sugar alcohols, primary sugars, and oxalate were found to be 3.25, 5.60, 10.52, and 0.37 μg m(-3), respectively, during the study period. Glucose was the most abundant species followed by levoglucosan and mannitol. Significant positive correlation between the molecular markers, anhydrosugars, sugar alcohols, primary sugars, and oxalic acid confirmed that biomass burning, biogenic activity, and re-suspension of soil particles were the main sources of aerosol in the eastern central India study area.

Identification of the sources of primary organic aerosols at urban schools: A molecular marker approach

Children are particularly susceptible to air pollution and schools are examples of urban microenvironments that can account for a large portion of children's exposure to airborne particles. Thus this paper aimed to determine the sources of primary airborne particles that children are exposed to at school by analyzing selected organic molecular markers at 11 urban schools in Brisbane, Australia. Positive matrix factorization analysis identified four sources at the schools: vehicle emissions, biomass burning, meat cooking and plant wax emissions accounting for 45%, 29%, 16% and 7%, of the organic carbon respectively. Biomass burning peaked in winter due to prescribed burning of bushland around Brisbane. Overall, the results indicated that both local (traffic) and regional (biomass burning) sources of primary organic aerosols influence the levels of ambient particles that children are exposed at the schools. These results have implications for potential control strategies for mitigating exposure at schools.

Lipid biomarkers in surface sediments from the Gulf of Genoa, Ligurian sea (NW Mediterranean sea) and their potential for the reconstruction of palaeo-environments

A series of molecular organic markers were determined in surface sediments from the Gulf of Genoa (Ligurian Sea) in order to evaluate their potential for palaeo-environmental reconstructions. Allochthonous input can be characterized by the distributions of n-C29 and n-C31 alkanes, n-C26 and n-C28 alkanols and branched glycerol dialkyl glycerol tetraethers (GDGTs), whose concentrations are generally highest near the river mouths. In the open basin however, terrestrial n-alkanes and n-alkanols may have an additional, eolian source. Autochthonous input is represented by crenarchaeol and isoprenoid GDGTs. Their concentrations are highest in the open basin showing the preference of Thaumarchaeota for oligotrophic waters. Indications of a significant degradation of sterols and C37 alkenones exclude these lipids as reliable productivity proxies. Using terrestrial and aquatic lipids as end-members allows estimating the percentage of terrestrial organic matter between 20% and 58% in the coastal area decreasing to 1–30% in the deep basin. The spatial distribution of sea surface temperature (SST) estimates using the alkenone-based UK′37 index is very similar to the autumnal (November) mean satellite-based SST distribution. Conversely, TEXH86-derived SST estimates are close to winter SSTs in the coastal area and summer SSTs in the open basin. This pattern reflects presumably a shift in the main production of Thaumarchaeota from the coastal area in winter to the open basin in summer. This study represents a major prerequisite for the future application of lipid biomarkers on sediment cores from the Gulf of Genoa.

제주도 고산지역 탄소 성분의 특성 분석 - 유기탄소의 열광학적 특성 및 유기성분 중심으로

Abstract Ground-based measurements were conducted from August 25 to September 8 of 2011 for understandingcharacteristics of carbonaceous aerosols measured at Gosan. Chemical components and their sources werediscussed by analysis of organic compounds with identification of primary and secondary products in particulatematter. Thus, organic carbon (OC) and elemental carbon (EC) based on the carbonaceous thermal distribution(CTD), which provides detailed carbon signature characteristics relative to analytical temperature, was used toimprove the carbon fractionation of the analytical method. In addition, organic compounds by gas chromatographytechnique with the backward trajectories were discussed for characteristics of carbonaceous aerosols. Different air-masses were classified related to the OC thermal signatures and the organic molecular markers such as aromaticacids and PAHs. We concluded that the aging process was influenced by the long-range transport from East Seaarea. Key words : Organic, Organic compounds, OC, EC

Preliminary assessment of the anthropogenic and biogenic contributions to secondary organic aerosols at two industrial cities in the upper Midwest

The contributions of anthropogenic and biogenic secondary organic carbon (SOC) to total PM2.5 mass are of interest to air quality management agencies required to demonstrate maintenance of the PM2.5 NAAQS. Reductions of SOC can be used in conjunction with the mitigation of other PM2.5 constituents to maintain PM2.5 concentrations below the regulatory limit. Currently, quantitative tools to understand the SOC source contributions to PM2.5 mass are not well developed, and the spatial variation of different types of SOC is not known.In this study concentrations of anthropogenic and biogenic SOC mass were determined using PM2.5 measurements made in Cleveland, OH and Mingo Junction, OH. Twenty-four hour averaged samples were collected on the EPA 1-in-6 day schedule over the course of one year between June 2007 and May of 2008. Organic molecular markers for anthropogenic and biogenic SOC were extracted from the PM2.5, silylated, and then analyzed by GC–MS. Source apportionment calculations were conducted using the EPA CMB (v.8.2) software and organic molecular markers as source tracers.SOC concentrations calculated from SOC tracers measurements followed the expected seasonal patterns with maximum contributions during the summer and minimum contributions during the winter. Anthropogenic SOC constituted approximately 37% to the apportioned SOC and 6% to the measured OC, on average across both sites. Biogenic SOC contributed the 42% to the apportioned SOC, and 4% to the measured OC. Anthropogenic SOC contributed strongly to organic PM2.5 meaning that SOC may by partially controllable by reductions in VOC emissions from anthropogenic sources.Similarities in the month-to-month patterns in α-pinene markers were observed between Cleveland and Mingo Junction, suggesting a regional character to this type of SOC. However, such patterns were not readily apparent in the isoprene markers.Limitations were found in the current version of the model. Approximately half of the water soluble organic carbon unrelated to biomass burning (NB-WSOC) during spring, summer and early fall could not be apportioned by the CMB model with the SOC markers available during this study. This suggested that additional sources not included in the CMB model used in this study contributed to SOC, or that models using markers measured in chamber oxidations are not entirely representative of the study sites. The unapportioned OC did not correlate particularly well with any of the known OC sources. While performance of the model is limited due to uncertainties in the source profiles, the apportionments calculated still give a preliminary insight into the relative contributions to SOC from anthropogenic and biogenic emissions.

Long-range transport of biomass burning emissions based on organic molecular markers and carbonaceous thermal distribution

Semi-continuous organic carbon (OC), elemental carbon (EC), and organic molecular markers were analyzed using the thermal optical transmittance method at the Gosan supersite (on Jeju Island, Korea), which has been widely used as a regional background site for East Asia. The Carbonaceous Thermal Distribution (CTD) method, which can provide detailed carbon signature characteristics relative to analytical temperature, was used to improve the carbon fractionation of the analytical method. Ground-based measurements were conducted from October 25 to November 5, 2010. During the sampling period, one high OC concentration event and two characteristic periods were observed. Considering the thermal distribution patterns, the relationship between the EC and black carbon (BC) by optical measurements, the backward trajectories, the aerosol optical thickness, the PM10 concentrations from the 316 PM-network sites that were operated by the Ministry of Environment in Korea, and the organic molecular markers, such as levoglucosan, PAHs, and organic acids, we concluded that the event was influenced by long-range transport from biomass burning emissions. This study discusses the CTD analysis with organic molecular marker concentrations, extracts and interprets additional carbon fractions from a semi-continuous data set, and provides knowledge regarding the origin of carbon sources and their behaviors.

Source apportionments of PM2.5 organic carbon using molecular marker Positive Matrix Factorization and comparison of results from different receptor models

Four hundred fine particulate matter (PM2.5) samples collected over a 1-year period at two sites in the Los Angeles Basin were analyzed for organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC) and organic molecular markers. The results were used in a Positive Matrix Factorization (PMF) receptor model to obtain daily, monthly and annual average source contributions to PM2.5 OC. Results of the PMF model showed similar source categories with comparable year-long contributions to PM2.5 OC across the sites. Five source categories providing reasonably stable profiles were identified: mobile, wood smoke, primary biogenic, and two types of secondary organic carbon (SOC) (i.e., anthropogenic and biogenic emissions). Total primary emission factors and total SOC factors contributed approximately 60% and 40%, respectively, to the annual-average OC concentrations. Primary sources showed strong seasonal patterns with high winter peaks and low summer peaks, while SOC showed a reverse pattern with highs in the spring and summer in the region. Interestingly, smoke from forest fires which occurred episodically in California during the summer and fall of 2009 was identified and combined with the primary biogenic source as one distinct factor to the OC budget. The PMF resolved factors were further investigated and compared to a chemical mass balance (CMB) model and a second multi-variant receptor model (UNMIX) using molecular markers considered in the PMF. Good agreement between the source contribution from mobile sources and biomass burning for three models were obtained, providing additional weight of evidence that these source apportionment techniques are sufficiently accurate for policy development. However, the CMB model did not quantify primary biogenic emissions, which were included in other sources with the SOC. Both multivariate receptor models, the PMF and the UNMIX, were unable to separate source contributions from diesel and gasoline engines.

Volatility of Organic Molecular Markers Used for Source Apportionment Analysis: Measurements and Implications for Atmospheric Lifetime

Molecular markers are organic species used to define fingerprints for source apportionment of ambient fine particulate matter. Traditionally, these markers have been assumed to be stable in the atmosphere. This work investigates the gas-particle partitioning of eight organic species used as molecular markers in receptor models for biomass burning (levoglucosan), motor vehicles (5α-cholestane, n-hexacosane, n-triacontane, 1,2-benz[a]anthracene, coronene), and meat cooking (cholesterol, oleic acid). Experiments were conducted using a thermodenuder to measure the evaporation of single component particles. The data were analyzed using the integrated volume method to determine saturation concentrations and enthalpies of vaporization for each compound. The results indicate that appreciable quantities (>10%) of most of these markers exist in the gas phase under typical atmospheric conditions. Therefore, these species should be considered semivolatile. Predictions from a chemical kinetics model indicate that gas-particle partitioning has important effects on the atmospheric lifetime of these species. The atmospheric decay of semivolatile compounds proceeds much more rapidly than nonvolatile compounds because gas-phase oxidation induces evaporation of particle-phase material. Therefore, both gas-particle partitioning and chemical reactions need to be accounted for when semivolatile molecular markers are used for source apportionment studies.

Positive Matrix Factorization of PM2.5: Comparison and Implications of Using Different Speciation Data Sets

To evaluate the utility and consistency of different speciation data sets in source apportionment of PM(2.5), positive matrix factorization (PMF) coupled with a bootstrap technique for uncertainty assessment was applied to four different 1-year data sets composed of bulk species, bulk species and water-soluble elements (WSE), bulk species and organic molecular markers (OMM), and all species. The five factors resolved by using only the bulk species best reproduced the observed concentrations of PM(2.5) components. Combining WSE with bulk species as PMF inputs also produced five factors. Three of them were linked to soil, road dust, and processed dust, and together contributed 26.0% of reconstructed PM(2.5) mass. A 7-factor PMF solution was identified using speciated OMM and bulk species. The EC/sterane and summertime/selective aliphatic factors had the highest contributions to EC (39.0%) and OC (53.8%), respectively. The nine factors resolved by including all species as input data are consistent with those from the previous two solutions (WSE and bulk species, OMM and bulk species) in both factor profiles and contributions (r = 0.88-1.00). The comparisons across different solutions indicate that the selection of input data set may depend on the PM components or sources of interest for specific source-oriented health study.

Positive matrix factorization of a 32-month series of daily PM2.5 speciation data with incorporation of temperature stratification

This study presents source apportionment results for PM2.5 from applying positive matrix factorization (PMF) to a 32-month series of daily PM2.5 compositional data from Denver, CO, including concentrations of sulfate, nitrate, bulk elemental carbon (EC) and organic carbon (OC), and 51 organic molecular markers (OMMs). An optimum 8-factor solution was determined primarily based on the interpretability of the PMF results and rate of matching factors from bootstrapped PMF solutions with those from the base case solution. These eight factors were identified as inorganic ion, n-alkane, EC/sterane, light n-alkane/polycyclic aromatic hydrocarbon (PAH), medium alkane/alkanoic acid, PAH, winter/methoxyphenol and summer/odd n-alkane. The inorganic ion factor dominated the reconstructed PM2.5 mass (sulfate + nitrate + EC + OC) in cold periods (daily average temperature <10 °C; 43.7% of reconstructed PM2.5 mass) whereas the summer/odd n-alkane factor dominated in hot periods (>20 °C; 53.1%). The two factors had comparable relative contributions of 26.5% and 27.1% in warm periods with temperatures between 10 °C and 20 °C. Each of the seven factors resolved in a previous study (Dutton et al., 2010b) using a 1-year data set from the same location matches one factor from the current work based on comparing factor profiles. Six out of the seven matched pairs of factors are linked to similar source classes as suggested by the strong correlations between factor contributions (r = 0.89–0.98). Temperature-stratified source apportionment was conducted for three subsets of the data in the current study, corresponding to the cold, warm and hot periods mentioned above. The cold period (7-factor) solution exhibited a similar distribution of reconstructed PM2.5 mass as the full data set solution. The factor contributions of the warm period (7-factor) solution were well correlated with those from the full data set solution (r = 0.76–0.99). However, the reconstructed PM2.5 mass was distributed more to inorganic ion, n-alkane and medium alkane/alkanoic acid factors in the warm period solution than in the full data set solution. For the hot period (6-factor) solution, PM2.5 mass distribution was quite different from that of the full data set solution, as illustrated by regression slopes as low as 0.2 and as high as 4.8 of each matched pair of factors across the two solutions.

Organic molecular markers and signature from wood combustion particles in winter ambient aerosols: aerosol mass spectrometer (AMS) and high time-resolved GC-MS measurements in Augsburg, Germany

Abstract. The impact of wood combustion on ambient aerosols was investigated in Augsburg, Germany during a winter measurement campaign of a six-week period. Special attention was paid to the high time resolution observations of wood combustion with different mass spectrometric methods. Here we present and compare the results from an Aerodyne aerosol mass spectrometer (AMS) and gas chromatographic – mass spectrometric (GC-MS) analysed PM1 filters on an hourly basis. This includes source apportionment of the AMS derived organic matter (OM) using positive matrix factorisation (PMF) and analysis of levoglucosan as wood combustion marker, respectively. During the measurement period nitrate and OM mass are the main contributors to the defined submicron particle mass of AMS and Aethalometer with 28% and 35%, respectively. Wood combustion organic aerosol (WCOA) contributes to OM with 23% on average and 27% in the evening and night time. Conclusively, wood combustion has a strong influence on the organic matter and overall aerosol composition. Levoglucosan accounts for 14% of WCOA mass with a higher percentage in comparison to other studies. The ratio between the mass of levoglucosan and organic carbon amounts to 0.06. This study is unique in that it provides a one-hour time resolution comparison between the wood combustion results of the AMS and the GC-MS analysed filter method at a PM1 particle size range. The comparison of the concentration variation with time of the PMF WCOA factor, levoglucosan estimated by the AMS data and the levoglucosan measured by GC-MS is highly correlated (R2 = 0.84), and a detailed discussion on the contributors to the wood combustion marker ion at mass-to-charge ratio 60 is given. At the end, both estimations, the WCOA factor and the levoglucosan concentration estimated by AMS data, allow to observe the variation with time of wood combustion emissions (gradient correlation with GC-MS levoglucosan of R2 = 0.84). In the case of WCOA, it provides the estimated magnitude of wood combustion emission. Quantitative estimation of the levoglucosan concentration from the AMS data is problematic due to its overestimation in comparison to the levoglucosan measured by the GC-MS.

Intra-urban spatial variability and uncertainty assessment of PM2.5 sources based on carbonaceous species

To identify the sources of PM2.5 – bound carbonaceous species and examine the spatial variability of source contributions in the Denver metropolitan area, positive matrix factorization (PMF) was applied to one year of every sixth day ambient PM2.5 compositional data, including elemental carbon (EC), organic carbon (OC), and 32 organic molecular markers, from four sites (two residential and two near-traffic). Statistics (median, inner quantiles and 5th – 95th percentiles range) of factor contributions, expressed as reconstructed carbonaceous mass (EC + OC), were estimated from PMF solutions of replicate datasets generated by using a stationary block bootstrap technique. A seven-factor solution was resolved for a set of data pooled across the four sites, as it gave the most interpretable results and had the highest rate of neural network factor matching (76.9%). Identified factors were primarily associated with high plant wax, summertime emission, diesel vehicle emission, fossil fuel combustion, motor vehicle emission, lubricating oil combustion and wood burning. Pearson correlation coefficients (r) and coefficients of divergence (COD) were used to assess spatial variability of factor contributions. The summertime emission factor exhibited the highest spatial correlation (r = 0.74 – 0.88) and lowest CODs (0.32 – 0.38) among all resolved factors; while the three traffic dominated factors (diesel vehicle emission, motor vehicle emission and lubricating oil combustion) showed lower correlations (r = 0.47 – 0.55) and higher CODs (0.41 – 0.53) on average. Average total EC and OC mass were apportioned to each factor and showed a similar distribution across the four sites. Modeling uncertainties were defined as the 5th – 95th percentile range of the factor contributions derived from valid bootstrap PMF solutions, and were highly correlated with the median factor contribution in each factor (r = 0.77 – 0.98). Source apportionment was also performed on site specific datasets; the results exhibited similar factor profiles and temporal variation in factor contribution as those obtained for the pooled dataset, indicating that the four sites are primarily influenced by similar types of sources. On the other hand, differences were observed in absolute factor contributions between PMF solutions for the pooled versus site-specific datasets, likely due to the large uncertainties in EC and OC factor profiles derived from the site specific datasets with limited numbers of observations.

Intra-urban spatial variability of PM2.5-bound carbonaceous components

The Denver Aerosol Sources and Health (DASH) study was designed to evaluate associations between PM2.5 species and sources and adverse human health effects. The DASH study generated a five-year (2003–2007) time series of daily speciated PM2.5 concentration measurements from a single, special-purpose monitoring site in Denver, CO. To evaluate the ability of this site to adequately represent the short term temporal variability of PM2.5 concentrations in the five county Denver metropolitan area, a one year supplemental set of PM2.5 samples was collected every sixth day at the original DASH monitoring site and concurrently at three additional sites. Two of the four sites, including the original DASH site, were located in residential areas at least 1.9 km from interstate highways. The other two sites were located within 0.3 km of interstate highways. Concentrations of elemental carbon (EC), organic carbon (OC), and 58 organic molecular markers were measured at each site. To assess spatial variability, site pairs were compared using the Pearson correlation coefficient (r) and coefficient of divergence (COD), a statistic that provides information on the degree of uniformity between monitoring sites. Bi-weekly co-located samples collected from July 2004 to September 2005 were also analyzed and used to estimate the uncertainty associated with sampling and analytical measurement for each species. In general, the two near-highway sites exhibited higher concentrations of EC, OC, polycyclic aromatic hydrocarbons (PAHs), and steranes than did the more residential sites. Lower spatial heterogeneity based on r and COD was inferred for all carbonaceous species after considering their divergence and lack of perfect correlations in co-located samples. Ratio–ratio plots combined with available gasoline- and diesel-powered motor vehicle emissions profiles for the region suggested a greater impact to high molecular weight (HMW) PAHs from diesel-powered vehicles at the near-highway sites and a more uniformly distributed impact to ambient hopanes from gasoline-powered motor vehicles at all four sites.