Secondary Organic Compounds Research Articles

Relative importance of organic coatings for the heterogeneous hydrolysis of N2O5 during summer in Europe

The heterogeneous reaction probability of N2O5 depends largely on the aerosol chemical composition. Several recent laboratory studies have shown that the presence of organic coatings on aqueous aerosols can suppress heterogeneous N2O5 hydrolysis. In this study we investigated the relative importance of organic coatings, formed via gas‐to‐particle conversion on aqueous aerosols, to N2O5 hydrolysis on local and regional scales during summer in Europe. We present results of one‐dimensional process studies and of regional‐scale model simulations for Europe with the comprehensive model system COSMO‐ART. To treat N2O5 hydrolysis, we used recent results from laboratory studies that quantified on the basis of the organic coating thickness. The simulations showed that during any episode the conditions for formation of N2O5 and secondary organic compounds were very variable and depended strongly on the meteorological conditions. In regions of the model domain where both components were built‐up, the formation of organic coatings could decrease particulate nitrate concentrations by up to 90%. Where these conditions were not met, the impact of the organic coating was negligible.

Size‐ and time‐resolved chemical particle characterization during CAREBeijing‐2006: Different pollution regimes and diurnal profiles

Beijing, the capital of China, faces severe air pollution problems, resulting from a steep economic growth during the past decades. To better characterize the processes leading to the frequently observed high concentrations of air pollutants on a regional scale, the international field campaign “Campaigns of Air Quality Research in Beijing and Surrounding Region 2006” (CAREBeijing‐2006) was conducted in summer 2006. In this contribution, we present chemical data of size‐resolved particles, obtained by a five‐stage Berner impactor during 3 weeks at both an urban and suburban site in the area of Beijing, China. The samples were analyzed for inorganic ions (Cl−, SO42−, NO3−, NH4+, K+, Ca2+, Na+, and Mg2+), carbon sum parameters (OC, EC, and WSOC), and a variety of organic compounds such as dicarboxylic acids, alkanes, PAHs, and, for the first time in China, nitrooxy‐organosulfates. On average, the observed PM10 (where PM is particulate matter) mass concentrations were 133 μg m−3 and 112 μg m−3 at the urban and suburban site, respectively. A high influence of meteorology on the PM pollution was observed and is discussed. The highest concentrations of both PM mass and particle constituents were observed when sampled air masses originated south of Beijing and moved over the area with low wind speeds. During such periods, a strong increase of daytime concentrations of the secondary ions sulfate, nitrate, ammonium, and also some dicarboxylic acids could be observed. A strong diurnal variation of particle sulfate concentration with increasing values from morning to afternoon was observed during an intensive period, which could be attributed to regional production. Similar observations were made for oxalic acid. Generally, water‐soluble organic carbon concentrations were enhanced by a factor of 2 in fine particles during the studied period of intense photochemistry. Elemental carbon, alkanes, and PAHs showed clear nighttime concentration maxima obviously due to enhanced emissions and a relatively low mixing volume during night. For the newly studied compound group of nitrooxy‐organosulfates, qualitative data can be presented indicating an influence of nighttime chemistry and/or anthropogenic activities on their concentrations. The investigation of an intense nucleation and particle growth event revealed that the youngest particles largely consist of ammonium sulfate and primary carbonaceous material, with a possible contribution of secondary organic compounds.

Polar organic tracers in PM<sub>2.5</sub> aerosols from forests in eastern China

Abstract. Photooxidation products of biogenic volatile organic compounds, mainly isoprene and monoterpenes, are significant sources of atmospheric particulate matter in forested regions. The objectives of this study were to examine time series and diel variations of polar organic tracers for the photooxidation of isoprene and α-pinene to investigate whether they are linked with meteorological parameters or trace gases, and to determine their carbon contributions. In addition, the biogenic secondary organic carbon contributions from isoprene were estimated. PM2.5 (particulate matter with an aerodynamic diameter <2.5 μm) aerosol samples were collected from forests in eastern China and compared with data from forested sites in Europe and America. Aerosol sampling was conducted at four sites located along a gradient of ecological succession in four different regions, i.e. Changbai Mountain Nature Reserve (boreal-temperate), Chongming National Forest Park (temperate), Dinghu Mountain Nature Reserve (subtropical) and Jianfengling Nature Reserve in Hainan (tropical) during summer periods when the meteorological conditions are believed to be favorable for photochemical processes. Fifty PM2.5 samples were collected; eighteen organic compounds, organic carbon (OC), elemental carbon and trace gases were measured. Results indicate that the concentration trends of the secondary organic compounds reflected those of the trace gases and meteorological parameters. Very good correlations between the sum concentrations of isoprene oxidation products and atmospheric SO2, O3, NO2, NOx, as well as CO2, at the Changbai site were found. The secondary OC due to isoprene was relatively high in tropical Hainan (0.27 μgC/m3) where isoprene-emitting broadleaf species are dominant, but was comparable in boreal Changbai (0.32 μgC/m3) where coniferous species are prevalent. The contribution of malic acid, which may have both biogenic and anthropogenic sources, to the OC mass was comparable at the four sites.

Rural continental aerosol properties and processes observed during the Hohenpeissenberg Aerosol Characterization Experiment (HAZE2002)

Abstract. Detailed investigations of the chemical and microphysical properties of rural continental aerosols were performed during the HAZE2002 experiment, which was conducted in May 2002 at the Meteorological Observatory Hohenpeissenberg (DWD) in Southern Germany. Online measurements included: Size-resolved chemical composition of submicron particles; total particle number concentrations and size distributions over the diameter range of 3 nm to 9 μm; gas-phase concentration of monoterpenes, CO, O3, OH, and H2SO4. Filter sampling and offline analytical techniques were used to determine: Fine particle mass (PM2.5), organic, elemental and total carbon in PM2.5 (OC2.5, EC2.5, TC2.5), and selected organic compounds (dicarboxylic acids, polycyclic aromatic hydrocarbons, proteins). Overall, the non-refractory components of submicron particles detected by aerosol mass spectrometry (PM1, 6.6±5.4 μg m−3, arithmetic mean and standard deviation) accounted for ~62% of PM2.5 determined by filter gravimetry (10.6±4.7 μg m−3). The relative proportions of non-refractory submicron particle components were: (23±39)% ammonium nitrate, (27±23)% ammonium sulfate, and (50±40)% organics (OM1). OM1 was closely correlated with PM1 (r2=0.9) indicating a near-constant ratio of non-refractory organics and inorganics. The average ratio of OM1 to OC2.5 was 2.1±1.4, indicating a high proportion of heteroelements in the organic fraction of the sampled rural aerosol. This is consistent with the high ratio of oxygenated organic aerosol (OOA) over hydrocarbon-like organic aerosol (HOA) inferred from the AMS results (4:1), and also with the high abundance of proteins (~3%) indicating a high proportion of primary biological material (~30%) in PM2.5. This finding was confirmed by low abundance of PAHs (<1 ng m−3) and EC (<1 μg m−3) in PM2.5 and detection of several secondary organic aerosol compounds (dicarboxylic acids) and their precursors (monoterpenes). New particle formation was observed almost every day with particle number concentrations exceeding 104 cm−3 (nighttime background level 1000–2000 cm−3). Closer inspection of two major events indicated that the observed nucleation agrees with ternary H2SO4/H2O/NH3 nucleation and that condensation of both organic and inorganic species contributed to particle growth.

Modelling changes of aerosol compositions over Belgium and Europe

Seasonal changes in aerosol compositions over Belgium and Europe are simulated with an extended version of the EUROS model. EUROS is capable of modelling mass and chemical composition of aerosols in two size fractions (PM2.5 and PM10-2.5). The chemical composition is expressed in terms of seven components: ammonium, nitrate, sulphate, primary inorganic compounds, elementary carbon, primary organic compounds and Secondary Organic Compounds (SOA). A comparison of modelled and measured aerosol concentrations showed that modelled concentrations are generally consistent with observed concentrations. The chemical composition of the aerosol showed a strong dependence on the season. High aerosol concentrations during the summer were mainly due to high concentrations of the secondary components nitrate, ammonium, sulphate and SOA in the size fraction PM2.5. In contrast, during autumn and winter, increased PM-concentrations were mainly due to higher concentrations of primary components, especially in the size fraction PM10-2.5.

Characterization of organosulfates from the photooxidation of isoprene and unsaturated fatty acids in ambient aerosol using liquid chromatography/(−) electrospray ionization mass spectrometry

In the present study, we have characterized in detail the MS(2) and MS(3) fragmentation behaviors, using electrospray ionization (ESI) in the negative ion mode, of previously identified sulfated isoprene secondary organic aerosol compounds, including 2-methyltetrols, 2-methylglyceric acid, 2-methyltetrol mononitrate derivatives, glyoxal and methylglyoxal. A major fragmentation pathway for the deprotonated molecules of the sulfate esters of 2-methyltetrols and 2-methylglyceric acid and of the sulfate derivatives of glyoxal and methylglyoxal is the formation of the bisulfate [HSO(4)](-) anion, while the deprotonated sulfate esters of 2-methyltetrol mononitrate derivatives preferentially fragment through loss of nitric acid. Rational interpretation of MS(2), MS(3) and accurate mass data led to the structural characterization of unknown polar compounds in K-puszta fine aerosol as organosulfate derivatives of photooxidation products of unsaturated fatty acids, i.e. 2-hydroxy-1,4-butanedialdehyde, 4,5- and 2,3-dihydroxypentanoic acids, and 2-hydroxyglutaric acid, and of alpha-pinene, i.e. 3-hydroxyglutaric acid. The deprotonated molecules of the sulfated hydroxyacids, 2-methylglyceric acid, 4,5- and 2,3-dihydroxypentanoic acid, and 2- and 3-hydroxyglutaric acids, showed in addition to the [HSO(4)](-) ion (m/z 97) neutral losses of water, CO(2) and/or SO(3), features that are characteristic of humic-like substances. The polar organosulfates characterized in the present work are of climatic relevance because they may contribute to the hydrophilic properties of fine ambient aerosol. In addition, these compounds probably serve as ambient tracer compounds for the occurrence of secondary organic aerosol formation under acidic conditions.

Extension of the EUROS Integrated Air Quality Model to Fine Particulate Matter by Coupling to CACM/MADRID 2

The European Operational Smog (EUROS) integrated air quality modelling system has been extended to model fine particulate matter (PM). From an extended literature study, the Caltech Atmospheric Chemistry Mechanism and the Model of Aerosol Dynamics, Reaction, Ionisation and Dissolution were selected and recently coupled to EUROS. Currently, modelling of mass and chemical composition of aerosols in two size fractions (PM2.5 and PM10–2.5) is possible. The chemical composition is expressed in terms of seven components: ammonium, nitrate, sulphate, elementary carbon, primary inorganic compounds, primary organic compounds and secondary organic compounds. Calculated PM10 concentrations and chemical composition are presented for two summer months of the year 2003 (1 July to 31 August).

Generation of sub-micron particles and secondary pollutants from building materials by ozone reaction

This study reports results from two different experiments examining reactions between ozone and common building materials that can lead to the formation of secondary products and particulate-phase materials. Monitored species include sub-micron particles and volatile organic compounds (VOCs). In the first set of experiments, various building materials were placed in a 20 L stainless-steel chamber and exposed to ozone. The materials included expanded polystyrene, a natural rubber adhesive, cedar board, Japanese Cyprus board and silver fir board, as well as d-limonene, which is a known constituent of certain woods and cleaning products. The combination of ozone and either d-limonene, cedar board or cypress board produced sub-micron particles, with most of the increase occurring in the size range of 0.01– 0.5 μ m diameter. This was not observed for the other materials. In the case of cedar board, the consequence of ozone exposure over an extended time interval was monitored. As the exposure time elapsed, the concentration of sub-micron particles moderately decreased. In the second set of experiments, unwaxed or waxed plastic tiles were placed in the 20 L chamber and exposed to ozone. Sub-micron particles and organic compounds were measured during the course of the experiments. In the case of the waxed tile, the number of 0.01– 1.0 μ m size particles grew about 50 × 10 8 particles m - 3 ; particle growth was significantly less for the un-waxed tile. For both the waxed and un-waxed tiles, the emission rates of heptane, nonane, nonanal, and decanal increased after ozone was added to the supply air. (However, it is not clear if some or all of this production was due to ozone reacting with the sorbent used for sampling or with compounds captured by the sorbent.) This study provides further evidence that ozone-initiated reactions with building materials can be a significant source of both sub-micron particles and secondary organic compounds in indoor environments.

A two-year monitoring program of aromatic hydrocarbons in Rio de Janeiro downtown area

Benzene, toluene, ethylbenzene, m+p+o-xylene (BTEX) and two trimethylbenzenes (BTEXT) were monitored in Rio de Janeiro downtown area during 2004 and 2005. Some criteria pollutants and meteorological parameters were also determined in order to assess the main data correlations. 94 samples were collected, using activated charcoal cartridges, between 9:00 am and 3:00 pm. The mean concentrations obtained were: 14.5, 22.8, 9.19, 19.3, 8.5, 10.4 and 12.1 µg m-3 for benzene, toluene, ethylbenzene, m+p-xylene, o-xylene, 1,2,3-trimethylbenzene and 1,3,5-trimethylbenzene, respectively. These values are similar to mean concentrations obtained in the Brazilian cities of Porto Alegre, Volta Redonda and São Paulo, which use the same type of fuel. Multivariate analyses showed that individual BTEXT are emitted by the same source and are not well correlated with other primary pollutants. These results may be due to the contribution of evaporative losses of the BTEXT and to the formation of secondary volatile organic compounds in the atmosphere.

The composition of nucleation and Aitken modes particles during coastal nucleation events: evidence for marine secondary organic contribution

Abstract. Newly-formed nanometer-sized particles have been observed at coastal and marine environments world wide. Organic species have so far not been detected in those newly-formed nucleation mode particles. In this study, we applied the ultrafine organic tandem differential mobility analyzer method to study the possible existence of an organic fraction in recently formed coastal nucleation mode particles (d<20 nm) at the Mace Head research station. Furthermore, effects of those nucleation events on potential cloud condensation nuclei were studied. The coastal events were typical for the Mace Head region and they occurred at low tide conditions during efficient solar radiation and enhanced biological activity in spring 2002. Additionally, a pulse height analyzer ultrafine condensation particle counter technique was used to study the composition of newly-formed particles formed in low tide conditions during a lower biological activity in October 2002. The overall results of the ultrafine organic tandem differential mobility analyzer and the pulse height analyzer ultrafine condensation particle counter measurements indicate that those coastally/marinely formed nucleation mode particles include a remarkable fraction of secondary organic products, beside iodine oxides, which are likely to be responsible for the nucleation. During clean marine air mass conditions, the origin of those secondary organic oxidation compounds can be related to marine coast and open ocean biota and thus a major fraction of the organics may originate from biosynthetic production of alkenes such as isoprene and their oxidation driven by iodine radicals, hydroxyl radicals, acid catalysis, and ozone during efficient solar radiation. During modified marine conditions, also anthropogenic secondary organic compounds may contribute to the nucleation mode organic mass, in addition to biogenic secondary organic compounds. Thus, the ultrafine organic tandem differential mobility analyzer results suggest that the secondary organic compounds may, in addition to being significant contributors to the nucleation mode processes, accelerate the growth of freshly nucleated particles and increase their survival probability to cloud condensation nuclei and even larger radiatively active particle sizes. The results give new insights to the marine/coastal particle formation, growth, and properties. The marine biota driven secondary organic contributions to marine/coastal particle formation and composition can be anticipated in other species specific biologically active oceans and fresh-waters areas around the world and thus, they may be significant also to the global radiative bugdet, atmosphere-biosphere feedbacks, and climate change.

Analysis of Secondary Organic Aerosol Compounds from the Photooxidation of d-Limonene in the Presence of NOX and their Detection in Ambient PM2.5

Chemical analysis of secondary organic aerosol (SOA) from the photooxidation of a d-limonene/NOx/air mixture was carried out. SOA, generated in a smog chamber, was collected on Zefluor filters. To determine the structural characteristics of the compounds, the filter samples were solvent extracted and derivatized using analytical techniques that characterize functional groups contained in the compound: BF3-methanol derivatization was used for carboxylic groups, BSTFA for acidic and nonacidic hydroxyl groups, and PFBHA for ketone and aldehyde groups. The resulting derivative compounds were analyzed by GC-MS in the methane Cl and El modes. GC-MS analysis showed the occurrence of 103 oxygenated organic compounds in the filter extracts, 28 of which were identified. The major components include five tracer compounds previously identified from the photooxidation of alpha-pinene/NOx or beta-pinene/NOx systems, C4-C6 linear dicarboxylic acids, ketolimononaldehyde, limonic acid, and ketolimonic acid. Time profiles, yields, and proposed reaction schemes are provided for selected compounds. The laboratory SOA yield was 0.51 at a SOA concentration of 1470 microg m(-3). To determine the contributions of SOA products from d-limonene to ambient PM2.5, an analysis was performed for eight ambient PM2.5 samples collected in the southeastern United States in summer 2003. GC-MS analysis showed the occurrence of 21 d-limonene SOA compounds, indicating the impact of d-limonene on the regional aerosol burden. Based on our analysis, two compounds (nos. 55 and 69), not observed from the photooxidation of alpha-pinene or beta-pinene, are candidate tracers for d-limonene in atmospheric particulate matter.

Formation of secondary organic particle phase compounds from isoprene gas-phase oxidation products: An aerosol chamber and field study

Acid-catalyzed multiphase reactions of isoprene with hydrogen peroxide have been suggested to produce hydroxylated oxidation products, namely the diastereoisomeric 2-methyltetrols (2-methylthreitol and 2-methylerythritol), compounds which were found quite recently in aerosols above forests. In this study aerosol chamber experiments have been performed reacting isoprene or known isoprene oxidation products with hydrogen peroxide in the presence of acidic particles. Starting from isoprene, 2-methyl-3-butene-1,2-diol or 2-methyl-2-vinyloxirane the formation of the 2-methyltetrols could be observed. The reaction was most effective for 2-methyl-2-vinyloxirane. The last process can lead to an annual 2-methyltetrol formation in atmospheric particles of about 1 Tg C. Additionally, results from size segregated 2-methyltetrol measurements in Melpitz site (Germany) are presented. The concentrations are between 0.5 and 1.7 ng m −3. The 2-methyltetrols are enriched in the fine size fraction as expected for secondary organic aerosol compounds.

Absorption amplification of black carbon internally mixed with secondary organic aerosol

The scattering and absorption properties of black carbon (BC) particles internally mixed with secondary organic aerosol (SOA) were investigated experimentally at the large aerosol chamber facility AIDA. Diesel soot particles were coated with secondary organic compounds produced by the in situ ozonolysis of α‐pinene. It was found that the organic coating strongly affects the optical and microphysical properties of the soot aggregates. Amplification factors of the internally mixed BC of 1.8 to 2.1 compared to the specific absorption cross section of externally mixed BC were measured. These amplification factors are well reproduced by a Mie model for concentrically coated spheres over a wide range of organic coating/BC mixing ratios. Other optical properties in particular of thinly coated soot particles, namely, the single scattering albedo, the Ångstrøm exponent, and the hemispheric backscattering ratio, are less well reproduced by the model, most likely because of the restructuring and the incomplete enclosure of the porous soot aggregates.

Secondary organic compounds in atmospheric aerosols: speciation and formation mechanisms

Taking into account their atmospheric characteristics, generally under photochemical conditions, forested areas of Mediterranean countries constitute an appropriate environment to investigate the secondary organic aerosols. The objective of this study was to study in situ the aerosol composition, particularly in the photo-oxidation products of biogenic volatile organic compounds, taking into consideration anthropogenic inputs, and to explain how these compounds appear in the aerosols. Atmospheric particulate matter was collected at two sites: an Abies boressi forest in central Greece and at Giesta, a coastal-rural site in the centre of Portugal. The collected aerosol was extracted with solvents and characterised by gas chromatography and mass spectrometry. The detected secondary organics include alkene derivatives, oxo-, di- and monocarboxylic acids, oxy-aromatics, aza and thia arenes, and many terpene photo-oxidation products. This in situ experiment allowed confirming the presence of secondary constituents, which have been studied almost exclusively under simulated laboratory conditions. Some reaction pathways leading to the formation of compounds in the particulate phase from precursors are presented.

The contribution of sulfuric acid and non‐volatile compounds on the growth of freshly formed atmospheric aerosols

The formation of atmospheric aerosol particles (homogeneous nucleation, forming of stable clusters ∼1 nm in size), their subsequent growth to detectable sizes (>3 nm), and to the size of cloud condensation nuclei, remains one of the least understood atmospheric processes upon which global climate change critically depends. However, a quantitative model explanation for the growth of freshly formed aerosols has been missing. In this study, we present observations explaining the nucleation mode (3–25 nm) growth. Aerosol particles typically grow from 3 nm to 60–70 nm during a day, while their non‐volatile cores grow by 10–20 nm as well. The total particle growth rate is 2–8 nm/h while the non‐volatile core material can explain 20–40%. According to our results, sulfuric acid can explain the remainder of the growth, until the particle diameter is around 10–20 nm. After that secondary organic compounds significantly take part in growth process.

Molecular Genetic Analysis of QTLs for Ferulic Acid Content in Dried Straw of Rice (Oryza sativa L.)

Phenolic acids are secondary metabolic organic compounds produced by plants and often are mentioned as allelochemicals. This study was conducted to determine the genetic basis controlling the ferulic acid content of rice straw in a recombinant inbred (RI) population derived from a cross between a japonica variety, Asominori, with a higher content of ferulic acid, and an indica variety, IR24, with a lower content, using 289 RFLP markers. Continuous distributions and transgressive segregations of ferulic acid content were observed in the RI population, which showed that ferulic acid content in rice straw was quantitatively inherited. Single marker analysis and composite interval mapping identified three quantitative trait loci (QTLs) for ferulic acid content with LOD values of 2.03 (chromosome 3), 3.16 (chromosome 6), and 3.06 (chromosome 7); all three had increased additive effects (13.5, 18.3, and 18.1 microg g(-1)) from the Asominori parent and accounted for 5.5, 16.9, and 12.8% of total phenotypic variation, respectively. This is the first report on the identification of QTLs associated with ferulic acid and their chromosomal localization on the molecular map of rice. The tightly linked molecular markers that flank the QTLs might be useful in breeding and selection of varieties with higher phenolic acid content.

Theoretical Modeling of the Size-Dependent Influence of Surface Tension on the Absorptive Partitioning of Semi-Volatile Organic Compounds

The influence of surface tension on the formation of secondary organic aerosol (SOA) is investigated in this study using a size-dependent absorptive partitioning model. A theoretical framework is offered to estimate the surface tension of multi-component aerosols consisting of organic compounds and water. The size-dependent influence of surface tension on the absorptive partitioning of semi-volatile organic compounds is examined via numerical simulations of systems of representative pre-existing aerosol (PA) components and semi-volatile organic compounds that have been observed to constitute SOA. Results indicate that if nonpolar organic species constitute a significant fraction of the PA, the Kelvin effect on SOA formation may be negligible. However, if PA is dominated by polar organic compounds, the Kelvin effect on SOA formation is significant when the PA initial diameter is smaller than approximately 200 nm. If the PA is an aqueous aerosol, the Kelvin effect on SOA formation is most important. A simplified computational scheme for estimation of the Kelvin effect is developed in this study and feasibly could be coupled into three-dimensional air quality models that simulate SOA formation. Available observations also suggest that future modeling and analysis of SOA formation may need to consider the Kelvin effect. Concrete testing of the purely theoretical model presented here requires carefully designed observations that examine the phase distribution of secondary organic compounds between the gas phase and aerosol particles small enough to be affected by surface tension.

Polar organic oxygenates in PM2.5 at a southeastern site in the United States

Abstract A field study was undertaken in Research Triangle Park, NC, USA during the summer of 2000 to identify classes of polar oxygenates in PM 2.5 containing carbonyl and/or hydroxyl functional groups and, to the extent possible, determine the individual particle-bound oxygenates that make up each class. The selected site was in a semi-rural environment with expected impacts from both biogenic and anthropogenic sources. PM 2.5 samples were collected and analyzed for gravimetric mass, inorganic composition by ion chromatography, polar oxygenated compounds by gas chromatography-mass spectroscopy after derivatization of the solvent extracts, organic and elemental carbon (EC) by a thermal–optical method, and chemical functional groups by infrared (IR) spectroscopy. The chemical analyses also included determining the polarity of the PM 2.5 by measuring the organic carbon (OC) concentrations in a series of extraction solvents of increasing polarity. The ambient PM 2.5 mass concentrations ranged between 9 and 30 μg m −3 , with an average mass composition of 28% sulfate, 6% nitrate, 12% ammonium, 39% OC compound, 2% EC, and 12% liquid water at a relative humidity of 43%. OC analyses of the organic extracts indicated approximately 89% of the extractable OC was more polar in nature than that extracted by n -hexane. IR analysis of the PM 2.5 was consistent with the presence of significant levels of polar carbonyl and hydroxyl functional groups. The polar nature of the organic fraction was further supported by the observation that the inorganic fraction accounted for only about 80% of measured liquid water concentrations in the PM 2.5 . The mass spectra data were consistent with the presence of the following classes of oxygenates: oxo monocarboxylic acids, trihydroxy monocarboxylic acids, dihydroxy dicarboxylic acids, hydroxy dicarboxylic acids, normal dicarboxylic acids, oxo dicarboxylic acids, methoxy dicarboxylic acids, tricarboxylic acids, triols, and photooxidation products of α -pinene and toluene. In particular, five secondary organic aerosol compounds observed in a smog chamber irradiation of an α -pinene/NO x /air mixture were detected in ambient PM 2.5 .

Uncertainties in modeling secondary organic aerosols: three-dimensional modeling studies in Nashville/western Tennessee.

The formation of secondary organic aerosols (SOA) is simulated for the Nashville/western Tennessee domain using three recent SOA modules incorporated into the three-dimensional air quality model, CMAQ. The Odum/Griffin et al. and CMU/STI modules represent SOA absorptive partitioning into a mixture of primary and secondary particulate organic compounds (OC), with some differences in the formulation of the absorption process and the selection of SOA species and their precursors. Empirical representations based on measured laboratory SOA yields are used for condensable organic products in both these modules. The AEC module simulates SOA absorption into organic and aqueous particulate phases, and a representation based on an explicit gas-phase mechanism is used in the AEC module. Predicted SOA concentrations can vary by a factor of 10 or more. In general, the gas-phase mechanistic approach predicts a higher yield of SOA than those based on laboratory yields. There exist some differences in the two empirical modules despite their similar basis on experimental data. All three modules predict a dominance of SOA of biogenic origin as compared to SOA of anthropogenic origin. The causes for differences among the three SOA modules include the representation of terpenes, the mechanistic versus empirical representation of SOA-forming reactions, the identities of SOA, and the parameters used in the gas/particle partitioning calculations. Two sensitivity studies show that formation of water-soluble SOA and temperature dependence may be areas of key uncertainties affecting current models.

Sampling atmospheric carbonaceous aerosols using an integrated organic gas and particle sampler.

Measurement of particle-bound organic carbon (OC) may be complicated by sampling artifacts such as adsorption of gas-phase species onto particles or filters or evaporation of semivolatile compounds off the particles. A denuder-based integrated organic gas and particle sampler (IOGAPS), specifically designed to minimize sampling artifacts, has been developed to sample atmospheric carbonaceous aerosols. IOGAPS is designed to first remove gas-phase chemicals via sorption to the XAD-coated denuder, and subsequently particles are trapped on a quartz filter. A backup sorbent system consisting of sorbent- (XAD-4 resin) impregnated filters (SIFs) was used to capture the semivolatile OC that evaporates from the particles accumulated on the upstream quartz filter. A traditional filter pack (FP) air sampler, which uses a single quartz filter to collect the particles, was employed for comparison in this study. Elemental and organic carbon were determined from filter punches by a thermal optical transmittance aerosol carbon analyzer. Field measurements show that there was no significant difference between the elemental carbon concentrations determined by the FP and IOGAPS, indicating that particle loss during the transit through the denuder tube was negligible. Compared with the OC determined by FP (3.9-12.6 microg of C/m3), the lower OC observed on the quartz filter in the IOGAPS (2.2-6.0 microg of C/m3) was expected because of the removal of gas-phase organics by the denuder. Higher semivolatile organic carbon (SVOC) on the backup SIFs during the night (1.24-8.43 microg of C/m3) suggests that more SVOC, emitted from primary sources or formed as secondary organic compounds, partitions onto the particles during the night because of the decreased ambient temperature. These data illustrate the utility of an IOGAPS system to more accurately determine the particle-bound OC in comparison to FP-based systems.