Measurement of organic mass to organic carbon ratio in ambient aerosol samples using a gravimetric technique in combination with chemical analysis

Organic materials make up a significant fraction of ambient particulate mass. It is important to quantify their contributions to the total aerosol mass for the identification of aerosol sources and subsequently formulating effective control measures. The organic carbon (OC) mass can be determined by an aerosol carbon analyzer; however, there is no direct method for the determination of the mass of organic compounds, which also contain N, H, and O atoms in addition to C. The often-adopted approach is to estimate the organic mass (OM) from OC multiplying by a factor. However, this OC-to-OM multiplier was rarely measured for a lack of appropriate methods for OM. We report here a top-down approach to determine OM by coupling thermal gravimetric and chemical analyses. OM is taken to be the mass difference of a filter before and after heating at 550 °C in air for 4 h minus mass losses due to elemental carbon (EC), volatile inorganic compounds (e.g., NH₄NO₃), and loss of aerosol-associated water that arise from the heating treatment. The losses of EC and inorganic compounds are determined through chemical analysis of the filter before and after the heating treatment. We analyzed 37 ambient aerosol samples collected in Hong Kong during the winter of 2003, spring of 2004, and summer of 2005. A value of 2.1±0.3 was found to be the appropriate factor to convert OC to OM in these Hong Kong aerosol samples. If the dominant air mass is classified into two categories, then an OM-to-OC ratio of 2.2 was applicable to aerosols dominated by continent-originated air mass, and 1.9 was applicable to aerosols dominated by marine air mass.     

Determination of elemental carbon component of soot in ambient aerosol samples

A reflectance method for the determination of the elemental carbon component of soot in atmospheric fine particulate matter collected on a filter has been developed. Two instruments are described. One operates continuously as the aerosol sample is being collected, measuring the decrease in reflectance of light from the filter spot through which air is aspirated. The other instrument measures the reflectance of samples mounted after a collection on a filter. The instruments have been calibrated with soot standards of known total non-volatile carbon content determined by the GRALE technique after heating. Limited field data are presented on both the total carbon and soot carbon content of the St. Louis urban fine aerosol.     

Investigation of the ultraviolet photolysis method for the determination of organic nitrogen in aerosol samples

The research objective was to adapt the ultraviolet (UV)-photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2(2) factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 degrees C occurred at pH 2.0 with a 24-hr irradiance period at concentrations <33 microM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH4+), but urea released a near equimolar ratio of NH4+ and nitrate (NO3-). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM10 were 78.1 +/- 29.2 nmol-Nm(-3) and 8.3 +/- 4.9 nmol-Nm(-3), respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 +/- 5.7%, and the majority of the DON (79.1 +/- 18.2%) was found in the fine particulate matter (PM2.5) fraction. The average concentrations of DIN and DON in the PM2.5 fraction were 54.4 +/- 25.6 nmol-Nm(-3) and 6.5 +/- 4.4 nmol-Nm(-3), respectively.     

Separation of brown carbon from black carbon for IMPROVE and Chemical Speciation Network PM2.5 samples

The replacement of the Desert Research Institute (DRI) model 2001 with model 2015 thermal/optical analyzers (TOAs) results in continuity of the long-term organic carbon (OC) and elemental carbon (EC) database, and it adds optical information with no additional carbon analysis effort. The value of multiwavelength light attenuation is that light absorption due to black carbon (BC) can be separated from that of brown carbon (BrC), with subsequent attribution to known sources such as biomass burning and secondary organic aerosols. There is evidence of filter loading effects for the 25% of all samples with the highest EC concentrations based on the ratio of light attenuation to EC. Loading corrections similar to those used for the seven-wavelength aethalometer need to be investigated. On average, nonurban Interagency Monitoring of PROtected Visual Environments (IMPROVE) samples show higher BrC fractions of short-wavelength absorption than urban Chemical Speciation Network (CSN) samples, owing to greater influence from biomass burning and aged aerosols, as well as to higher primary BC contributions from engine exhaust at urban sites. Sequential samples taken during an Everglades National Park wildfire demonstrate the evolution from flaming to smoldering combustion, with the BrC fraction increasing as smoldering begins to dominate the fire event.

Implications: The inclusion of seven wavelengths in thermal/optical carbon analysis of speciated PM_2.5 (particulate matter with an aerodynamic diameter ≤2.5 μm) samples allows contributions from biomass burning and secondary organic aerosols to be estimated. This separation is useful for evaluating control strategy effectiveness, identifying exceptional events, and determining natural visibility conditions.     

The inportance of organic and elemental carbon in the fine atmospheric aerosol particles

During a field campaign the chemical character of fine (d<2.5 μm) aerosol particles was studied at K-puszta, Hungary within the framework of a project of the European Union. The organic and elemental carbon fraction, as well as the concentration of major inorganic constituents with respect to the total fine aerosol mass are presented in this paper. It was found that organic compounds constituted a significant fraction of the total fine aerosol mass, their contribution is comparable to or larger than that of the major water soluble ions. The diurnal variation of aerosol composition was also studied. It can be concluded that the relative abundance of the major constituents is practically the same during the day and at night. The samples were also classified and studied according to the air mass history. It is stated that the aerosol can be separated into two populations with different regression lines between organic and elemental carbon.     

Evaluation of the IMPROVE Equation for estimating aerosol light extinction

The [revised] IMPROVE Equation for estimating light extinction from aerosol chemical composition was evaluated considering new measurements at U.S. national parks. Compared with light scattering (Bsp) measured at seven IMPROVE sites with nephelometer data from 2003–2012, the [revised] IMPROVE Equation over- and underestimated Bsp in the lower and upper quintiles, respectively, of measured Bsp. Underestimation of the worst visibility cases (upper quintile) was reduced by assuming an organic mass (OM)/organic carbon (OC) ratio of 2.1 and hygroscopic growth of OM, based on results from previous field studies. This assumption, however, tended to overestimate low Bsp even more. Assuming that sulfate was present as ammonium bisulfate rather than as ammonium sulfate uniformly reduced estimated Bsp. The split-mode model of concentration- and size-dependent dry mass scattering efficiencies in the [revised] IMPROVE Equation does not eliminate systematic biases in estimated Bsp. While the new measurements of OM/OC and OM hygroscopicity should be incorporated into future iterations of the IMPROVE Equation, the problem is not well constrained due to a lack of routine measurements of sulfate neutralization and the water-soluble fraction of OM in the IMPROVE network.

Implications: Studies in U.S. national parks showed that aerosol organics contain more mass and absorb more water as a function of relative humidity than is currently assumed by the IMPROVE Equation for calculating chemical light extinction. Consideration of these results could significantly shift the apportionment of light extinction to water-soluble organic aerosols and therefore better inform pollution control strategies under the U.S. Environmental Protection Agency Regional Haze Rule.     

Variation of mass scattering efficiencies in IMPROVE

The Interagency Monitoring of Protected Visual Environments (IMPROVE) equation used to assess compliance under the U.S. Environmental Protection Agency (EPA) Haze Rule assumes that dry mass scattering efficiencies for aerosol chemical components are constant. However, examination of aerosol size distributions and chemical composition during the Big Bend Regional Aerosol and Visibility Observational Study and the Southeastern Aerosol and Visibility Study suggests that volume and mass scattering efficiencies vary directly with increasing particle light scattering and aerosol mass concentration. This is consistent with the observation that particle distributions were shifted to larger sizes under more polluted conditions and appears to be related to aging of the aerosol during transport to remote locations.     

Determination of total organic chlorine and bromine in water samples by adsorption onto activated carbon and neutron activation analysis

A method was developed for the analysis of total organic chlorine and bromine compounds (TOCl, TOBr) in water samples. The method is based on the adsorption of organic compounds on specially prepared activated carbon. Neutron activation analysis (neutron flux 4·10¹² n cm⁻² s⁻¹) was used for the quantitative determination of chlorine and bromine.The factors investigated were the adsorption of organic chlorine and bromine compounds on activated carbon, the effect of pH on the adsorption, the removal of chlorine ions from activated carbon by nitrate washing, the amount of activated carbon required, the adsorption time, the potential number of successive adsorptions and the preservation of samples.The detection limits for TOC1 and TOBr were 5 and 0.5 μg 1⁻¹, respectively, when the sample size was 100 ml.     

High-resolution mass spectrometry analysis of secondary organic aerosol generated by ozonolysis of isoprene

The chemical composition of secondary organic aerosol (SOA) generated from the ozonolysis of isoprene (C₅H₈) in the presence of an OH scavenger was examined using high-resolution electrospray ionization mass spectrometry (ESI-MS) in the mass range m/z = 50–1000. The chemical composition of SOA is complex, with more than 1000 assigned peaks observed in the positive and negative ion mode spectra. Only a small fraction of peaks correspond to known products of isoprene oxidation, such as pyruvic acid, glycolic acid, methylglyoxal, etc. The absolute majority of the detected peaks correspond to highly oxidized oligomeric constituents of SOA, with an average O:C molar ratio of 0.6. The corresponding organic mass (OM) to organic oxygen (OO) ratio is 2.4. Approximately 8% of oxygen atoms in SOA are in the form of peroxides, as quantified with an iodide test. Double bond equivalency (DBE) factors, representing the sum of all double bonds and rings, increase by 1 for every 1–2 additional carbon atoms in the molecule. The number of unoxidized CC double bonds is estimated to be less than 10%; the remaining DBE is due to CO carbonyl groups. Kendrick analysis suggests that the prevalent oligomer building blocks are small carbonyls with a C₁–C₂ skeleton. Formaldehyde (CH₂O) is identified as the most common repetitive building block in the observed oligomeric compounds.     

Determination of malic acid and other C4 dicarboxylic acids in atmospheric aerosol samples

An ion chromatographic method was developed which is able to separate five unsubstituted and hydroxy C4 dicarboxylic acids, succinic, malic, tartaric, maleic and fumaric acid, besides the other unsubstituted C2-C5 dicarboxylic acids, oxalic, malonic and glutaric acids, as well as inorganic ions in samples extracted from atmospheric particulate matter. By the application of this method it was found for both rural and urban sites and for various types of air masses that in the summer-time malic acid is the most prominent C4 diacid (64 ng m(-3) by average), exceeding succinic acid concentration (28 ng m(-3) by average) considerably. In winter-time considerably less, a factor of 4-15, C4 acids occurred and succinic acid was more concentrated than malic acid. Tartaric, fumaric and maleic acids were less concentrated (5.1, 5.0 and 4.5 ng m(-3) by average, respectively). Tartaric acid was observed for the first time in ambient air. The results indicate that in particular anthropogenic sources are important for the precursors of succinic, maleic and fumaric acids. Biogenic sources seem to influence the occurrence of malic acid significantly.     

Carbon content of common airborne fungal species and fungal contribution to aerosol organic carbon in a subtropical city

Interest in the role and contribution of fungi to atmospheric aerosols and processes grows in the past decade. Substantial data or information such as fungal mass or carbon loading to ambient aerosols is however still lacking. This study aimed to quantify the specific organic carbon content (OC per spore) of eleven fungal species commonly found airborne in the subtropics, and estimated their contribution to organic carbon in aerosols. The specific OC contents showed a size-dependent relationship (r = 0.64, p < 0.05) and ranged from 3.6 to 201.0 pg carbon per spore or yeast cell, giving an average of 6.0 pg carbon per spore (RSD 51%) for spore or cell size less than 10 μm. In accounting for natural variations in the composition and abundance of fungal population, weighted-average carbon content for field samples was adopted using the laboratory determined specific OC values. An average of 5.97 pg carbon per spore (RSD 3.8%) was enumerated from 28 field samples collected at the university campus. The mean fungal OC concentration was 3.7, 6.0 and 9.7 ng m^?3 in PM_2.5, PM_2.5–10 and PM₁₀, respectively. These corresponded to 0.1%, 1.2% and 0.2% of the total OC in PM_2.5, PM_2.5–10 and PM₁₀, respectively. In the study period, rain provided periods with low total OC but high fungal prevalence and fungi contributed 7–32% OC in PM_2.5–10 or 2.4–7.1% OC in PM₁₀. More extensive studies are deserved to better understand the spatial-, temporal- and episodic dependency on the fungal OC contribution to the atmospheric aerosols.     

Role of organic and black carbon in the chemical composition of atmospheric aerosol at European background sites

The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch, Switzerland (high-alpine, PM_2.5 aerosol); (ii) K-puszta, Hungary (rural, PM_1.0 aerosol); (iii) Mace Head, Ireland (marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about 60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass. These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical) might be significant.     

Cluster analysis applied to atmospheric aerosol samples from the Norwegian Arctic

Cluster analysis is shown to be a useful technique for the identification and characterization of atmospheric aerosol particles. A general procedure for combining the cluster analysis results from a large number of samples is described and shown to be successful for comparing such samples. Two similarity measures, one not previously described, are evaluated for use in cluster analysis.The new analysis procedure was applied to the examination of 11 coarse-fraction and 19 fine-fraction aerosol samples collected during September and October, 1984 at Ny Alesund, Spitzbergen, Norway, ~ 1400 km north of the Arctic Circle. The aerosol at this site consists primarily of Si-, Cl- and S-rich particles, the relative abundance of each varying from sample to sample. Considerable differences in composition were observed between simultaneously collected coarse- and fine-fractions.     

Carbonaceous aerosol in urban and rural European atmospheres: estimation of secondary organic carbon concentrations

Aerosol samples from urban, rural and coastal areas in Europe were analysed for carbonaceous content by a thermaloptical transmission method. The fraction of particulate organic carbon with a secondary origin in gas/particle conversion of volatile organic compounds was estimated from the minimum ratio between particulate organic and black carbon, which occurred during periods of reduced photochemical activity. Values calculated by this method ranged from a minimum of 17%, in Birmingham, UK, during winter, to a maximum of 78% at a rural coastal area, in Portugal, with air masses transported directly from the ocean. A clear seasonal dependence was observed at both rural and urban environments, with minimum secondary organic carbon production during winter.     

Source contributions to primary organic aerosol: Comparison of the results of a source-resolved model and the chemical mass balance approach

A source-resolved model has been developed to predict the contribution of different sources to primary organic aerosol concentrations. The model was applied to the eastern US during a 17 day pollution episode beginning on 12 July 2001. Primary organic matter (OM) and elemental carbon (EC) concentrations are tracked for eight different sources: gasoline vehicles, non-road diesel vehicles, on-road diesel vehicles, biomass burning, wood burning, natural gas combustion, road dust, and all other sources. Individual emission inventories are developed for each source and a three-dimensional chemical transport model (PMCAMx) is used to predict the primary OM and EC concentrations from each source. The source-resolved model is simple to implement and is faster than existing source-oriented models. The results of the source-resolved model are compared to the results of chemical mass balance models (CMB) for Pittsburgh and multiple urban/rural sites from the Southeastern Aerosol Research and Characterization (SEARCH) network. Significant discrepancies exist between the source-resolved model and the CMB model predictions for some of the sources. There is strong evidence that the organic PM emissions from natural gas combustion are overestimated. It also appears that the OM and EC emissions from wood burning and off-road diesel are too high in the Northeastern US. Other similarities and discrepancies between the source-resolved model and the CMB model for primary OM and EC are discussed along with problems in the current emission inventory for certain sources.     

Chemical characterization of emissions from vegetable oil processing and their contribution to aerosol mass using the organic molecular markers approach

The organic fraction of aerosol emitted from a vegetable oil processing plant was studied to investigate the contribution of emissions to ambient particles in the surrounding area. Solvent-soluble particulate organic compounds emitted from the plant accounted for 10% of total suspended particles. This percentage was lower in the receptor sites (less than 6% of total aerosol mass). Nonpolar, moderate polar, polar, and acidic compounds were detected in both emitted and ambient aerosol samples. The processing and combustion of olive pits yielded a source with strong biogenic characteristics, such as the high values of the carbon preference index (CPI) for all compound classes. Polycyclic aromatic hydrocarbons (PAHs) detected in emissions were associated with both olive pits and diesel combustion. The chromatographic profile of dimethylphenanthrenes (DMPs) was characteristic of olive pit combustion. Organic aerosols collected in two receptor sites provided a different pattern. The significant contribution of vehicular emissions was identified by CPI values (approximately 1) of n-alkanes and the presence of the unresolved complex mixture (UCM). In addition, PAH concentration diagnostic ratios indicated that emissions from catalyst and noncatalyst automobiles and heavy trucks were significant. The strong even-to-odd predominance of n-alkanols, n-alkanoic acids, and their salts indicated the contribution of a source with biogenic characteristics. However, the profile of DMPs at receptor sites was similar to that observed for diesel particulates. These differences indicated that the contribution of vegetable oil processing emissions to the atmosphere was negligible.     

Secondary organic aerosol importance in the future atmosphere

In order to investigate the secondary organic aerosol (SOA) response to changes in biogenic volatile organic compounds (VOC) emissions in the future atmosphere and how important will SOA be relative to the major anthropogenic aerosol component (sulfate), the global three-dimensional chemistry/transport model TM3 has been used. Emission estimates of biogenic VOC (BVOC) and anthropogenic gases and particles from the literature for the year 2100 have been adopted.According to our present-day model simulations, isoprene oxidation produces 4.6 Tg SOA yr⁻¹, that is less than half of the 12.2 Tg SOA yr⁻¹ formed by the oxidation of other BVOC. In the future, nitrate radicals and ozone become more important than nowadays, but remain minor oxidants for both isoprene and aromatics. SOA produced by isoprene is estimated to almost triple, whereas the production from other BVOC more than triples. The calculated future SOA burden change, from 0.8 Tg at present to 2.0 Tg in the future, is driven by changes in emissions, oxidant levels and pre-existing particles. The non-linearity in SOA formation and the involved chemical and physical feedbacks prohibit the quantitative attribution of the computed changes to the above-mentioned individual factors. In 2100, SOA burden is calculated to exceed that of sulfate, indicating that SOA might become more important than nowadays. These results critically depend on the biogenic emissions and thus are subject to the high uncertainty associated with these emissions estimated due to the insufficient knowledge on plant response to carbon dioxide changes. Nevertheless, they clearly indicate that the change in oxidants and primary aerosol caused by human activities can contribute as much as the change in BVOC emissions to the increase of the biogenic SOA production in the future atmosphere.