Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples

The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.     

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.     

Searching for evidence of acid-catalyzed enhancement of secondary organic aerosol formation using ambient aerosol data

Laboratory experiments suggest that strong acids promote formation of enhanced levels of secondary organic aerosol (SOA), and organic aerosols may contribute to the health impacts of fine PM. We report results from examining hourly speciated fine particle data for evidence of ambient aerosol acidity-catalyzed SOA formation, as indicated by larger increases in the concentrations of organic aerosol mass occurring on days and in locations where more acidic aerosol (lower NH₄⁺/SO₄⁼ molar ratios) exists. Data sets from the southeastern U.S. were examined for which hourly acidity of PM_2.5 aerosols could be estimated, and for which hourly organic carbon (OC) content had been measured simultaneously. Within-day organic aerosol changes during selected periods were statistically related to concurrent aerosol acidity levels estimated from nitrate-corrected ammonium-to-sulfate ratios. Data from the Look Rock, TN, TVA/IMPROVE site for mid-July to mid-August 2004 showed average compositions frequently as acidic as NH₄HSO₄, however, no apparent increases in OC levels with increasing aerosol acidity were observed, even when [OC] changes were compared with time-delayed aerosol acidity estimates. SEARCH network data (2003–2004) for rural Centreville, AL (CTR) and Yorkville, GA (YRK) sites were also examined. Warm-season acidity levels were higher at CTR than at YRK, and daytime levels exceeded those at night at both sites. At the YRK site no consistent positive correlations were found between changes in OC or TC levels and aerosol acidity, even with time lags up to 6 h. Aerosol acidity at this site, however, is relatively low due to nearby agricultural sources of NH₃. In contrast, during selected periods from April to October 2004, at CTR, 6-h lagged OC changes were weakly correlated with daytime, nitrate-corrected NH₄⁺/SO₄⁼ molar ratios, but distinguishing this apparent relationship from meteorological effects on measured OC levels is challenging.     

Apportioning black carbon to sources using highly time-resolved ambient measurements of organic molecular markers in Pittsburgh

We present highly time-resolved measurements of organic molecular markers in downtown Pittsburgh, which are used to investigate sources contributing to atmospheric aerosols in the area. Two-hour average concentrations of condensed-phase and semivolatile organic species were measured using a Thermal Desorption Aerosol GC/MS (TAG). Concentrations for mobile source markers like hopanes had regular diurnal and day-of-week patterns. Pairing high time-resolved measurements with meteorological data helped identify contributions from known point sources for markers correlated with wind direction. Black carbon (BC), volatile organic compounds (VOCs) and organic molecular markers were apportioned to sources using the Chemical Mass Balance (CMB) and Positive Matrix Factorization (PMF) receptor models. Diesel and gasoline mobile source factors were identified as the main sources of BC in the downtown Pittsburgh area, contributing 67% and 20% of the study-average BC. 13% of the BC was associated with a source factor tentatively identified as an industrial or regional source. The high time resolution of the TAG has the potential to provide important new insight into source apportionment efforts using organic molecular marker measurements.     

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.     

Correction in aerosol mass concentration measurements with humidity difference between ambient and instrumental conditions

The influence of humidity is considered on the concentration of the suspended particulate matter (SPM) measured with a β-ray counter. The humidity condition inside a small observatory where the counter is located is, in general, different from the ambient condition outside the observatory. From the measured values, the ambient SPM concentration is derived considering the hygroscopic effect of common aerosol species of sea salt (SS), (NH₄)₂SO₄, NH₄NO₃ and NaNO₃. In a case study conducted during September 2005, temperature and humidity were measured both inside and outside the observatory. The average value of the relative humidity is 48% for inside and 78% for outside, resulting in approximately 53% larger SPM mass concentration after the correction. Accordingly, the value of mass extinction efficiency, which is given by the ratio between the optically measured extinction coefficient and the mass concentration, becomes lower after the correction.     

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.     

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.     

Determination of sources of fine particles in different ambient atmospheres in South Korea using a chemical mass balance model

Abstract

To determine the sources of particulate matter less than 2.5?μm (PM_2.5 in different ambient atmospheres (urban, roadside, industrial, and rural sites), the chemical components of PM_2.5 such as ions (Cl^-, NO₃^-, SO₄^2-, NH₄⁺, Na⁺, K⁺, Ca²⁺, and Mg²⁺), carbonaceous species, and elements (Al, As, Ba, Cd, Cu, Fe, Mn, Ni, Pb, Se, V, and Zn) were measured. The average mass concentrations of PM_2.5 at the urban, roadside, industrial, and rural sites were 31.5?±?14.8, 31.6?±?22.3, 31.4?±?16.0, and 25.8?±?12.4?μg/m³, respectively. Except for secondary ammonium sulfate and ammonium nitrate, the model results showed that the traffic source (i.e., the sum of gasoline and diesel vehicle sources) was the most dominant source of PM_2.5 (17.1%) followed by biomass burning (13.8%) at the urban site. The major primary sources of PM_2.5 were consistent with the site characteristics (diesel vehicle source at the roadside site, coal-fired plants at the industrial site, and biomass burning at the rural site). Seasonal data from the urban site suggested that ammonium sulfate and ammonium nitrate were the most dominant sources of PM_2.5 during all seasons. Further, the contribution of road dust source to PM_2.5 increased during spring and fall seasons. We conclude that the determination of the major PM_2.5 sources is useful for establishing efficient control strategies for PM_2.5 in different regions and seasons.     

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.     

Uncertainty associated with the gravimetric measurement of particulate matter concentration in ambient air

This work applied a propagation of uncertainty method to typical total suspended particulate (TSP) sampling apparatus in order to estimate the overall measurement uncertainty. The objectives of this study were to estimate the uncertainty for three TSP samplers, develop an uncertainty budget, and determine the sensitivity of the total uncertainty to environmental parameters. The samplers evaluated were the TAMU High Volume TSP Sampler at a nominal volumetric flow rate of 1.42 m³ min^–1 (50 CFM), the TAMU Low Volume TSP Sampler at a nominal volumetric flow rate of 17 L min^–1 (0.6 CFM) and the EPA TSP Sampler at the nominal volumetric flow rates of 1.1 and 1.7 m³ min^–1 (39 and 60 CFM). Under nominal operating conditions the overall measurement uncertainty was found to vary from 6.1 x 10^–6 g m^–3 to 18.0 x 10^–6 g m^–3, which represented an uncertainty of 1.7% to 5.2% of the measurement. Analysis of the uncertainty budget determined that three of the instrument parameters contributed significantly to the overall uncertainty: the uncertainty in the pressure drop measurement across the orifice meter during both calibration and testing and the uncertainty of the airflow standard used during calibration of the orifice meter. Five environmental parameters occurring during field measurements were considered for their effect on overall uncertainty: ambient TSP concentration, volumetric airflow rate, ambient temperature, ambient pressure, and ambient relative humidity. Of these, only ambient TSP concentration and volumetric airflow rate were found to have a strong effect on the overall uncertainty. The technique described in this paper can be applied to other measurement systems and is especially useful where there are no methods available to generate these values empirically.

Implications:?This work addresses measurement uncertainty of TSP samplers used in ambient conditions. Estimation of uncertainty in gravimetric measurements is of particular interest, since as ambient particulate matter (PM) concentrations approach regulatory limits, the uncertainty of the measurement is essential in determining the sample size and the probability of type II errors in hypothesis testing. This is an important factor in determining if ambient PM concentrations exceed regulatory limits. The technique described in this paper can be applied to other measurement systems and is especially useful where there are no methods available to generate these values empirically.     

Measurement of fine particles in diesel emissions using a real-time aerosol monitor

A real-time monitoring methodology to determine diesel fine particles in diesel emissions has been evaluated. The range of particle size captured by the monitor was approximately 0.1 microm to 1 microm. DustTrak real-time monitors were connected to the dilution tunnel of the vehicle exhaust to measure the emissions during the vehicle tests under both dynamic and steady-state driving conditions, and concentration data were recorded every 5 sec. Test variation of the real-time monitoring among different test days was similar to that measured by traditional filter-based gravimetric method, whereas the repeatability of the monitor data within the same-day tests was better than that of gravimetric method. Correlations between the two methods were established for different fuels tested on a single light duty vehicle. When the emissions from the reference fuel was used to convert the monitor's response to diesel fuels, the levels determined by the real-time monitor were consistent with those measured by gravimetric method among different fuels tested. Use of the real-time monitor could provide information on the levels of fine particles that is more relevant to the public health than the total particles.     

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.     

Two-stage chemical fractionation method for the analysis of elements and non-volatile inorganic ions in PM10 samples: Application to ambient samples collected in Rome (Italy)

A two-stage micro-analytical scheme for the determination of metals and ions in atmospheric particulate matter collected on only one Teflon filter was developed. In the first stage the collected particles are chemically fractionated for their solubility in a pH-buffered extracting solution; in the second stage the residue is mineralised. The major non-volatile inorganic ions (Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, Ca²⁺, Mg²⁺) are determined in the first fraction by ion-chromatography (IC), while metals and metalloids (Al, As, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, S, Sb, Se, Si, Ti, V, Zn) are determined in both the acetate extractable and the mineralised residual fractions by inductively coupled plasma optical emission spectroscopy (ICP-OES).The procedure was applied to ambient 24-h PM₁₀ samples collected on Teflon filters during two field campaigns carried out at two sites in the area of Rome (Italy). The variations in the chemical composition of the collected particles during the two periods were interpreted in the light of the dilution properties of the lower atmosphere and of the back-trajectories of the air masses. The difference in the results between the two locations was interpreted in the light of their proximity to the emission sources. It was found that the acetate extractable and the mineralised residual fraction of some metals exhibit a different temporal pattern, suggesting the existence of different emission sources of the two fractions.     

Direct analysis of polycyclic aromatic hydrocarbons in cloud-water aerosol filtrates using laser desorption mass spectrometry

A novel technique for the rapid screening of polyaromatic hydrocarbons (PAHs) in atmospheric particulates is presented. Two-step laser desorption laser photoionisation time-of-flight mass spectrometry was used to assay for PAHs in cloud-water particulates collected near Peebles in southern Scotland. The particulates were examined in situ on their host filters removing the requirement for time-consuming sample extraction and separation. The mass spectra obtained from a single filter are shown. The principal components of these are assigned to PAH contaminants and phthalate contaminants. A distribution of PAHs was observed using 193 nm laser photoionisation. The mass spectrum obtained on using 248 nm laser photoionisation exhibits a different intensity distribution demonstrating an ionisation wavelength dependence. The utility of the technique for rapid screening of PAHs and other polyaromatic species is discussed.     

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.