Ambient Filter Samples Research Articles

A Quantitative Method to Measure and Speciate Amines in Ambient Aerosol Samples

Ambient reactive nitrogen is a mix of nitrogen-containing organic and inorganic compounds. These various compounds are found in both aerosol- and gas-phases with oxidized and reduced forms of nitrogen. Aerosol-phase reduced nitrogen is predominately thought to include ammonium and amines. In ambient samples, the ammonium concentration is routinely determined, but the contribution of amines is not. We developed a method to discretely measure amines from ambient aerosol samples. It employs ion chromatography using a Thermo Scientific IonPac Dionex CS-19 column with conductivity detection and a three-step separation using a methanesulfonic acid eluent. This method allows for the quantification of 18 different amines, including the series of methylamines and the different isomers of butylamine. Almost all amines quantifiable by this technique were measured regularly when applying this method to ambient filter samples collected in Rocky Mountain National Park (RMNP) and Greeley, CO. The sum of the amines was ~0.02 µg m−3 at both sites. This increased to 0.04 and 0.09 µg m−3 at RMNP and Greeley, respectively, at the same time they were impacted by smoke. Analysis of separate, fresh biomass burning source samples, however, suggests that smoke is likely a minor emission source of amines in most environments.

A 1-year characterization of organic aerosol composition and sources using an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF)

Abstract. The aerosol mass spectrometer (AMS), combined with statistical methods such as positive matrix factorization (PMF), has greatly advanced the quantification of primary organic aerosol (POA) sources and total secondary organic aerosol (SOA) mass. However, the use of thermal vaporization and electron ionization yields extensive thermal decomposition and ionization-induced fragmentation, which limit chemical information needed for SOA source apportionment. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) provides mass spectra of the organic aerosol fraction with a linear response to mass and no thermal decomposition or ionization-induced fragmentation. However, the costs and operational requirements of online instruments make their use impractical for long-term or spatially dense monitoring applications. This challenge was overcome for AMS measurements by measuring re-nebulized water extracts from ambient filter samples. Here, we apply the same strategy for EESI-TOF measurements of 1 year of 24 h filter samples collected approximately every fourth day throughout 2013 at an urban site. The nebulized water extracts were measured simultaneously with an AMS. The application of positive matrix factorization (PMF) to EESI-TOF spectra resolved seven factors, which describe water-soluble OA: less and more aged biomass burning aerosol (LABBEESI and MABBEESI, respectively), cigarette-smoke-related organic aerosol, primary biological organic aerosol, biogenic secondary organic aerosol, and a summer mixed oxygenated organic aerosol factor. Seasonal trends and relative contributions of the EESI-TOF OA sources were compared with AMS source apportionment factors, measured water-soluble ions, cellulose, and meteorological data. Cluster analysis was utilized to identify key factor-specific ions based on PMF. Both LABB and MABB contribute strongly during winter. LABB is distinguished by very high signals from C6H10O5 (levoglucosan and isomers) and C8H12O6, whereas MABB is characterized by a large number of CxHyOz and CxHyOzN species of two distinct populations: one with low H:C and high O:C and the other with high H:C and low O:C. Two oxygenated summertime SOA sources were attributed to terpene-derived biogenic SOA, a major summertime aerosol source in central Europe. Furthermore, a primary biological organic aerosol factor was identified, which was dominated by plant-derived fatty acids and correlated with free cellulose. The cigarette-smoke-related factor contained a high contribution of nicotine and high abundance of organic nitrate ions with low m∕z.

Formula omitted]C signatures of organic aerosols: Measurement method evaluation and application in a source study

Analysis of the stable carbon isotope 13C in organic carbon (OC) can give insight into sources and atmospheric processing of carbonaceous aerosols, provided the 13C source signatures are known. However, only few data on 13C signatures of OC emitted by common sources of carbonaceous aerosol are available in Europe. We present and evaluate an improved version of a measurement method to obtain δ13C signatures on organic aerosols desorbed from filter samples at three different desorption temperatures (200 °C, 350 °C and 650 °C) and apply it in a source study.With our calibration approach, the reproducibility of a L-Valine reference material desorbed at a single temperature step of 650 °C shows a standard deviation of 0.19‰ over a period of more than one year. The average δ13C value for this reference material over 248 measurements is −24.10‰, which shows only a slight bias to the nominal value of −24.03‰. Repeated analysis of ambient filter samples desorbed at three temperature steps show typical standard deviations of about 0.3‰ for all temperature steps (200 °C, 350 °C and 650 °C). Isotopic fractionation due to partial thermal desorption during the individual temperature steps was tested on single compound reference materials. It showed significant isotopic fractionation only at temperature steps, in which a very minor fraction of the compound was desorbed. Possible isotope effects caused by charring of organic material were investigated and found to be not significant.The thermal desorption method was applied to various source filter samples from the region of Naples, Italy. We analyzed two different biomass burning sources, exhaust from a city bus and traffic emissions collected in a tunnel and compared these to ambient filter samples from the same region. δ13C signatures of the total OC show values in a narrow range of about −28‰ to −26‰ for all sources, which does not allow a source apportionment only based on 13C. Nevertheless, the results add information to a source inventory of δ13C, where information of 13C in organic aerosol from specific emission sources are rare. City bus emissions show little variation of δ13C over the temperature steps, whereas biomass burning aerosol is enriched in 13C for OC desorbed at 650 °C. For PM10 samples in the urban tunnel an enrichment in δ13C at the 650 °C temperature steps was observed, which is likely caused by the contribution of carbonate carbon to the carbonaceous material desorbed at this temperature step.

A Continuous-Flow Gas Interface of a Thermal/Optical Analyzer With14C AMS for Source Apportionment of Atmospheric Aerosols

AbstractThis article reports on the performance of a continuous-flow interface for CO2gas feeding into the ion source of a 200-kV accelerator mass spectrometer (AMS) in splitless mode. Distinct CO2fractions and subfractions produced by a commercial Sunset OC/EC (organic carbon/elemental carbon) analyzer from ambient atmospheric aerosols filters are injected into the source and then analyzed by their14C/12C ratio in real time. New features are revealed from organic aerosol subfractions, which thermally desorb close to each other and are only visible by real-time analysis. An optimized setup for this purpose is presented for the measurement of CO2amounts from 3 to 45 μg C. Efficiencies of 4.5–8.0% for the formation of C-ions from CO2are obtained for sample masses of 5–10 μg C and carbon mass flow rates below 2 µg min–1. However, this ionization efficiency is substantially suppressed at high carbon mass flow rates. The potential of this method for a refined apportionment of aerosol sources is demonstrated with ambient filter samples.

Development of an analytical method for determining hindered phenolic antioxidants in exhaust emissions from light-duty vehicles

Six hindered phenolic antioxidants (HPAs) from emissions of light-duty diesel and gasoline vehicles were determined. Vehicles were tested on a dynamometer that conducted a typical city-driving protocol and their exhaust samples were collected on filters. A high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) method was developed for the determination of HPAs in the exhaust samples. Method detection limits reached low ng/m3 in exhaust after optimization of experimental conditions. Identification and quantification were proven to be reliable for these phenols in lightly-loaded and ambient filter samples. In heavily loaded samples, matrix interferences existed, which decreased recoveries of surrogate in both filter and disk. However, matrix spike samples showed good recoveries of target HPAs. In vehicle emission samples, the highest level of HPAs was 2,6-di-tert-butylphenol at 52.7 ng/m3 (28.9 pg/mm2 on filter) in emission of a 2009 Volkswagen Jetta with a diesel engine. Most HPAs were not detected or near detection limits. Therefore, the additives of phenol antioxidants in fuels were mostly oxidized during the combustion process. Further, the 2009 diesel Jetta produced about 7 times more of HPAs than the 2008 Pontiac G5 with a gasoline engine. In addition, it is discovered that engines operated at a colder ambient temperature (−7 °C) yielded more HPA emissions than at the warmer condition (25 °C), because the combustion efficiency of engines are normally reduced at a lower temperature.

A thermal desorption system for measuring δ13C ratios on organic aerosol

We developed a system that links a thermal desorption oven for aerosol filter samples to an isotope ratio mass spectrometer (IRMS) via a combustion interface. Organic compounds are desorbed from the filter sample in He at 7 temperature steps between 100 and 400°C and subsequently oxidized to CO2, which is analyzed for δ13C. We tested the system for isotopic fractionation, reproducibility and linearity using organic test compounds and aerosol filter samples. An oxalic acid standard with known δ13C value shows no isotopic fractionation when it is desorbed at temperatures well above its melting point. When organic acids are heated at a temperature close to their melting point only a fraction of the compound (10–80%) evaporates which shows depleted δ13C values at this temperature step. At the next higher temperature step, when the rest of the compound is desorbed, δ13C values are enriched. This effect is stronger for compounds with a lower molecular weight than for compounds with a higher molecular weight. In ambient samples this should only have a moderate effect on the overall δ13C value, since hundreds of different compounds are desorbed at each temperature step. Choosing different values for temperature steps does not strongly change the δ13C values for ambient aerosol filter samples. For typical ambient samples the reproducibility lies below ±0.3‰ for oven temperatures below 200°C and below ±0.5‰ for oven temperatures above 200°C. Tests with oxalic acid and ambient filter samples show that the IRMS is linear for peak areas in the operational range of 1–20Vs.

Organosulfate Formation in Biogenic Secondary Organic Aerosol

Organosulfates of isoprene, alpha-pinene, and beta-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (alpha-pinene, beta-pinene, d-limonene, l-limonene, alpha-terpinene, gamma-terpinene, terpinolene, Delta(3)-carene, and beta-phellandrene) and three monoterpenes (alpha-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, alpha-pinene, beta-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%.

Detection and quantification of 2-methyltetrols in ambient aerosol in the southeastern United States

Filters collected from the Southeastern Aerosol Research and Characterization (SEARCH) air monitoring network were analyzed for the presence of 2-methyltetrols, namely 2-methylthreitol and 2-methylerythritol, two compounds that are products of the photooxidation of isoprene and have been detected in aerosol at a variety of sites around the globe. The 2-methytetrols were detected in ambient filter samples collected at the four SEARCH sites, Birmingham, AL, Centreville, AL, Pensacola, FL, and at Jefferson Street in Atlanta, GA, in late June 2004. Average atmospheric concentrations of 11.9 and 4.8 ng m −3 were measured for 2-methylerythritol and 2-methylthreitol, respectively, at the inland sampling sites, whereas average concentrations of 4.9 and 1.6 ng m −3 were measured at the coastal sampling location (Pensacola). On average, the aerosol loading from these two compounds accounts for approximately 0.42% and 0.21% of the organic mass collected on a given sampling day at the inland and coastal sites, respectively. The present data on these compounds, which are particulate-phase fingerprints of isoprene photooxidation, add to the growing body of ambient data on secondary organic aerosol from isoprene.

Feasibility of Soil Dust Source Apportionment by the Pyrolysis-Gas Chromatography/Mass Spectrometry Method

This study tested the feasibility of using pyrolysis (Py)-gas chromatography (GC)/mass spectrometry (MS) to obtain organic chemical species data suitable for source apportionment modeling of soil-derived coarse particulate matter (PM10) dust on ambient filters. A laboratory resuspension apparatus was used with known soils to generate simulated receptor filter samples loaded with ∼0.4 mg of PM10 dust, which is within the range of mass loading on ambient filters. Py-GC/MS at 740 °C generated five times more resolvable compounds than were obtained with thermal desorption GC/MS at 315 °C. The identified compounds were consistent with literature from Py experiments using larger samples of bulk soils. A subset of 91 organic species out of the 178 identified Py products was used as input to CMB8 software in a demonstration of source apportionment using laboratory-generated mixtures simulating ambient filter samples. The 178 quantified organic species obtained by Py of soil samples is an improvement compared with the 38 organic species obtained by thermal desorption of soils and the four functionally defined organic fractions reported by thermal/optical reflectance. Significant differences in the concentration of specific species were seen between samples from different sites, both geographically distant and close, using analysis of variance and cluster analysis. This feasibility study showed that Py-GC/MS can generate useful source profile data for receptor modeling and justifies continued method development.

Deposition and Removal of Fugitive Dust in the Arid Southwestern United States: Measurements and Model Results

This work was motivated by the need to better reconcile emission factors for fugitive dust with the amount of geologic material found on ambient filter samples. The deposition of particulate matter with aerodynamic diameter less than or equal to 10 μm (PM10), generated by travel over an unpaved road, over the first 100 m of transport downwind of the road was examined at Ft. Bliss, near El Paso, TX. The field conditions, typical for warm days in the arid southwestern United States, represented sparsely vegetated terrain under neutral to unstable atmospheric conditions. Emission fluxes of PM10 dust were obtained from towers downwind of the unpaved road at 7, 50, and 100 m. The horizontal flux measurements at the 7 m and 100 m towers indicated that PM10 deposition to the vegetation and ground was too small to measure. The data indicated, with 95% confidence, that the loss of PM10 between the source of emission at the unpaved road, represented by the 7 m tower, and a point 100 m downwind was less than 9.5%. A Gaussian model was used to simulate the plume. Values of the vertical standard deviation σ z and the deposition velocity V d were similar to the U.S. Environmental Protection Agency (EPA) ISC3 model. For the field conditions, the model predicted that removal of PM10 unpaved road dust by deposition over the distance between the point of emission and 100 m downwind would be less than 5%. However, the model results also indicated that particles larger than 10 μm (aerodynamic diameter) would deposit more appreciably. The model was consistent with changes observed in size distributions between 7 m and 100 m downwind, which were measured with optical particle counters. The Gaussian model predictions were also compared with another study conducted over rough terrain and stable atmospheric conditions. Under such conditions, measured PM10 removal rates over 95 m of downwind transport were reported to be between 86% and 89%, whereas the Gaussian model predicted only a 30% removal. One explanation for the large discrepancy between measurements and model results was the possibility that under the conditions of the study, the dust plume was comparable in vertical extent to the roughness elements, thereby violating one of the model assumptions. Results of the field study reported here and the previous work over rough terrain bound the extent of particle deposition expected to occur under most unpaved road emission scenarios.

Modeling reflectance and transmittance of quartz-fiber filter samples containing elemental carbon particles: Implications for thermal/optical analysis

A radiative transfer scheme that considers absorption, scattering, and distribution of light-absorbing elemental carbon (EC) particles collected on a quartz-fiber filter was developed to explain simultaneous filter reflectance and transmittance observations prior to and during thermal/optical analysis for carbonaceous aerosol. The model is applied to study ambient filter samples from the United States and Hong Kong, China, and how they differ from each other and from reference carbon black samples. Most particles in ambient samples deposit into the top half of the filter, resuspended carbon black particles are only found close to the filter surface. Pyrolized/charred organic carbon (POC) generated during thermal analysis reduces filter reflectance and transmittance in a fashion that suggests a uniform distribution of POC throughout the filter. When heated in oxygen, most EC evolves earlier than the within-filter charring for certain ambient samples. This shows the different natures of EC, and also results in an inexact optical correction to separate organic and elemental carbon by thermal analysis, especially when the POC/EC ratio is large. Particle absorption in the filter is estimated for comparisons with the EC/POC measurements, suggesting a mass absorption efficiency of ∼2.7±0.2 m 2 ( gC) −1 for reference carbon black and >15 m 2 ( gC) −1 for ambient EC, similar to previous estimates in the literature.

Measurements of Particle Deposition Rates Inside Southern California Museums

Rates of deposition of submicrometer particles were measured inside five Southern California museums using an automated particle-counting technique on a scanning electron microscope equipped with an energy-dispersive X-ray detector combined with bulk chemical analysis. Deposition velocities to vertical and upward-facing horizontal surfaces were determined as a function of particle size for each site by analysis of indoor suspended particles sampled onto filters and particles deposited on vertically and horizontally oriented deposition plates. Measured deposition velocities to vertical indoor surfaces were in the range of 10^(−6) to 10^(−5) m/s at all sites but varied from site to site in terms of their dependence upon particle size. Deposition velocities to horizontal surfaces were in the range of 10^(−6) to 10^(−3) m/s and showed the expected increase with particle size due to gravitational settling. The deposition velocities measured by single-particle analysis are compared to deposition velocities determined by bulk chemical analysis of deposition plates and indoor ambient filter samples for several chemical species. Advantages and drawbacks of the automated particle counting technique are discussed.

Observation of Heavy Metal Compounds in Suspended Particulate Matter at East Helena, Montana

X-ray diffraction, x-ray transmission, and x-ray fluorescence procedures have been used to evaluate quantitatively the chemical species for 24 ambient filter samples taken from receptor sites at East Helena, Montana. Twenty-five distinct chemical compounds representing various smelting processes, atmospheric chemical reactions, local fugitive dust sources, and possible fitter artifacts have been observed. These compounds Include the common crustal silicates and carbonates, and Industrial sulf ides, sulf ates, and oxides. In addition, elemental cadmium and copper have been observed in a number of ambient samples. The soils and some accumulated residential dust of the East Helena area contain relatively high levels of lead and copper compounds.