Semi-volatile Material Research Articles

Volatility of secondary organic aerosol during OH radical induced ageing

Abstract. The aim of this study was to investigate oxidation of SOA formed from ozonolysis of α-pinene and limonene by hydroxyl radicals. This paper focuses on changes of particle volatility, using a Volatility Tandem DMA (VTDMA) set-up, in order to explain and elucidate the mechanism behind atmospheric ageing of the organic aerosol. The experiments were conducted at the AIDA chamber facility of Karlsruhe Institute of Technology (KIT) in Karlsruhe and at the SAPHIR chamber of Forchungzentrum Jülich (FZJ) in Jülich. A fresh SOA was produced from ozonolysis of α-pinene or limonene and then aged by enhanced OH exposure. As an OH radical source in the AIDA-chamber the ozonolysis of tetramethylethylene (TME) was used while in the SAPHIR-chamber the OH was produced by natural light photochemistry. A general feature is that SOA produced from ozonolysis of α-pinene and limonene initially was rather volatile and becomes less volatile with time in the ozonolysis part of the experiment. Inducing OH chemistry or adding a new portion of precursors made the SOA more volatile due to addition of new semi-volatile material to the aged aerosol. The effect of OH chemistry was less pronounced in high concentration and low temperature experiments when lower relative amounts of semi-volatile material were available in the gas phase. Conclusions drawn from the changes in volatility were confirmed by comparison with the measured and modelled chemical composition of the aerosol phase. Three quantified products from the α-pinene oxidation; pinonic acid, pinic acid and methylbutanetricarboxylic acid (MBTCA) were used to probe the processes influencing aerosol volatility. A major conclusion from the work is that the OH induced ageing can be attributed to gas phase oxidation of products produced in the primary SOA formation process and that there was no indication on significant bulk or surface reactions. The presented results, thus, strongly emphasise the importance of gas phase oxidation of semi- or intermediate-volatile organic compounds (SVOC and IVOC) for atmospheric aerosol ageing.

Investigation of solid particle number measurement: Existence and nature of sub-23 nm particles under PMP methodology

A Particle Measurement Program (PMP) compliant system, an AVL advanced particle counter (APC) and an alternative volatile particle removal system, a catalytic stripper (CS) were evaluated and compared for measuring solid particle number (PN) emissions. The evaluations and comparisons were conducted using sulfuric acid and hydrocarbon particles as model volatile particles in laboratory tests, and diluted exhaust from a diesel particle filter (DPF)-equipped heavy-duty diesel vehicle operated on a heavy-duty chassis dynamometer under steady speed conditions at two different engine loads. For the laboratory test, both the APC and CS removed more than 99% of the volatile particles in terms of PN when using aerosols composed of pure sulfuric acid or hydrocarbons. When using laboratory test aerosols consisting of mixtures of sulfuric acid and hydrocarbons more than 99% of the particles were removed by the APC but the surviving particles were no longer entirely volatile, 12–14% were solid. For the chassis dynamometer test, PN emissions between 3 and 10 nm downstream the APC were ∼2 and 7 times higher than the PN emissions of particles above 10 nm at the 74% and 26% engine load, respectively. At the 26% engine load, PN level of the 3–10 nm particles downstream the APC were significantly higher than that in the dilution tunnel, demonstrating that the APC was making 3–10 nm particles. The PN emission of 3–10 nm particles downstream the APC was related to the heating temperature of the APC evaporation tube, suggesting these particles are artifacts formed by renucleation of semivolatiles. Considerably fewer particles between 3 to 10 nm were seen downstream of the CS for both engine loads due mainly to removal of semivolatile material by the catalytic substrates, although some of this difference could be attributed to diffusion and thermophoretic losses. The findings of this study imply that improvement of the current PMP protocol would be necessary if the PMP were to be used in other applications where the PN emissions of particles below 23 nm are important.

Formation of Secondary Organic Aerosol from the Direct Photolytic Generation of Organic Radicals.

The immense complexity inherent in the formation of secondary organic aerosol (SOA)-due primarily to the large number of oxidation steps and reaction pathways involved-has limited the detailed understanding of its underlying chemistry. As a means of simplifying such complexity, here we demonstrate the formation of SOA through the photolysis of gas-phase alkyl iodides, which generates organic peroxy radicals of known structure. In contrast to standard OH-initiated oxidation experiments, photolytically initiated oxidation forms a limited number of products via a single reactive step. As is typical for SOA, the yields of aerosol generated from the photolysis of alkyl iodides depend on aerosol loading, indicating the semivolatile nature of the particulate species. However, the aerosol was observed to be higher in volatility and less oxidized than in previous multigenerational studies of alkane oxidation, suggesting that additional oxidative steps are necessary to produce oxidized semivolatile material in the atmosphere. Despite the relative simplicity of this chemical system, the SOA mass spectra are still quite complex, underscoring the wide range of products present in SOA.

Semicontinuous PM2.5 and PM10 Mass and Composition Measurements in Lindon, Utah, during Winter 2007

The U.S. Environmental Protection Agency is promoting the development and application of sampling methods for the semicontinuous determination of fine particulate matter (PM2.5, particles with an aerodynamic diameter <2.5 µm) mass and chemical composition. Data obtained with these methods will significantly improve the understanding of the primary sources, chemical conversion processes, and meteorological atmospheric processes that lead to observed PM2.5 concentrations and will aid in the understanding of the etiology of PM2.5-related health effects. During January and February 2007, several semicontinuous particulate matter (PM) monitoring systems were compared at the Utah State Lindon Air Quality Sampling site. Semicontinuous monitors included instruments to measure total PM2.5 mass (filter dynamic measurement system [FDMS] tapered element oscillating microbalance [TEOM], GRIMM), nonvolatile PM2.5 mass (TEOM), sulfate and nitrate (two PM2.5 and one PM10 [PM with an aerodynamic diameter <10 µm] ionchromatographic-based samplers), and black carbon (aethalometer). PM10 semicontinuous mass measurements were made with GRIMM and TEOM instruments. These measurements were all made on a 1-hr average basis. Source apportionment analysis indicated that sources impacting the site were mainly urban sources and included mobile sources (gasoline and diesel) and residential burning of wood, with some elevated concentrations because of the effect of winter inversions. The FDMS TEOM and GRIMM instruments were in good agreement, but TEOM monitor measurements were low because of the presence of significant semi-volatile material. Semi-volatile mass was present dominantly in the PM2.5 mass.

Relating CCN activity, volatility, and droplet growth kinetics of β-caryophyllene secondary organic aerosol

Abstract. This study investigates the droplet formation characteristics of secondary organic aerosol (SOA) formed during the ozonolysis of sesquiterpene β-caryophyllene (with and without hydroxyl radicals present). Emphasis is placed on understanding the role of semi-volatile material on Cloud Condensation Nucleus (CCN) activity and droplet growth kinetics. Aging of β-caryophyllene SOA significantly affects all CCN-relevant properties measured throughout the experiments. Using a thermodenuder and two CCN instruments, we find that CCN activity is a strong function of temperature (activation diameter at ~0.6% supersaturation: 100±10 nm at 20°C and 130±10 nm at 35°C), suggesting that the hygroscopic fraction of the SOA is volatile. The water-soluble organic carbon (WSOC) is extracted from the SOA and characterized with Köhler Theory Analysis (KTA); the results suggest that the WSOC is composed of low molecular weight (&lt;200 g mol−1) slightly surface-active material that constitute 5–15% of the SOA mass. These properties are similar to the water-soluble fraction of monoterpene SOA, suggesting that predictive understanding of SOA CCN activity requires knowledge of the WSOC fraction but not its exact speciation. Droplet growth kinetics of the CCN are found to be strongly anticorrelated with WSOC fraction, suggesting that the insoluble material in the SOA forms a kinetic barrier that delays droplet growth. Overall, volatilization effects can increase activation diameters by 30%, and depress droplet growth rate by a factor of two; these results may have important implications for the droplet formation characteristics of SOA, and the atmospheric relevance of CCN measurements carried out at temperatures different from ambient.

Source Apportionment of One-Hour Semi-Continuous Data Using Positive Matrix Factorization with Total Mass (Nonvolatile plus Semi-Volatile) Measured by the R&amp;P FDMS Monitor

Positive matrix factorization (PMF) was used to elucidate sources of fine particulate material (PM 2.5 ) for a study conducted during July 2003 in Rubidoux, CA. One-h averaged semi-continuous measurements were made with a suite of instruments to provide PM 2.5 mass and chemical composition data. Total PM 2.5 mass concentrations (nonvolatile plus semi-volatile) were measured with a R&P filter dynamic measurement system (FDMS) and a conventional TEOM monitor was used to measure nonvolatile mass concentrations. Semi-volatile material (SVM) was calculated as the FDMS minus the TEOM determined PM 2.5 mass. PM 2.5 chemical species monitors included a R&P 5400 carbon monitor, an Anderson Aethalometer and a R&P 8400N nitrate monitor. Gas phase data including CO, NO 2 , NO x , and O 3 were also collected during the sampling period. Two distinct PMF analysis were performed. In analysis 1, the TEOM was excluded from the analysis and in analysis 2, the SVM was excluded from the analysis. PMF2 was able to identify six...

Comparison of Speciation Sampler and PC-BOSS Fine Particulate Matter Organic Material Results Obtained in Lindon, Utah, during Winter 2001–2002

The Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS) has been previously verified as being capable of measuring total fine particulate matter (PM2.5), including semi-volatile species. The present study was conducted to determine if the simple modification of a commercial speciation sampler with a charcoal denuder followed by a filter pack containing a quartz filter and a charcoal-impregnated glass (CIG) fiber filter would allow for the measurement of total PM2.5, including semi-volatile organic material. Data were collected using an R&P (Rupprecht and Pastasnik Co., Inc.) Partisol Model 2300 speciation sampler; an R&P Partisol speciation sampler modified with a BOSS denuder, followed by a filter pack with a quartz and a CIG filter; a Met One spiral aerosol speciation sampler (SASS); and the PC-BOSS from November 2001 to March 2002 at a U.S. Environmental Protection Agency (EPA) Science to Achieve Results (STAR) sampling site in Lindon, UT. Total PM2.5 mass, ammonium nitrate (both nonvolatile and semi-volatile), ammonium sulfate, organic carbon (both non-volatile and semi-volatile), and elemental carbon were determined on a 24-hr basis. Results obtained with the individual samplers were compared to determine the capability of the modified R&P speciation sampler for measuring total PM2.5, including semi-volatile components. Data obtained with the modified speciation sampler agreed with the PC-BOSS results. Data obtained with the two unmodified speciation samplers were low by an average of 26% because of the loss of semi-volatile organic material from the quartz filter during sample collection.

Measurement of Fine Particulate Matter Nonvolatile and Semi-Volatile Organic Material with the Sunset Laboratory Carbon Aerosol Monitor

Semi-volatile organic material (SVOM) in fine particles is not reliably measured with conventional semicontinuous carbon monitors because SVOM is lost from the collection media during sample collection. We have modified a Sunset Laboratory Carbon Aerosol Monitor to allow for the determination of SVOM. In a conventional Sunset monitor, gas-phase organic compounds are removed in the sampled airstream by a diffusion denuder employing charcoal-impregnated cellulose filter (CIF) surfaces. Subsequently, particles are collected on a quartz filter and the instrument then determines both the organic carbon and elemental carbon fractions of the aerosol using a thermal/optical method. However, some of the SVOM is lost from the filter during collection, and therefore is not determined. Because the interfering gas-phase organic compounds are removed before aerosol collection, the SVOM can be determined by filtering the particles at the instrument inlet and then replacing the quartz filter in the monitor with a charcoal-impregnated glass fiber filter (CIG), which retains the SVOM lost from particles collected on the inlet filter. The resulting collected SVOM is then determined in the analysis step by measurement of the carbonaceous material thermally evolved from the CIG filter. This concept was tested during field studies in February 2003 in Lindon, UT, and in July 2003 in Rubidoux, CA. The results obtained were validated by comparison with Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS) results. The sum of nonvolatile organic material determined with a conventional Sunset monitor and SVOM determined with the modified Sunset monitor agree with the PC-BOSS results. Linear regression analysis of total carbon concentrations determined by the PC-BOSS and the Sunset resulted in a zero-intercept slope of 0.99 ± 0.02 (R2 = 0.92) and a precision of σ = ± 1.5 µg C/m3 (8%).

Evaluation and Comparison of Continuous Fine Particulate Matter Monitors for Measurement of Ambient Aerosols

To provide a scientific basis for the selection and use of continuous monitors for exposure and/or health effects studies, and for compliance and episode measurements at strategic locations in the State of New Jersey, we evaluated the performance of seven continuous fine particulate matter (PM2.5) monitors in the present study. Gravimetric samplers, as reference methods, were collocated with real-time instruments in both laboratory and field tests. The results of intercomparison of real-time monitors showed that the two nephelometers used in this study correlated extremely well (r2 ∼0.97), and two tapered element oscillating monitors (TEOM 1400 and TEOM filter dynamics measurement system [FDMS]) correlated well (r2> 0.85), whereas two beta gauges displayed a weaker correlation (r2 < 0.6). During a summertime controlled (laboratory) evaluation, the measurements made with the gravimetric method correlated well with the 24-hr integrated measurements made with the real-time monitors. The SidePak nephelometer overestimated the particle concentration by a factor of approximately 3.4 compared with the gravi-metric method. During a summertime field evaluation, the TEOM FDMS monitor reported approximately 30% higher mass concentration than the Federal Reference Method (FRM); and the difference could be explained by the loss of semi-volatile materials from the FRM sampler. Results also demonstrated that 24-hr average PM2.5 mass concentrations measured by beta gauges and TEOM (50 °C) in winter correlated well with the integrated gravi-metric method. Seasonal differences were observed in the performance of the TEOM (50 °C) monitor in measuring the particle mass attributed to the higher semi-volatile material loss in the winter weather. In applying the real-time particulate matter monitoring data into Air Quality Index (AQI) reporting, the Conroy method and the 8-hr end-hour average method were both found to be suitable.

Characterization and contribution to PM 2.5 of semi-volatile aerosols in Paris (France)

Collocated PM 2.5 measurements using a conventional R&P TEOM (model 1400a) and a TEOM-FDMS were performed at a Paris urban background site during winter/summer field experiments. Results showed that conventional TEOM underestimates PM 2.5 mass concentrations by about 50% in winter and 35% in summer. They also confirmed that this negative sampling artifact, due to the volatilization of semi-volatile material (SVM) inside the instrument, cannot be accurately accommodated by a single correction factor because of SVM routine fluctuations. A basic filter-based investigation of the SVM chemical composition also indicated that SVM, measured by the TEOM–FDMS, is mainly formed by ammonium nitrate in winter while significant contributions of semi-volatile organic matter were observed in summer. The latter species was found to possibly account for more than 50% of secondary organic aerosol formed during summer afternoons. These findings call for more investigation of the SVM chemical composition, particularly during the summer season, in Paris and in Europe.

Semi‐volatile aerosols in Beijing (R.P. China): Characterization and influence on various PM2.5 measurements

During summer, the Beijing urban area meets contrasting meteorological conditions including warm and humid monsoon winds from the southeast bringing high levels of pollution, with PM2.5 mass concentrations often exceeding 100 μg/m3. The specific weather conditions and aerosol chemical composition observed at that time offer a unique opportunity to address the question of the contribution of semi‐volatile material (SVM) in the continuous PM records available for the south East Asian urban regions. Different PM2.5 measurements were evaluated during a 3‐week field campaign performed in Beijing downtown during the summer 2004, and consisting of a Rupprecht &amp; Patashnik (R&amp;P TEOM) (heating air sample at 50°C), R&amp;P TEOM‐FDMS (enabling SVM measurement), optical GRIMM counter, and filter weighing. A good agreement was found between the different TEOM measurements during the campaign with the exception of the periods of high Relative Humidity (RH), which exhibited SVM levels (derived from PM2.5 loss in the TEOM heated at 50°C) as high as 140 μg/m3. Continuous artefact‐free PM2.5 nitrate measurements were performed simultaneously and showed a close relationship with the TEOM‐derived SVM, accounting for half of this SVM. To better document the role of RH on SVM, estimates of liquid water content (LWC) in aerosols were derived from light scattering coefficient and integrated aerosol volume measurements performed in the field at different RH. LWC is shown to be related in a quantitative way to the levels of SVM and nitrate in aerosols, and thus is believed to play a major role in the gas‐particle partitioning of semi‐volatile species in Beijing aerosols.

Nucleation Mode Particles with a Nonvolatile Core in the Exhaust of a Heavy Duty Diesel Vehicle

The characteristics of the nucleation mode particles of a Euro IV heavy-duty diesel vehicle exhaust were studied. The NOx and PM emissions of the vehicle were controlled through the use of cooled EGR and high-pressure fuel injection techniques; no exhaust gas after-treatment was used. Particle measurements were performed in vehicle laboratory and on road. Nucleation mode dominated the particle number size distribution in all the tested driving conditions. According to the on-road measurements, the nucleation mode was already formed after 0.7 s residence time in the atmosphere and no significant changes were observed for longer residence times. The nucleation mode was insensitive to the fuel sulfur content, dilution air temperature, and relative humidity. An increase in the dilution ratio decreased the size of the nucleation mode particles. This behavior was observed to be linked to the total hydrocarbon concentration in the diluted sample. In volatility measurements, the nucleation mode particles were observed to have a nonvolatile core with volatile species condensed on it. The results indicate that the nucleation mode particles have a nonvolatile core formed before the dilution process. The core particles have grown because of the condensation of semivolatile material, mainly hydrocarbons, during the dilution.

Dilution-Based Emissions Sampling from Stationary Sources: Part 2—Gas-Fired Combustors Compared with Other Fuel-Fired Systems

This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.

Apportionment of Ambient Primary and Secondary Pollutants during a 2001 Summer Study in Pittsburgh Using U.S. Environmental Protection Agency UNMIX

Apportionment of primary and secondary pollutants during the summer 2001 Pittsburgh Air Quality Study (PAQS) is reported. Several sites were included in PAQS, with the main site (the supersite) adjacent to the Carnegie Mellon University campus in Schenley Park. One of the additional sampling sites was located at the National Energy Technology Laboratory, located ∼18 km southeast of downtown Pittsburgh. Fine particulate matter (PM2.5) mass, gas-phase volatile organic material (VOM), particulate semivolatile and nonvolatile organic material (NVOM), and ammonium sulfate were apportioned at the two sites into their primary and secondary contributions using the U.S. Environmental Protection Agency UNMIX 2.3 multivariate receptor modeling and analysis software. A portion of each of these species was identified as originating from gasoline and diesel primary mobile sources. Some of the organic material was formed from local secondary transformation processes, whereas the great majority of the secondary sulfate was associated with regional transformation contributions. The results indicated that the diurnal patterns of secondary gas-phase VOM and particulate semivolatile and NVOM were not correlated with secondary ammonium sulfate contributions but were associated with separate formation pathways. These findings are consistent with the bulk of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport and, thus, decoupled from local activity involving organic pollutants in the metropolitan area.

The Measurement of Fine Particulate Semivolatile Material in

Ammonium nitrate and semivolatile organic material (SVOM) are significant components of fine particles in urban atmospheres. These components, however, are not properly determined with methods such as the fine particulate matter (PM2.5) Federal Reference Method (FRM) or other single filter samplers because of significant losses of semivolatile material (SVM) from particles collected on the filter during sampling. The R&P tapered element oscillating microbalance (TEOM) monitor also does not measure SVM, because this method heats the sample to remove particle bound water, which also results in evaporation of SVM. Recent advances in monitoring techniques have resulted in samplers for both integrated and continuous measurement of total PM2.5, including the particle concentrator Brigham Young University organic sampling system (PC-BOSS), the real time total ambient mass sampler (RAMS), and the R&P filter dynamics measurement system (FDMS) TEOM monitor. Results obtained using these samplers have been compared with those obtained with either a PM2.5 FRM sampler or a TEOM monitor in studies conducted during the past five years. These studies have shown the following: (1) the PC-BOSS, RAMS, and FDMS TEOM are all comparable. Each instrument measures both the nonvolatile material and the SVM. (2) The SVM is not retained on the heated filter of a regular TEOM monitor and is not measured by this sampling technique. (3) Much of the SVM is also lost during sampling from single filter samplers such as the PM2.5 FRM sampler. (4) The amount of SVM lost from single filter samplers can vary from less than one-third of that lost from heated TEOM filters during cold winter conditions to essentially all during warm summer conditions. (5) SVOM can only be reliably collected using an appropriate denuder sampler. (6) A PM2.5 speciation sampler can be easily modified to a denuder sampler with filters that can be analyzed for semivolatile organic carbon (OC), nonvolatile OC, and elemental carbon using existing OC/elemental carbon analytical techniques. The research upon which these statements are based for various urban studies are summarized in this paper.

Coupled Partitioning, Dilution, and Chemical Aging of Semivolatile Organics

A unified framework of semi-volatile partitioning permits models to efficiently treat both semi-volatile primary emissions and secondary organic aerosol production (SOA), and then to treat the chemical evolution (aging) of the aggregate distribution of semi-volatile material. This framework also reveals critical deficiencies in current emissions and SOA formation measurements. The key feature of this treatment is a uniform basis set of saturation vapor pressures spanning the range of ambient organic saturation concentrations, from effectively nonvolatile material at 0.01 microg m(-3) to vapor-phase effluents at 100 mg m(-3). Chemical evolution can be treated by a transformation matrix coupling the various basis vectors. Using this framework, we show that semi-volatile partitioning can be described in a self-consistent way, with realistic behavior with respect to temperature and varying organic aerosol loading. The time evolution strongly suggests that neglected oxidation of numerous "intermediate volatility" vapors (IVOCs, with saturation concentrations above approximately 1 mg m(-3)) may contribute significantly to ambient SOA formation.

Continuous Determination of Fine Particulate Matter Mass in the Salt Lake City Environmental Monitoring Project: A Comparison of Real-Time and Conventional TEOM Monitor Results

Fine particulate matter (PM2.5) mass was determined on a continuous basis at the Salt Lake City Environmental Protection Agency Environmental Monitoring for Public Awareness and Community Tracking monitoring site in Salt Lake City, UT, using three different monitoring techniques. Hourly averaged PM2.5 mass data were collected during two sampling periods (summer 2000 and winter 2002) using a real-time total ambient mass sampler (RAMS), sample equilibration system (SES)-tapered element oscillating microbalance (TEOM), and conventional TEOM monitor. This paper compares the results obtained from the various monitoring systems, which differ in their treatment of semivolatile material (SVM; particle-bound water, semivolatile ammonium nitrate, and semivolatile organic compounds). PM2.5 mass results obtained by the RAMS were consistently higher than those obtained by the SES-TEOM and conventional TEOM monitors because of the RAMS ability to measure semivolatile ammonium nitrate and semivolatile organic material but not particle-bound water. The SESTEOM monitoring system was able to account for an average of 28% of the SVM, whereas the conventional TEOM monitor loses essentially all of the SVM from the single filter during sampling. Occasional mass readings by the various TEOM monitors that are higher than RAMS results may reflect particle-bound water, which, under some conditions, is measured by the TEOM but not the RAMS.

Effects of Dilution on Fine Particle Mass and Partitioning of Semivolatile Organics in Diesel Exhaust and Wood Smoke

Experiments were conducted to examine the effects of dilution on fine particle mass emissions from a diesel engine and wood stove. Filter measurements were made simultaneously using three dilution sampling systems operating at dilution ratios ranging from 20:1 to 510:1. Denuders and backup filters were used to quantify organic sampling artifacts. For the diesel engine operating at low load and wood combustion, large decreases in fine particle mass emissions were observed with increases in dilution. For example, the PM2.5 mass emission rate from a diesel engine operating at low load decreased by 50% when the dilution ratio was increased from 20:1 to 350:1. Measurements of organic and elemental carbon indicate that the changes in fine particle mass with dilution are caused by changes in partitioning of semivolatile organic compounds. At low levels of dilution semivolatile species largely occur in the particle phase, but increasing dilution reduces the concentration of semivolatile species, shifting this material to the gas phase in order to maintain phase equilibrium. Emissions of elemental carbon do not vary with dilution. Organic sampling artifacts are shown to vary with dilution because of the combination of changes in partitioning coupled with adsorption of gas-phase organics by quartz filters. The fine particle mass emissions from the diesel engine operating at medium load did not vary with dilution because of the lower emissions of semivolatile material and higher emissions of elemental carbon. To measure partitioning of semivolatile materials under atmospheric conditions, partitioning theory indicates that dilution samplers need to be operated such that the diluted exhaust achieves atmospheric levels of dilution. Too little dilution can potentially overestimate the fine particle mass emissions, and too much dilution (with clean air) can underestimate them.

Measurement of total PM2.5mass (nonvolatile plus semivolatile) with the Filter Dynamic Measurement System tapered element oscillating microbalance monitor

Field studies have been performed in Lindon, Utah (February 2003) and Rubidoux, California (July 2003) to determine if the Rupprecht and Patashnick (R&amp;P) Filter Dynamic Measurement System (FDMS) determines total fine particulate mass, including the semivolatile ammonium nitrate and organic material. Collocated measurements were made with the FDMS, a conventional tapered element oscillating microbalance (TEOM) monitor with a heated filter, an R&amp;P differential TEOM monitor, the Brigham Young University (BYU) Real‐Time Total Ambient Mass Sampler (RAMS), the BYU particle concentrator‐organic sampling system (PC‐BOSS), a PM2.5Federal Reference Method (FRM), a PM2.5speciation sampler, an R&amp;P continuous nitrate monitor, and two Sunset continuous carbon monitors (one to measure quartz filter‐retained particulate carbon and one to measure particulate semivolatile carbonaceous material lost from the particles on a filter during sampling). The RAMS and PC‐BOSS samplers have been shown to determine fine particulate material, including both the semivolatile and the nonvolatile components. Linear regression analysis at the Lindon site between the FDMS (X) and the PC‐BOSS (Y), and the FDMS (X) and the RAMS (Y), resulted in zero‐intercept slopes of 1.01 ± 0.06 (r2= 0.63) and 1.00 ± 0.01 (r2= 0.69), respectively. At the Rubidoux sampling site, linear regression analysis between the PC‐BOSS (X) and the FDMS (Y) gave a zero‐intercept slope of 0.96 ± 0.02 (r2= 0.90). Linear regression analysis between the FDMS (X) and the RAMS (Y) resulted in a zero‐intercept slope of 0.99 ± 0.01 (r2= 0.80). Measurements made at the two sites indicate that the FDMS and the R&amp;P differential TEOM monitors do measure total fine particulate mass, including the semivolatile ammonium nitrate and organic material. Both the heated TEOM monitor and PM2.5FRM did not measure the semivolatile material. The difference between the FDMS and a heated TEOM monitor was explained by the semivolatile ammonium nitrate and organic material measured by the various chemical composition monitors.

One– and Three–Hour PM2.5Characterization, Speciation, and Source Apportionment Using Continuous and Integrated Samplers

Ammonium nitrate and semivolatile organic compounds (SVOC) are significant components of fine particles in many urban atmospheres. These components, however, are not properly measured by current EPA accepted methods, such as the R&P TEOM monitor, due to loss of semivolatile material (SVM) from particles in the heated environment of the filter during sampling. The accurate determination of semivolatile material is important due to the possible effects of these species on human health, visibility, and global climate change. The concentration and composition of fine particulate material were determined using a combination of continuous and integrated samplers at the Brigham Young University–EPA Environmental Monitoring for Public Access and Community Tracking (BYU–EPA EMPACT) monitoring site in Salt Lake City, Utah over a six–day sampling period (30 January to 4 February) during the winter of 2001. Continuous samples were collected using a RAMS (total PM2.5 mass), a TEOM monitor (nonvolatile PM2.5 mass), an ...