Brett D. Grover

Measurement of Both Nonvolatile and Semi-Volatile Fractions of Fine Particulate Matter in Fresno, CA

An intensive sampling campaign was performed in Fresno, CA during December 2003 measuring fine particulate matter including both the semi-volatile and nonvolatile fractions of the aerosol. Both the newly developed R&P FDMS Monitor and a PC-BOSS have been shown to measure total PM 2.5 concentrations including semi-volatile nitrate and organic material. Good agreement was observed between the PC-BOSS and the R&P FDMS Monitor in this study with linear regression analysis resulting in a zero-intercept slope of 1.00 ± 0.02 and an R 2 = 0.93. Several real-time measuring systems including the R&P Differential TEOM, the Met One BAMS, and a GRIMM Monitor were also employed and comparisons of total PM 2.5 mass were made with the R&P FDMS Monitor. Agreement among these various monitors was generally good. However, differences were sometimes seen. Reasons for observed differences in the real-time mass measurement systems are explained by the composition and complexity of the measured aerosol, most importantly the composition of semi-volatile material. A newly automated ion chromatographic system developed by Dionex was also field tested and compared to both R&P 8400N Nitrate and integrated PC-BOSS inorganic species measurements. Sulfate and nitrate determined by the Dionex and PC-BOSS systems agreed. However, nitrate measured by the 8400N was low during fog events compared to the other two systems.

The measurement of fine particulate semivolatile material in urban aerosols.

Abstract 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.

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

Abstract 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%).

Modifications to the sunset laboratory carbon aerosol monitor for the simultaneous measurement of PM2.5 nonvolatile and semi-volatile carbonaceous material.

Abstract Semi-volatile organic carbonaceous material (SVOC) in fine particles is not reliably measured with conventional semicontinuous carbon monitors because semi-volatile carbonaceous material is lost from the collection media during sample collection. Two modifications of a Sunset Laboratory carbon aerosol monitor allowing for the determination of semi-volatile fine particulate organic material are described. Collocated conventional and modified instruments were operated simultaneously using a common inlet. Comparisons were made with integrated PC-BOSS data for quartz filter retained nonvolatile organic carbon (NVOC) and elemental carbon (EC), SVOC, and total carbon (TC = SVOC + NVOC + EC) and good agreement was observed between TC concentrations during studies conducted in Rubidoux, CA. Precision of the comparison was σ=±1.5 μg-C/m3 (±8%). On the basis of experiments performed with the modified Sunset monitor, a dual-oven Sunset monitor was developed and extensively tested in Lindon, UT; Riverside, CA; and in environmental exposure chambers. The precision for the measurement of TC with the dual-oven instrument was σ = ±1.4 μg-C/m3 (±13%).

Monitoring and Source Apportionment of Fine Particulate Matter at Lindon, Utah

Under the EPA Science to Achieve Results (STAR) and the Environmental Monitoring for Public Access and Community Tracking (EMPACT) programs an intensive sampling campaign was performed during the month of August 2002 at the state of Utah Air Quality monitoring site in Lindon, Utah. The concentrations and composition of PM2.5 were measured using a variety of continuous samplers including a TEOM monitor to measure non-volatile PM2.5, a RAMS monitor to measure total PM2.5 including semi-volatile species, an ion-chromatographic based instrument to measure sulfate and nitrate, and an Anderson Aethalometer to measure elemental carbon and UV adsorption. Integrated PM2.5 data were collected using a PC-BOSS sampler, for the determination of detailed particle composition. Continuous gas phase concentrations of NO, NO2, NOx, H2O2, and O3 were also monitored. One-hour average PM2.5 data have been combined with continuous gas phase data to perform source apportionment using the EPA UNMIX program. Sources of fine particulate matter were apportioned into primary emission sources and secondary formation processes. Identified were primary mobile sources, including diesel and gasoline combustion vehicles, and both a day-time and night-time secondary source.

Source Apportionment of One-Hour Semi-Continuous Data Using Positive Matrix Factorization with Total Mass (Nonvolatile plus Semi-Volatile) Measured by the R&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 factors from the data set and factors corresponding to both primary and secondary sources were identified. Factors were attributed to being primarily from automobile, diesel emissions, secondary nitrate formation, a secondary photochemical associated source, organic emissions and primary emissions. Good agreement was observed between the PMF predicted mass and the FDMS measured mass for both analyses.