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; ~ PHILIP MORRIS U1 S. A. INTER-OFFICE CORRESPONDENCE Richmond; Virginia C90-03y00 To: R. Ferguson Date: May 29, 1990 From: F. Hsu Subject: EPA/A1'~l'vlA International Symposium, 1990 During May 1- 4, I attended the International Symposium on Measurement of Toxic and Related Air Pollutants sponsored by Environmental Protetition Agency (EPA) and Air & Waste Management Association (AWMA) at Raleigh, North Carolina. The presentations were divided into 20 sessions and~ each devoted to a specific topic. There were either three or four concurrent sessions held in the morning and afternoon. An instrument exhibit was also held involving about 65 vendors ranging from contract services, environmental sampling equipments to analytical instrumentation. As in any multi-session meeting, time overlap prevented the complete coverage all the presentations of interest. The foll'owing is a summary of presentations grouped by specific subjects. SUPERCRITICAL FLUID EXTRACTIONS (SFE) As in other branches of science, the application of SFE in environmental sample preparation has become increasingly popular in replacing or complimenting the classical techniques such as Soxhlet extraction and thermal desorption. Most of the experiments used supercritical carbon dioxide. The advantages in using SFE, as pointed out by J. Levy (Suprex Corp.), were increased extraction efficiency, selectivity, shorter extraction time, ease of solvent removal and' the mild extraction conditions. The increased efficiency and reduced extraction time resulted from the unique physical property of the supercritical fluids. The selectivity of SFE can be controlled' by varying the density/temperature of the liquids, adding polar organic modifiers, selecting different SFE liquids and derivatization; Extraction of pollutants from different matrices were shown to exemplify the versatility of the technique and the effect of matrix on the extraction efficiency. SFE also offers the options for on-line (SFE-GC) and off- line operating modes: However, for extraction of more polar solutes, the addition of polar modifiers in the fluids imposes some limits for the on-line operation. One SFE application particularly interesting to myself is the capability of class (functional group) fractionation. A threshold density at which the solubility of a class of compounds maximizes needs to be defined experimentally. With pressure programming and SFE-GC, an automated smoke analysis system is potentially possible. Some sorbent media were tested for SFE of air toxics by several authors. J. Raymer (Research Triangle Institute, NC) extracted Tenax and Polyimides loaded with semi-volatiles, pesticides and PAH's with supercrit2cal CO2 . He concluded~ that supercritical CO,, was very effective in recovering the target compounds from Tenax. Higher volume of fluids or fluids

with modifier was necessary for the polyimide sorbents due to the stronger intermolecular forces. M. Krieger (Indiana University) and~ S. Hawthorne (University of N. Dakota) experimented with polyurethane foam (PUF) with SFE in quantitatively recovering wide varieties of organic compounds. These included semi-volatiles, phenols, aromatics, and PAH's. A PUF sampling of air in a smoker's office and followed by SFE-GC (S. Hawthorne) showed the presence of phenols, nicotine and fatty acids. PUF and SFE-GC were also demonstrated in quantitative measurements of phenolics in woodsmoke analysis. W. T. Foreman (U.S. Geological Survey, CO) extracted~ the C, , cartridge with SFE to recover pesticides in high yield. V The polar compounds are those containing hetero-atoms such as nitrogen, sulfur and oxygen. The single most difficult problem in developing protocols for analyzing polar compounds at trace level in air is probably moisture. Sampling of sidestream smoke components shared similar difficulty. The moisture in the ambient air clogged up the cryogenic trap and prevented sample enrichment. The evaporation of water vapor in the source of the mass spectrometer interfered~ with the high vacuum and the detection of co-eluting compounds. The present' EPA TO-14 method requires the use of Naphion dryer to eliminate water. Unfortunately, the Naphion tube is also permeable to many polar compounds such carbonyls and' alcohols. Method TO- 14 with canister sampling is only for nonpolar organic compounds, e.g. aromatics and hydrocarbons. J. Pleil (U':S. EPA, Research Triangle Park, NC) summarized the research activity in PVOC. Two developments are worth mentioning here. A SUMMA passivated canister, which replaced sampling bags in air sampling, was evaluated for its stability towards PVOC' by using a standard mixture consisting acetonitrile, methanol, acetone, acrylnitrile, butanal, isopropanol, methyl ethyl ketone, ethyl acrylate and methyl methacrylate. Wide variation of the data (2 - 70% RSD)' in the subsequent analysis over several weeks indicated the presence of residual activity from the canister's metal surface. Another approach to overcome the moisture problem is to eliminate the sampling step altogether by using real-time detection. Ion trap mass spectrometer (ITMS) is being evaluated~ as a dynamic detection and identification system. Atmospheric pressure inlet and~ glow discharge ionization (API/GD) is being investigated by EPA for air sample introduction into ITMS. Another inlet system using a direct sniffer probe fitted with a: needle valve was reported by D. Berberich (Monsanto Company). Both systems showed low ppb sensitivity (1 - 60 ppb) and the ITMS provided mass scanning and ms/ms capability for identification of unknown. NICOTINE IN ENVIRONMENTAL TOBACCO SMOKE D. J. Eatough~ (Brigham Young University) presented the results on cabin air quality study ini commercial aircraft. Future study was halted when the smoking ban became effective in January of this year. This study was conducted in a DC-10 aircraft with the following objectives (1) to quantify concentrations of ETS species, (2) to identify the factors -2-

affecting ETS, (3) to evaluate cotinine as a biomarker and (4) to develop models for non- smoking sections. Nicotine in gas and particulate phases, solanesol, aldehydes, 3- ethenylpyridine, CO, CO2 , O, , RSP, temperature and pressure were measured in the smoking section and at three locations in the non-smoking section with the PASS sarnplers., Nicotine and cotinine were measured in the total urine samples of the passengers who operated the samplers for the time period extending 24 hours before the flight to 48 hours after the flight. Atmospheric samples were also collected to determine the personnel's exposure to nicotine during the same time period. This study concluded that the rate of penetration of ETS species from smoking to non-smoking sections followed first order mechanism, cotinine in urine was highly correlated with nicotine, nicotine disappeared more rapidly in the cabin air than RSP, CO and NO, probably due to the adsorption by the fabrics, and for the passengers in the non- smoldng secnon, more exposure to nicotine occurred in the airport than in the aircraft cabin. A separate study concerning nicotine in ETS by P. R. Nelson (R. J. Reynolds Tobacco) showed a different decay phenomenon. With a controlled environmental chamber, 1R4F Kentucky reference cigarettes, and real-time and discreet analyses, the ratios between the concentrations of nicotine and other selected ETS constituents such as CO, CO2 , NO2 , pyridine, solanesol, RSP and total hydrocarbons were calculated up to six hours following the smoking. The wide variation of the ratios was caused by the decay of nicotine at a different rate than other ETS components. The data also indicated that nicotine tended to linger in the environment longer than other ETS constituents due to the adsorption and re-evaporation involving the chamber wall. Exposure to ETS solely based on nicotine concentration may be overestimated and exposure to nicotine while other ETS constituents are absent is possible. Other talks in this session included a pilot field study from Battelle Institute by measuring PAH's associated with smoking, heating and cooking systems in residential air, a comparative study of PASS and personal sampling methods for nicotine in ETS by W. E. Crouse of Lorillard Tobacco; and a Yale University study concerning the sources of aerosol mass and inorganic elements in indoor air. The Battelle data came from a very small sample size (eight homes) and appeared to be biased, in my opinion, to single out cigarette smoke. The Lorillard study, conducted in 20 restaurants, found that PASS cases provided nicotine concentration consistently and significantly higher (p<0.02) than that from the personal sampler. Several speculative reasons, pending for additional study, were given. The Yale study correlated smoking with aerosol mass, chlorine, potassium, bromine and cadmium. No explanations were given as to the possible precursors for these elements. This memo reported only the highlights of a selected number of papers presented at the conference. I have abstracts and notes for some other talks to share with anyone who is interested. A symposium: book containing the full papers will be available in the summer. cc: J. Charles M. Parrish B. Ferguson E. Thomas C. Kroustalis Central Files -3-