Document GKw9o9kvgzJ964bJvjjO4VrQ4

Gas-Chromatographic Determination of Vinyl Chloride in Air Samples Collected on Charcoal R. H. Hill, Jr.,* C. S. McCammon, A. T. Saalwaechter, A. W. Teass, and W. J. Woodfln C/ v U, S. Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National msIWte fbr uccupanonai Safety & Health, 1014 Broadway, Cincinnati, Ohio 45202 Studies of over 20 different solid sorbents, particularly charcoat, revealed significant Increases In breakthrough volumes with decreases in concentration or sampling flow rates. At low sampling flow rates, coconut shell charcoal had a good ca pacity and was selected as the most practical sorbent. Vinyl chloride was desorbed from charcoal with carbon disulfide and determined by gas chromatography. Recoveries were usually 80% or better. Samples of vlnyt chloride on charcoal were found to be stable for at least three weeks when stored at ambient or sub-ambient temperatures. At ambient conditions, vinyl chloride migrated to the back section of the charcoal tubes within a few days. The overall precision of the method was Indicated by a relative standard deviation of 7.5 % for Identical samples analyzed over a three-week period. In January 1974, the National Institute for Occupational Safety and Health (NIOSH) was informed by the B, F. Goodrich Chemical Company of several deaths among its polyfvinyl chloride) production workers from a rare liver cancer, angiosarcoma. Shortly, thereafter, NIOSH began re search on a sampling and analytical method for vinyl chloride in air. A search of the literature yielded little information on sampling techniques, but a number of analytical procedures were found which could be used for the determination of vinyl chloride in air. Gronsberg (1) sampled air containing vinyl chloride through two tubes containing activated charcoal and then desorbed and determined the vinyl chloride by a colori metric procedure. Vinyl chloride has also been determined by infrared spectrophotometry (2) and by gas chromatography (3-9) with various selective detectors (8, 10,11). NIOSH has found personal sampling most valuable in evaluation of exposure to industrial chemicals. In this respect, sampling on solid sorbents has been particularly effective and convenient (12-18). Thus, it is not surprising that since the recognition of the carcinogenic potential of vinyl chloride several methods using solid sorbents for sampling of vinyl chloride have appeared (19-25). The purpose of this work was to develop a sampling and analytical method for vinyl chloride which made use of a tube filled with a solid sorbent as a personal sampling device. The method would be used for routine analysis of large numbers of samples and would make use of commercially available and relatively inexpensive equipment. The results of the devel opment work reported have led to a detailed procedure for sampling and analytical determination of vinyl chloride in workplace air (19). EXPERIMENTAL Apparatus. A Perkin-Elmer Model 900 Gas Chromatograph equipped with a flame ionization detector and interfaced to a Perkin-Elmer PEP-1 GC Data System was used to perform analyses. Chromatographic separations were accomplished on one of two phases, either a 10% SE-30 or a 10% FFAP, both on 80/100 mesh Chromosorb W (AW-DMCS) packed in 20-ft X %-in. stainless steel columns, at column temperatures of 60 and 65 *C, respectively. The carrier gas was helium flowing at a rate of 40 ml/min. Injector and detector temperatures were 230 *C. Two-mi vials (Hewlett-Packard, Inc. No. 5080-8712) used in the desorption experiments were sealed with caps containing Teflon-lined silicone rubber septa. Sorbents used in breakthrough studies were packed in 4-mm i,d. glass tubing in beds about 1.5 cm long and were secured at either end with glass wool plugs. Sorbents used in these studies were: Chromoeorbs 101,102,103,104, 105,106, and 107, all 60-80 mesh (Johns-ManviUe, Inc.); Carbopak A, Carbopak B, Carbosieve B, all 45-60 mesh (Supelco, Inc.); Tenax GC, 35-60 mesh (Applied Science Laboratories, Inc.); Molecular Sieve, Activated, Type 5A, 30-40 mesh and silica gel, 20-40 mesh (MCB Manufacturing Chemists, Inc.); Dow Carbon XF4175L (Dow Chemical Co.); Charcoals, 20-40 mesh (SKC-104 and SKC-105, SKC, Inc.; MSA-6, Mine Safety Appliances, Inc.; BPL and PCB, Pittsburgh Activated Carbon, Inc.) For experiments other than breakthrough studies, two-section (100-mg/50-mg) charcoal tubes (SKC, Inc. or Mine Safety Appliances, Inc.) were used. Atmospheres of vinyl chloride were prepared in Tedlar (E. I. du Pont de Nemours & Co., Inc.) bags or in a dynamic generation system similar to that described by Ash and Lynch (26). Breakthrough studies were carried out by drawing synthetic vinyl chloride-air mixtures through the sorbent tube with a modified personal sampling pump (Sipin Model SP-1). The exit diaphragm of this pump was enclosed in a Teflon chamber so that the exit air was pushed through the sample line of a portable AID Model 521 gas chromatograph with a flame ionization detector, which monitored the vinyl chloride in the bed effluent. The void volume between the end of the sorbent bed and the detector was 0.45 ml. Samples for de sorption studies were prepared in a similar manner except that the tube effluent was not monitored. Reagents. Reagents used were vinyl chloride (Linde Division, Union Carbide Corp.) and carbon disulfide (MCB Manufacturing Chemists, Inc.). Sample Analysis. Each charcoal tube was scored in front of the primary (100 mg) section and broken. The glass wool was removed and discarded. The charcoal in this section was transferred to a 2-ml vial containing 0.5 or 1.0 ml of carbon disulfide and the vial was im mediately sealed with a septum cap. The urethane foam separating the two sections of charcoal was discarded and the second section was desorbed in a like manner. The two sections were analyzed separately. The samples were allowed to stand at room temperature for a period of 10 to 60 min before analysis. Analyses were performed by injecting 5 ii\ of the carbon disulfide solution with 2 j/1 of carbon disulfide back flush into the gas chromatograph. Standard Preparation. Standards of vinyl chloride in solvent were prepared by the two manners described below. (a) A stock solution of vinyl chloride was prepared by slowly bub bling vinyl chloride for 3 min into a tared 10-ml volumetric flask containing approximately 5 ml of toluene. A weight gain of 100-300 mg was usually observed. This solution was then diluted to exactly 10 ml with carbon disulfide. (b) A 1-ml sample of vinyl chloride gas was drawn into a gas-tight syringe and the tip of the needle was inserted into a 10-ml volumetric flask containing approximately 5 ml of carbon disulfide. The plunger was withdrawn slightly to allow the solvent to enter the syringe. The action of the vinyl chloride dissolving in the carbon disulfide created a vacuum and the syringe became filled with solvent. An air bubble (~2%) in the syringe was found to be due to the head space in the needle. The solution was returned to the flask and the syringe was rinsed twice with carbon disulfide, with the washings added to the solution in the flask. Dilution to exactly 10 ml with carbon disulfide gave a stock solution. The standards obtained by diluting aliquots from either solution gave standard curves which coincided and were linear from 0.2 ng to' 1.5 jig per injection. 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Table II. Optimization of Desorption Procedure Experi ment I II III IV V VI Proce dure* A B A B B B B B B C B C Desorption time, min 10 10 30 30 10 30 30 30 30 30 30 30 Temper ature Ambient Ambient Ambient Ambient Ambient Ambient Ambient 0 Ambient Ambient Ambient Ambient Found, pgb 2.13 0.27 2.26 0.09 2.20 0.21 2.23 0.14 113.1 16,1c 112.7 6.4c 51.9 1.9 52.9 dfc 1.6 207.7 9.2C 216.5 9.2' 22.5 1.2 22.5 1.0 Procedure: A, 0.5 ml CSj added to charcoal; B, Charcoal added to 0.5 ml CSj; C, Charcoal added to 1.0 ml CS2. b The means of six samples and the 95% confidence intervals are reported. The measurements are not corrected for desorption efficiency.c Only 3 samples were analyzed. VWYl OiO*Cl 1.1 ij u n is 1.4 u 1i TIME W MINUTES Figure 1. Comparison of peak shapes of vinyl chloride (12.6 ng) In air and in carbon disulfide The gas chromatograms were obtained on a 20-ft, 10% SE-30 column at 60 C at an attenuation of X16 Table III. Comparison of Gas Samples and Charcoal Tube Samples Calculated value6 Gas injection Charcoal tube' Difference between gas injection and charcoal tubes 64 ug/1. 71.2 1.7 69.8 3.6 2.0% 13/g/I. 14.5 1.2 13.6 0.7 6.4% 2.6 pg/l. 2.9 0.2 2.9 0.2 0% . a Each value represents the average of six determinations and the 95% confidence level, 6 Calculated from the amount of vinyl chloride and air used to prepare the test atmospheres. ' Charcoal tube samples were corrected for desorption efficiency. Stability and Storage Properties. The results of experi ments to determine the stability of vinyl chloride-on-charcoal samples, shown in Figure 2, demonstrated that vinyl chloride was stable on charcoal for extended periods of time at ambient or sub-ambient temperatures. However, at ambient temper atures vinyl chloride migrated to the back section of charcoal until it achieved even distribution on the charcoal in the tube. The migration was retarded by cooling the vinyl chlorideon-charcoal samples during storage. In later experiments, it was found that sampling could be accomplished with two charcoal tubes in series with no significant drain on the working capacity of the personal sampling pump being used. The first tube could then be used as the "front" section with the second tube serving as the "backup" section. Since each section was a separate entity, the need for cooling during shipment and storage was eliminated. Precision and Accuracy. Because the vinyl chloride is not quantitatively removed from the charcoal in the analytical procedure, a measurement, m, of vinyl chloride from charcoal tube samples must be corrected for this loss. The desorption efficiency is the ratio x/y where x is the mean concentration of a test atmosphere as determined by analysis of charcoal tube samples and y is the mean concentration of the sample atmosphere as determined directly by injection of gas aliquots. Thus, for a sample, the corrected value, z, is equal to my/s. The precision of z, expressed as the relative standard devia tion, is not simply obtained, but is best approximated by the following equation derived after Ku (29): + Syzy/2 nyy2) (l) where S; is the standard deviation of n, values and an overlying bar denotes the number is a mean. 1 l 1 * 5 I 1 I I 10 11 11 11 14 is 11 17 11 11 TIME IN MTS Figure 2. Stability of vinyl chlorlde-on-coconut-charcoal samples () Back section stored at --20 C. (At Back section stored at ambient 1am- perative. () Total in both sections stored at --20 C. () Total In both sections stored at ambient temperature _, A number of vinyl chloride-on-charcoal samples of two synthetic atmospheres were analyzed over 20- to 30-day pe riods by different analysts using different instrumentation. Using Equation 1, the relative standard deviation was deter mined to be 7.5% where the concentration was 7.3 pg/1. (27 samples) and 7.4% where the concentration was 71 pg/l. (29 samples). The accuracy of the method was difficult to assess in the absence of a primary standard. In light of this fact, it was thought meaningful to compare two techniques, charcoal-tube determination and analysis by gas aliquot injection. The re sults of determinations of synthetic atmospheres by these techniques, shown in Table III, indicate good agreement be tween these methods. ACKNOWLEDGMENT The authors express their thanks to K. A. Busch for the statistical derivation. LITERATURE CITED (1) E. S. Gronsberg. Khim, Prom., 42(7), 610-11 (1966); Chem. Abstr., 65, 1759a (1966). (2) E. O. Baretta, R. D. Stewart, and J. E. Mu!chief. Am. Ind. Hyg. Assoc. J., 30, 537 (1969). (3) O. L. Hollis, Anal. Chem., 38,309 (1968). (4) A. Foris and J. G. Lehman, Sep. Scl., 4(3), 225-41 (1969). (5) H. Koenig. Fresenius Z. Anal. Chem., 232(6), 427 (1967). (6) L. D. Hinshaw, J. Gas Chromalogr., 4(8), 300 (1966). (7) G. G. Esposito and M. 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