Document B85VYn1nmNmXw54OyxVn82Q6w

ALLIED CHEMICAL CORPORATION MEMORANDUM July 30, 1974 TO: J. C. Fedoruk P. N. Shellenberger SUBJECT: Vinyl Chloride Monomer In reference to the attached, no decision Is immediately required, but subject will undoubtedly be discussed at the next Task Force meeting. In my opinion. It is inevitable that EPA will at some time ask the question of what happens to VCM which escapes into the air. Does it remain undecomposed, or does it decompose only at a rate which permits accumulation? To me the two proposals show little overlap. The Lockheed proposal Is concerned with the disappearance of vinyl chloride in the presence of moot common air contaminants, and the Battelle proposal is concerned with mechanism and reaction products. Consequently, I would advocate both, particularly since the Battelle study is low-cost and could produce some valuable basic information. It Is our opinion that any program recommended by the full Task Force must be supported. We can, however, argue for or against proposals at Task Force meetings. Your reaction will be appreciated. I would estimate cost to Allied for both programs at about $5/500 i.e. about 5# of proposal estimates. WAK/nm ASI 00009960 y1*^1/ ^i. MANUFACTURING CHEMISTS ASSOCIATION 1825 CONNECTICUT AVENUE, N.W. WASHINGTON, D. C. 20009 (202) 483-6126 July 15, 1974 'V. A. K. JUL 1 6 1974 TO: SUBJECT: Technical Task Group on Vinyl Chloride Research Proposals for Research on Atmospheric Chemistry of Vinyl Chloride Gentlemen: At the request of the Research Coordinators made in connection with preparations for the April 2nd briefing of the EPA delegation on vinyl chloride, I have informally solicited known operators of smog chambers for proposals to investigate the atmospheric reactions that may influence the rates and routes of destruction of vinyl chloride released into the at mosphere. Attached hereto are copies of proposals that have been submitted by Battelle and Lockheed. Please review them and be prepared at our next meeting to offer your evaluation of their appropriateness for industry support and their tech nical competence. The results of such research may be of critical importance as industry develops its position on any limita tions on vinyl chloride discharges that EPA may propose pur suant to the authority granted them in section 112 of the Clean Air Act. Sincerely KDJ/mb Enclosures Kenneth D. Johnson, Ph.D. Secretary Technical Task Group on Vinyl Chloride Research ASI 00009961 MISSILES & SPACE COMPANY June 27, 197^ MANUFACTURING CHEMISTS ASSOCIATION 1825 Connecticut Avenue, N.W. Washington, D.C. 20009 Attn: Kenneth D. Johnson, Ph.D. Assistant Technical Director Air Quality Dear Ken: It is a pleasure to submit for your consideration an outline of a program to determine the atmospheric photochemistry of vinyl chloride. By using the Lockheed smog chamber with its xenon arc lamp illuminator, the best simulation of ground-level ultra-violet so far applied to photochemical testing will be used in your study. Other desirable features of the Lockheed chamber as applied to your needs are the all Pyrex-Teflon construction of the chamber, the demonstra ted reproducibility of the facility, the low background reactivity, and the fact that we can clean the chamber by vacuum off-gassing. These features and the dedicated analytical instrumentation are discussed in the Fact Sheet that I have enclosed. Just down the hall from the smog chamber is the Biotechnology Analytical Chemistry Laboratory which includes additional instrumentation that will be us d in the study: Hitachi-Perkin Elmer EMU 6D Mass Spectrometer equipped for tandem GC operation Hewlett-Packard 7620k Gas Chromatograph Perkin-Elmer Model 531 IR Spectrometer (10 meter cell) F&M Model 8l0 and Model 700 Gas Chromatographs (several) For planning purposes, we estimate that the 28 test program can be conducted and a final report submitted in five months after receiving your go-ahead. We estimate that about 70 man-weeks of effort would be required for the program, which would be billed at about $1000 per man-week. Materials and other charges would be billed at cost and are estimated at less than $20,000. In other words, for budgetary planning purposes, you could estimate a total price not to exceec $90,000 for the study, on the basis of a time-and-material arrangement. Call me if you have any questions or comments. Sincerely, LOCKHEED MISSILES & SPACE COMPANY RJJ:nl Enel. Environmental Systems Biotechnology, Orgn. 56-20, B/151 A R 0 U R 0 I V I I 0 H OF LOCKHEED AIHCHAFT CORPORATION SUNNYVALE, CALIFORNIA ASI 00009962 I ATMOSPHERIC PHOTOCHEMISTRY OF VINYL CHLORIDE I Little data is available at present on the atmospheric photochemistry of vinyl chlorid^^C) Lockheed Missiles & Space Co. (IMSC) proposes to perform a series of tests to determine the behavior of the VC/Oxides of nitrogen (NO^) system, with and without hydrocarbons present. The test program Is planned to elucidate the photochemical behavior under simulated atmos pheric conditions, using the Lockheed Smog Chamber Facility. Test Program Each test consists of cleaning the chamber; charging the reactants; turning on the solar illuminator; and monitoring the concentration changes. The following species are determined VC, NO, NOg, Ozone, and Hydrocarbons (as appropriate). Other possible reaction products will be investigated. Reference te. t conditions are: 95F chamber temperature, 53F dew point (25# relative humidity), light intensity of 0.4 min.'1 as measured by nitrogen dioxide photolysis (k^). All tests will be duplicated. 1. VC/N0x Tests - l4 Tests The VC/NO^ reaction system will be investigated at seven combinations of VC and NO^ concen trations, chosen to facilitate subsequent data manipulatton. A preliminary selection is: VC NO tC/NO^ Ratio 8 ppm 8 4 2 2 1 1 0.5 ppm 1 0.5 0.25 0.5 0.25 0.5 l6 8 8 8 4 4 2 NO 000099fc3 ftSX ) As can tie seen from the figure, this allows data to tie obtained: as a function of VC con centration at fixed NO^ (vertical traverses); as a function of concentration at fixed VC/NO^ ratio (sloping traverses); and as a function of NO^ concentration at fixed VC (horizontal traverses). 2. Hydrocarbon - VC/NO System - 6 Tests x The interrelationship obtained in the system of VC/NO^ and atmospheric hydrocarbons is of practical and theoretical interest. The hydrocarbon for such a test can range from a single representative one, such as propylene, to the 1? component mixture used by the Environmental Protection Agency. Use of a three-component mixture is planned. The three hydrocarbons, n-butane, propylene, toluene, typify paraffins, olefins, and aromatics and are each found at significant levels in the atmosphere. Each compound will be charged at 0.5 ppm C in the smog chamber, to give a 1.5 ppm C atmosphere. The NO^ concentration will be 0-5 ppm. Two levels of VC of 1.0 and k.O ppm will be used. These test data will be compared to a test with no added VC. Such tests will indicate; the effect of VC upon photochemical behavior of the hydrocarbons, and the changes in VC kinetics in a hydrocarbonNO^ atmosphere. 3. Relative Humidity Effects - 6 Tests Effect of mixture relative humidity is not well established for hydrocarbon/NO^ reaction systems. Such effects may be large in the VC/NO^ photochemical system. For a selected VC/NC>x charge, data will be gathered at chamber gas dew points of -20F, 30F and 75F, in addition to the 53F standard dew point. This yields a set of relative humidity of 1%, 1056, 25$ and 50$ at the chamber gas temperature of 95F. U. High Reactant Concentration Test - 2 Tests To assist in identification of trace species found in the VC/NO system, a photochemical test will be conducted at "high" concentration conditions, such as k8 ppm VC/3ppm NO^. Samples for this test will be subjected to intensive chemical analysis using mass spectrographic and I-R spectrographic techniques, and a combined GC-MS analysis method. LOCKHEED MISSILES & SPACE COMPANY ASI 00009964 1 June 26, 1974 OBc^eiie Columbus Laboratories 305 King Avenue Columbus, Ohio 41201 Telephone (614) 299-31 SI Telex 24-5454 Dr. Kenneth D. Johnson Manufacturing Chemists Association 1825 Connecticut Avenue, N.W, Washington, D.C. 20009 Dear Dr. Johnson: The Fate of Vinyl Chloride This letter will serve as Bnttelle's Columbus Laboratories unsolicited proposal on a study to determine the principal oxidation and reaction products of vinyl chloride in the atmosphere. The recent concern over the possible health hazards of vinyl chloride is obviously very disconcerting, especially as regards h, potential of vinyl chloride to cause serious liver damage, enlarged spleens and dele* terious blood diseases, and skin eruptions. Therefore, evaluation of the potential hazards of vinyl chloride as an in-plant emission product, as well as an out-of-doors air pollutant, becomes of major ctr_ern. It is the purpose of this proposal to evaluate the stability of iinyl chloride emissions under both dark and sunlight-irradiation conditions, and to attempt to categorize all, or at least the major reaction products of vinyl chloride in the atmosphere. Vinyl chloride is a fairly reactive organic material. For example, it polymerizes and copolymerizes very readily, which accounts for it being such a major product in plastics technology. In general, one expects vinyl chloride to oxidize with the atmosphere in the manner CH2 - CHC1 + 02"* CH20 + CO + HC1 , or In the presence of ozone CH2 - CHC1 + 03-* CH20 + C02 + HC1 . Battelle's Columbus Laboratories has examined the smog reactivity of vinyl chloride in our large (aluminum-Teflon) smog chamber. At levels of 1 and 4 ppm (volume basis) the smog reactivity of vinyl chloride was very dependent ASI 00009965 Dr. Kenneth D. Jr' tson 2 June 26, 1974 ) on organic / NO ratio, more ozone being produced at the higher ratio. This early work, since it was directed to defining the smog reactivity, did not examine the fate of the vinyl chloride. Aldehyde analyses in this study, however, indicate that some 25-50 percent of the vinyl chloride was converted to aldehyde in a 5-hour irradiation period, suggesting that vinyl chloride may have a limited lifetime in sunlight atmospheres. Another interesting feature of this initial work was the evidence of PAN, or possibly a chlorinated organic product among the smog products. Proposed Program Objective It is proposed that the principal objective of this program be a definition of the major oxidation and decomposition products of vinyl chloride. It is suggested that the program first establish the extent to which formaldehyde, carbon monoxide, and hydrogen chloride can account for the removal of vinyl chloride from any atmosphere. Depending upon the ability of these three products to account for the breakdown of vinyl chloride, more detailed analysis of other species would be undertaken to help define the fate of vinyl chloride. Experimental Program It Is proposed that this study be conducted in Battelle's two 50-cu-ft allTeflon chambers - not in the large smog chamber. At some later time, one may desire to carry out some experiments in the large chamber to determine the extent to which the aluminum-oxide coated walls of the large chamber may influence the stability of vinyl chloride. (Recognizing that all chambers exert some type of wall effect, we have not seen any especially severe effects of our aluminum walls on sulfuric and nitric acid deposition.) We propose that four general sets of conditions be examined in this program 100 ppm (v/v) vinyl chloride lighted and dark 2 ppm (v/v) vinyl chloride lighted and dark. The above systems would be examined in relatively clean air (using our chamber air purification train) at about 50 percent relative humidity to which we would add 0.5-1.0 ppm NO (about 10 percent NO^). The high concentration systems, besides providing for easier analysis, will also provide the necessary infor mation for the role of concentration effects on the reactions of vinyl chloride. Also, if it should turn out that the chemistry and kinetics are not substantially different at 100 ppm and 2 ppm vinyl chloride, the high concentration system would allow one to collect and identify the minor products more readily. ASX 00009966 Dr. Kenneth D. Johnson - 3 iune 26, 1974 Analyses of the major substances in this program would be as f Hows: vinyl chloride CH^O CO HC1 FID - G.C. chromotropic acid method FID - G.C. IR, wet chemical, or micro~ coulometric. Attempts to identify other products, such as PAN, chloraldehydes, and unknowns not established as yet, would be carried out by G.C., mass spectrometry, and infrared (Fourier transform analysis) as required. Time and Costs Inasmuch as the importance of other than the three major products, CH 0, CO, and HC1 is not known as yet, it is suggested that this program, as proposed here, be considered as a Phase 1 study. It is suggested that this Initial program be carried out over a period of 3 or 4 months at an estimated coat of approximately $25,000. Pending the outcome of this program, one will then be In a position to ask what the health hazards of the reaction products might be, and what the importance of other environmental variables might be. Anticipating that members of MCA may want to discuss the proposed program further, this proposal is sent as a preliminary document. After further dis cussions, Battelle will be pleased to submit a formal proposal and appropriate agreement forms, subject, of course, to our other commitments at that time. We hope that this document will serve as a basis of further discussion with you and your staff. Please call me at Extension 2939 for further information. Very truly yours. Arthur Levy Senior Research Leader Chemistry Department AL:mec In duplicate ASI 00009967