Document O3ZJ4K8J4azRQyExpXj0oakqe

CONFERENCE TO REEVALUATE THE TOXICITY OF VINYL CHLORIDE, POLYVINYL CHLORIDE AND STRUCTURAL ANALOGUES March 20-21, 1980 National Institutes of Health Masur Auditorium Building 10 Clinical Center Bethesda, Maryland Cosponsors National Institutes of Environmental Health Sciences National Institute for Occupastional Safety and Health Occupational Safety and Health Administration SAL 00007078 Thursday, March 20, 1980 8:00 A.M. REGISTRATION 8:30 A.M. INTRODUCTORY REMARKS Dr. David Rail, NIEHS SESSION I - 8:45 A.M. 9:45 A.M. 10:00 A.M. 10:15 A.M. 10:45 A.M. 11:00A.M. 11:15 A.M. CARCINOGENESIS BIOASSAYS OF VINYL CHLORIDE MONOMER Chairperson: Dr. Umberto Saffiotti, NCI 1. Carcinogenicity Bioassays of Vinyl Chloride Monomer: A Model of Risk Assessment on Experimental Basis Dr. Cesare Maltoni, Institute of Oncology and Tumor Center, Bologna 2. Experimentally Induced Pulmonary Cancer Dr. Y. Suzuki, Mt. Sinai Medical School f / Discussion Break 3. The Role of Aging on Cancer Induced by Vinyl Chloride Monomer Dr. David Groth, NIOSH 4. Carcinogenic Effects of Exposure to Vinyl Chloride Monomer and Ethyl Alocohol on Rats Dr. Martha Radike, University of Cincinnati j 5. Cancer Induction Following Single and Multiple Exposures to a Constant Amount of Vinyl Choride Monomer Dr. Robert Hehir, CPSC SESSION II 11:30 A.M. 11:45 A.M. TOXICOLOGY STUDIES OF POLYVINYL CHLORIDE Chairperson: Dr. Peter Infante, OSHA 6. Pneumoconiosis in Animals Exposed to Polyvinyl Chloride Dust Dr. David Groth, NIOSH 7. Results of Carcinogenesis Bioassay of Polyvinyl Chloride Dr. Chris Wagner, BMRC, Penarth, Wales _ cJ<^?tis,T?vvv ^ (, <icmot*- . 0 j SAL 00007078 Thursday, March 20, 1980 SESSION Ml - SPUTUM CYTOLOGY OF VINYL CHLORIDE WORKERS Chairperson: Dr. Peter Infante, OSHA `2:00 P.M. S. Results of Sputum Cytology Among Workers Exposed to Vinyl Chloride Monomer and to Polyvinly Chloride Dr. Cesare Maltoni, Institute of Oncology and Tumor Center, Bologna 12:15 P.M. Discussion 12:30P.M. LUNCH SESSION IV - MORTALITY STUDIES OF WORKERS EXPOSED TO VINYL CHLORIDE Chairperson: Dr. Philip Landrigan, NIOSH -- 2:00 P.M. 9. Multiple Site Risk Analysis of Vinyl Chloride Related Cancer in Workers -- Review /a Dr. Peter Infante, OSHA di /'v ^ '7S~7l`f 2:15 P.M. 10. Cohorr Mortality Study of Vinyl Chloride Workers Dr. H, Weber, Der Staatliche Gewerbearzt , Fed. Republic Germany 2:30 2:45 P.M. 11. Epidemiological Study of Vinyl Chloride Workers t 6-73 ->>12/710 Dr. Clark Cooper, Consultant f* / 7^ P.M. 12. Power Considerations in Epidemiologic Studies of Vinyl Chloride Workers Dr. Jay Beaumont, NIOSH 3:00 P.M. Discussion 3:15 P.M. Break SESSION V 3:45 P.M. LIVER AND BIOCHEMICAL CHANGES ASSOCIATED WITH VINYL CHLORIDE Chairperson: Dr. David Groth, NIOSH 13. Epidemiologic Review of Hepatic Angiosarcoma in the United States Dr. Henry Falk, CDC OOoq ?0?83 Thursday, March 20, 1980 4:00 P.M. 4:15 P.M. 4:30 P.M. 14. United Kingdom Angiosarcoma Registry Dr. Peter Baxter, CDC 15. Pathology of Vinyl Chloride Induced Liver Lesions Dr. Hans Popper, Mt, Sinai Medical School 16. Liver Screening Tests for Vinyl Chloride Exposed Workers Dr. Carlo Tamburro, University of Louisville SESSION Vi - 4:45 P.M. 5:00 P.M. 5:15 P.M. INDUSTRIAL HYGIENE MEASUREMENTS OF POLYVINYL CHLORIDE OPERATIONS Chairperson: Mr. James Gideon, NIOSH 17. Pofyvinly Chloride Processes and Products Dr. R. Nick Wheeler, Union Carbide w i^a v C. y Pt/ <L 18. nf Polyvinyl Clhl^riHo-Homvp'Mymarr, Copolymers and Additiuas Mr. Jay Jones, NIOSH Discussion Friday, March 21. 1980 SESSION VII - MORBIDITY AND MORTALITY STUDIES OF WORKERS EXPOSED TO POLYVINYL CHLORIDE Chairperson: Dr. R, Greenberg, University of Louisville 8:30 A.M. 8:45 A.M. 19. Mortality Among Polyvinyl Chloride Fabricators , Dr. Leonard Chiazze. Georgetown University sfudAi, Mn. 20. Heart Disease in the Swedish Polyvinyl Chloride Fabricating industry /orf Srvdu Dr. Gustavo Molina. Colombia 9:00 A.M. 21. An Epidemiological Study of Respiratory Disease in United Kingdom Workers Exposed to Polyvinyl Chloride Dust Dr. Anthony Seaton, University of Edinburg 9:15 A.M. 22. Pneumoconiosis induced by Polyvinyl Chloride Dust Dr. A. Arnaud, Marseille, France 5hij SAL 000070784 Friday, March 21, 1980 9:30 A.M. 9:45 A.M. 10:00 A.M. 10:15 A.M. 10:30 A.M. 23. An Epidemiologic Study of Pneumoconiosis in the Italian Polyvinyl Chloride Industry Dr. Guiseppe Mastrangelo, Padova, Italy 24. A Case-Control Study of Lung Cancer Among Vinyl Chloride-Polyvinyl Chloride Workers Dr. Richard Waxweiler, NIOSH 25. Review of Pulmonary Effects of Polyvinyl Chloride Exposure Dr. Ruth Lilis, Mt. Sinai Medical School Discussion Break SESSION VIII - REPRODUCTIVE EFFECTS OF VINYL CHLORIDE Chairperson: Dr. James Wilson, University of Cincinnati 11:00 A.M. 11:15 A.M. 26. Transplacental Teratogenic Effects of Vinyl Chloride in Experimental Animals __ ..Dr. Jackie John, Dow NJidland 27. T^pSSm^M^oSni^f Dr, Jerry Rice, NCI 0C 11:30A.M. 28. Mutagenic Effects of Vinyl Chloride Or. Jill Fabricant, University of Texas, Galveston 11:45 A.M. 12:00 P.M. 12:30 P.M. 29. Power Considerations in Studies of Reproductive Effects Associated with Vinyl Chloride and Some Structural Analogues Ms. Maureen Hatch, Columbia University i&ht* 'J />oo\K Discussion*7-- stw c/jLrk- -- LUNCH SESSION IX - ENVIRONMENTAL EXPOSURE TO VINYL CHLORIDE- POLYVINYL CHLORIDE AND LIVER ANGIOSARCOMA Chairperson: Dr. Pier Bertazzi, Institute of Occupational Health, Milan /\ 1 V ; ; SAL Q000707QS Friday 2:00 P.M. 2:15 P.M. 4tL1 30. Fugitive Emissions of Vinyl Chhlloorriicde-Polyvinyl Chloride lUiyatt, EPA At* Liver Angiosarcoma /Vynq ^ n--:y--Y--V ^ /rs^l BxpVku^. -Br=N Tewwa, N.V.3. DupartnraTrbf llealitr- SESSION X - 2:30 P.M. 2:45 P.M. 3:00 P.M. 3:15 P.M. 3:30 P.M. CARCINOGENICITY OF SOME STRUCTURAL ANALOGUES OF VINYL CHLORIDE Chairperson: Dr. Kim Hooper, University of California, Berkeley 32. Comparative Pathology of Vinyl Chloride and Vinyl Bromide Induced Liver Pathology in Animals Dr. William Busey, Experimental Pathology Laboratories 33. Review of Experimental Carcinogenesis of Vinyl Chloride Related Compounds Dr. KenChu.NCI 34. Review of Epidemiologic Study Results of Vinyl Chloride Related Compounds Ms. Rosanne Apfeldorf, OSHA Discussion Break SESSION XI - RESEARCH NEEDS AND PUBLC HEALTH INTERVENTION Chairperson: Dr. Anthony Robbins, NIOSH Panel Discussion: 4:00 P.M. 35. Dr Dale Haddis, Center for Policy Alternatives, MIT 4:15 P.M. 36. Mr. Steve Wodka, OCAW 4:30 P.M. 37. Dr. Maurice Johnson, B.F. Goodrich 4:45 P.M. 38. Dr.+rvmySeHktJff^Mt. Sinai Medical School 0qG07078 SA\- Friday, March 21, 1980 5:00 P.M. 39. Dr. Joseph Wagoner, EDF 5:15 P.M. Discussion Proceedings from the Conference will be published Program Planning Committee Dr. Richard B. Everson NIEHS, Research Triangle Park, North Carolina Dr. Peter F. Infante OSHA, Washington, D.C. Dr. Philip J. Landrigan NIOSH, Cincinnati, Ohio Dr. Raymond E. Shapiro NIEHS, Research Triangle Park, North Carolina Dr. Richard J. Waxweiler NIOSH, Cincinnati, Ohio fI SAL 000070787 L .l .< -- r cv_r //; r/ /J / C SArf CONFERENCE TO REEVALUATE THE TOXICITY OF VINYL CHLORIDE, POLYVINYL CHLORIDE AND STRUCTURAL ANALOGUES March 20-21, 1980 National Institutes of Health Masur Auditorium Building 10 Clinical Center Bethesda, Maryland -- -- -------- ---- -- ---------- ---- ---- ---- - . Cosponsors National Institutes of Environmental Health Sciences National Institute for Occupational Safety and Health Occupational Safety and Health Administration SAL 000070795 Thursday, March 20, 1980 8:00 A.M. REGISTRATION 8:30 A.M. INTRODUCTORY REMARKS Dr. David Rail, NIEHS SESSION I - CARCINOGENESIS BIOASSAYS OF VINYL CHLORIDE MONOMER Chairperson: Dr. Umberto Saffiotti, NCI 8:45 A.M. 1. Carcinogenesis Bioassay of Vinyl Chloride Monomer with Particular Reference to Multiple .Sites and Dosage Review Dr. Caesar Maltoni, Institute of Oncology and Tumor Center, Bologna 9:45 A.M. `2. Experimentally Induced Pulmonary Cancer Dr. Y. Suzuki, Mt. Sinai Medical School 10:00 A.M. Discussion 10:15 A.M. Break - 10:45 A.M. 3. The Role of Aging on Vinyl Chloride Monomer - Induced Cancer Dr. David Groth, NIOSH 11:00 A.M. 4. Carcinogenic Effects of Exposure to Vinyl Chloride Monomer and Ethyl Alcohol on Rats Dr. Martha Radike, University of Cincinnati 11:15 A.M. 5. Cancer Induction Following Single and Multiple Exposures to a Constant Amount of Vinyl Chloride Monomer Dr. Robert Hehir, CPSC SESSION II-- TOXICOLOGY STUDIES OF POLYVINYL CHLORIDE Chairperson: Dr. Peter Infante, OSHA 11:30 A.M. 6. Pneumoconiosis in Animals Exposed to Polyvinyl Chloride Dust Dr. David Groth, NIOSH 11:45 A.M. 7. Results of Carcinogenesis Bioassay of Polyvinyl Chloride Dr. Chris Wagner, BMRC, Penarth, Wales SAL 000070796 Thursday, March 20, 1980 SESSION III "SPUTUM CYTOLOGY OF VINYL CHLORIDE WORKERS Chairperson: Dr. Peter Infante, OSHA 12:00 P.M. 8. Results of Sputum Cytology Among Vinyl Chloride Polymerization and Polyvinyl Chloride Fabrication Workers Dr. Caesar Maltoni, Institute of* Oncology and Tumor Center, Bologna 12:15 P.M. Discussion 12:30 P.M. LUNCH SESSION IV - MORTALITY STUDIES OF WORKERS EXPOSED TO VINYL CHLORIDE Chairperson: Dr. Philip Landrigan, NIOSH 2:00 P.M. 9. Multiple Site Risk Analysis of Vinyl Chloride Related Cancer in Workers - Review Dr. Peter Infante, OSHA 2:15 P.M. 10. Cohort Mortality Study of Vinyl Chloride Workers Dr. H. Weber, Der Staatliche Geverbearzt, Fed. Deutch Republic ----- 2:30 P.M. 11. Epidemiological Study of Vinyl Chloride Workers Dr. Clark Cooper, Consultant 2:45 P.M. 12. Power Considerations in Epidemiologic Studies of Vinyl Chloride Workers Dr. Jay Beaumont, NIOSH 3:00 P.M. Discussion 3:15 P.M. Break SESSION V " LIVER AND BIOCHEMICAL CHANGES ASSOCIATED WITH VINYL CHLORIDE Chairperson: Dr. David Groth, NIOSH 3:45 P.M. 13. Epidemiologic Review of Hepatic Angiosarcoma in the United States Dr. Henry Falk, CDC SAL 00707P7 f Thursday, March 20, 1980 4:00 P.M. 14. United Kingdom Angiosarcoma Registry Dr. Peter Baxter, CDC 4:15 P.M. 15. Pathology of Vinyl Chloride Induced Liver Lesions Dr. Hans Popper, Mt. Sinai Medical School 4:30 -P.M. 16. Liver Screening Tests for Vinyl Chloride Exposed Workers Dr. Carlo Tambero, University of Louisville SESSION VI - INDUSTRIAL HYGIENE MEASUREMENTS OF POLYVINYL CHLORIDE OPERATIONS -Chairperson: Mr. James Gideon, NIOSH 4:45 P.M. 17. Polyvinyl Chloride Processes and Products Dr. R. Nick Wheeler, Union Carbide 5:00 P.M. 18. Characterization of Polyvinyl Chloride Homopolymers, Copolymers and-Additives Mr. Jay Jones, NIOSH 5:15 P.M. Discussion 2 $4L. 9# ran Friday, March 21, 1980 SESSION VII - MORBIDITY AND MORTALITY STUDIES OF POLYVINYL CHLORIDE EXPOSED WORKERS Chairperson: Dr. R. Greenberg, University of Louisville 8:30 A.M. 19. Mortality Among Polyvinyl Chloride Fabricators Dr. Leonard Chiazze, Georgetown University 8:45 A.M. 20.'Heart Disease in the Swedish Polyvinyl Chloride Fabricating Industry Dr. Gustavo Molina, Colombia 9:00 A.M. 21. An Epidemiological Study of Respiratory Disease in United Kingdom Workers Exposed to Polyvinyl Chloride Dust Dr. Anthony Seaton, University of Edinberg 9:15 A.M. 22. Polyvinyl Chloride Dust Induced Pneumoconiosis Dr. A. Arnaud, Marseille, France 9:30 A.M. 23. An Epidemiologic Study of Pneumoconiosis in the Italian Polyvinyl Chloride Industry Dr. Guiseppe Mastrangelo, Padova, Italy 9:45 A.M. 24. A Case-Control Study of Lung Cancer Among Vinyl Chloride-Polyvinyl Chloride Workers Dr. Richard Waxweiler, NIOSH 10:00 A.M. 25. Review of Pulmonary Effects of Polyvinyl Chloride Exposure Dr. Ruth Lilis, Mt. Sinai Medical School 10:15 A.M. Discussion 10:30 A.M. Break I SAL 000070799 Friday, March 21, 1980 SESSION VIII - REPRODUCTIVE EFFECTS OF VINYL CHLORIDE Chairperson: Dr. James Wilson, University of Cincinnati 11:00 A.M. 26. Transplacental Teratogenic Effects of Vinyl Chloride in Experimental Animals Dr. Jackie John, DOW Midland 11:15 A.M. 11:30 A.M. 27. Transplacental Carcinogenic Effects Dr. Jerry Rice, NCI 28Mutagenic Effects of Vinyl Chloride Dr. Jill Fabricant, University of Texas, Galveston 11:45* A.M. 29. Power Considerations in Studies- of Reproductive Effects Associated with Vinyl Chloride and Some Structural Analogues ` ^ Ms. Maureen Hatch, Columbia University 12:00 P.M. Discussion 12:30 P.M. LUNCH SESSION IX - ENVIRONMENTAL EXPOSURE TO VINYL CHLORIDEPOLYVINYL CHLORIDE AND LIVER ANGIOSARCOMA Chairperson: Dr. Pier Bertazzi, Institute of Occupational Health, Milan 2 : 00 P.M. . 30. Fugitive Emissions of Vinyl ChloridePolyvinyl Chloride Speaker to be Announced 2:15 P.M. 31. Case-Control Study of Liver Angiosarcoma Among Residents in New York Dr. Nicholas Vianna, N.Y.S. Department of Health SAL 000070800 Friday, March 21, 1980 SESSION X - CARCINOGENICITY OF SOME STRUCTURAL ANALOGUES OF VINYL CHLORIDE Chairperson: Dr. Kim Hooper, University of California, Berkeley 2:30 P.M. 32. Comparative Pathology of Vinyl Chloride and Vinyl Bromide Induced Liver Pathology in Animals' Dr. William Busey, Experimental Pathology Laboratories 2:45 P.M. 33. Review of Experimental Carcinogenesis of Vinyl Chloride Related Compounds Dr. Ken Chu, NCI 3:00 P.M. 34. Review of Epidemiologic Study Results of Vinyl Chloride Related Compounds Ms. Rosanne Apfeldorf, OSHA 3:15 P.M. Discussion 3:30 P.M. Break SESSION XI - RESEARCH NEEDS AND PUBLIC HEALTH INTERVENTION Chairperson: Dr. Anthony Robbins, NIOSH Panel Discussion: 4:00 P.M. 35. Dr. Dale -Haddis, Center for Policy Alternatives, MIT 4:15 P.M. 36. Mr. Steve Wodka, OCAW 4:30 P.M. 37. Dr. Maurice Johnson, B.F. Goodrich 4:45 P.M. 38. Dr. Irving Selikoff, Mt. Sinai Medical School 5:00 P.M. 39. Dr. Joseph V7agoner,- EDF 5:15 P.M. Discussion Proceedings from the Conference will be published. 000070801- SAL - 1 r* Program Planning Committee Dr. Richard B. Everson NIEHS, Research Triangle Park, North Carolina Dr. Peter F. Infante OSHA, Washington, D.C. Dr. Philip J. Landrigan NIOSH, Cincinnati, Ohio Dr. Raymond E. Shapiro NIEHS, Research Triangle Park, North Carolina Dr. Richard J. Waxweiler NIOSH, Cincinnati, Ohio : 7* J. . . . . . . . . . . . . . . . . . . . . . . . . . . - . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ___________ SAL 000070802 SAL 000070803 bQBQ4 0 0 0 0 HOTELS/MOTELS IN THE E SDr., unN j r. " m Name/Address/Telephone Bethesdan Motor Hotel 7740 Wisconsin Avenue Bethesda, MD 20014 (301) 656-2100 Single Room Distance from NIH Rate (Inc. Tax) (Approximate) $28.60 1 mile Holiday Inn (Bethesda) 8120 Wisconsin Avenue Bethesda, MD 20014 (301) 652-2000 Ramada Inn (Bethesda) 8400 Wisconsin Avenue Bethesda, MD 20014 (301) 654-1000 United Inn of America8130 Wisconsin Avenue Bethesda, MD 20014. (301 ) 656-9300 Holiday Inn (Chevy Chase) 5150 Wisconsin Avenue 'Chevy Chase, MD 20015 (301 ) 656 -1500 $51.70 ifk kieitieiele'k'kle $49.50 $45.10 *-*jr***ir*THr* $41.80 Sun - Thurs $35.20 Fri - Sat *"****** $46.20 1 mile 1 mile i_. 1 mile 3% miles Intown (Chevy Chase) 6800 Wisconsin Avenue Chevy Chase, MD 20015 (301) 654-1400 Linden Hill Hotel 5400 Pooks Hill Road Bethesda, MD 20014 (301) 530-0300 $29.70 $27.50* $51.70 $49.50* Special Government Rate 2 miles 2 miles SAL 000070805 Name/Address/Telephone r Single Room Rate Connecticut Inn 4400 Connecticut Avenue Washington, D. C. 20008 $39.68 (202) 244-5600 Howard Johnson's Motor Lodge 2715 University Boulevard Wheaton, MD 20902 *Steam Bath l-^ T-ITTrt W1iP w IP iPf.pf $33.00 (301) 933-1300 $30.80* -< _ _ j j . . - -i Hampshire Inn 7411 'Mew Hampshire Avenue Langley Park,' MD 20787 (301) 439-3000 $37.40 ' $24.20* ****** Distance from NIH (Approximate) 5 miles 7 miles 12 miles s.;\y. HI & | Special Government Rate 000070806 SAL SAL 000070807 S! SAL 000070808 Name/Address/Telephone Bethesdan Motor Hotel 7740 Wisconsin Avenue Bethesda, MD 20014 (301) 656-2100 Holiday Inn (Bethesda) 8120 Wisconsin Avenue Bethesda, MD 20014 (301) 652-2000 -Ramada Inn (Bethesda) 8400 Wisconsin Avenue Bethesda, MD 20014 (301) 654-1000 United Inn of America 8130 Wisconsin Avenue Bethesda, MD 20014. (301) 656-9300 Holiday Inn (Chevy Chase) 5150 Wisconsin Avenue 'Chevy Chase, MD 20015 (301) 656 -1500 Intown (Chevy Chase) 6800 Wisconsin Avenue Chevy Chase, MD 20015 (301) 654-1400 Linden Hill Hotel 5400 Pooks Hill Road Bethesda, MD 20014 (301) 530-0300 Single Room Distance from NIH Rate (Inc. Tax) (Approximate) $28.60 1 mile it***** $51.70 . *********** $49.50 $45.10 *********** $4i ."so ~~ Sun - Thu'rs $35.20 Fri - Sat *********** $45.20 1 mile - 1 mile 1 mil e * 1*5 miles *********** $29.70 $27.50* *********** $51.70 $49.50* 2 miles 2 miles ^Special Government Rate 00007000 Hame/Address/Telephone * Single Room Rate Connecticut Inn 4400 Connecticut Avenue Washington, D. C. 20008 $39.68 '(202) 244-5600 Howard Oohnson*s Motor Lodge 2715 University Boulevard Wheaton, MD 20902 Steam Bath **** $33.00 (301) 933-1300 $30.80* in rin finrT TPT-rT-T< Hampshire Inn 7411 Mew Hampshire Avenue Langley Park,' MD 20787 (301) 439-3000 ' $37.40 ' $24.20* trie 4r Distance from NIH (Approximate) 5 miles 7 miles 12 miles Special Government Rate SAL 000070810 A Literature Study of the Combustion Ha2ards of Polyvinylchloride (PVC) and Acrylonitrile Butadiene Styrene (ABS) SAL 000070837 A Literature Study of the Combustion Hazards of Polyvinylchloride (PVC) and Acrylonitrile Butadiene Styrene (ABS) by, j. Judith E. Hall and Eric L. Tollefson, P.Eng. Department of Chemical and Petroleum Engineering The University of Calgary June 20, 1981 Research Associate ?rofessor &Y>(' 0070S3S Table of Content Summa ry I Introduction * It Smoke Particulates I 1-1 Optical Methods 11-2 Gravimetric Methods 11-3 Relative Rates of Smoke and HC1 Release from PVC 11-4 Toxic Gases Adsorbed onSoot 11-5 Smoke Detectors 111-1 Decomposition of PVC 1 t 1-2 Decomposition of ABS IV Toxicology IV-1 PVC'Toxlcology 1V-2 ABS Toxicology 1V-- 3 Real Fires Involving PVC IV-4 Real Fires Involving ABS and Plastics Known to Produce Hydrogen Cyanide V-l V-2 Rates of Smoke and Acid.Gas Release in Rooms \ 4 Behaviour of PVC ABS Pipes in Fire Tests Conclusions Acknowledgements . References Appendices Page .t 7 8 13 1516 17 21 21 24 27 30 31 32 33 37 38 33^ 48 S|i>L 000070839 I ^ S umma ry The Increasing use of plastics to replace traditional materials in, for example, furniture, draperies, carpeting, electrical and thermal insulation as well as piping in plumbing systems has given rise to much concern In the event of a fire. Many plastics are very flammable, urn rapidly and produce intense heat, heavy smoke and toxic gases which together are very dangerous to life. The recent HGH Grand Hotel fire is an example of this type of flret most of the victims dying from smoke inhalation even though far-removed from the site of the fire. This report is the result of a literature search on the combustion hazards associated with the use of two plastics widely used In plumbing systemsnamely, polyvinyl chloride (PVC) and acrylonitrile-butadiene-styrene (ABS); These two plastics, along with polystyrene, comprise about one third of the total plastics sold in the United States. Of the common plastics these three are most prone to produce extremely dense smoke on combustion. ABS is very flam mable and like other nitrogen-containing polymers releases hydrogen cyanide as a combustion product. vPVC is much less flammable but wTT f burni" 1 f combustion $ Js supported by other fuels?>Large amounts of hydrogen chloride gas (HC1) are) '.released by either heating or burning PVC. Heavy smoke production during a fire is dangerous becadse: (a) it reduces visibility thus impeding escape, (b) particulates cause difficulties in breathing if inhaled, and (c) toxic or irritant gases not only interfere with vision and breathing but also damage lungs, cause confusion, unconsciousness and death. A&S, PVC, and wood produce comparable amounts of smoke'when smouldering but, under flaming conditlons .""`wlthin one to two minutes after .ignition the smoke from these two plastics is about 28-40 times as dense as ? from wood. Ventilation does not decrease the smoke density as it does in the ^case of wood.^'^ ^ In the case of a rapid electrical overload in PVC-insulated wire, smoke ? which Is usually the first indication of a fire, is only noticeable after ^ significant quantities of HC1 have been released. Ionization detectors have? c been found to be quite insensitive to PVC smoke and have been reported to give an alarm after hazardous levels of HC1 had already been exceeded.^ The r^apid production of very dense smoke in PVC fires, tfie fact that 70i & of the hydrogen chloride vapor which can be produced by a sample occurs 'In less than one minute at 2QQ-309C, and the relative insensitivity of ionization^ V detectors rto PVC smoke ,^all combine to deny 4 person"exposed to such a fire a treasonable' escape^tVrrietv'- V ,4 Loss of hydrogen chloride from PVC is a thermal decomposition beginning between 1?0 and 190C and becoming quantitative at about 270C. The presence of oxygen is not necessary for this reaction to occur. At 500C and in the presence of oxygen, combustion of PVC produces carbon monoxide as do most other organic materials. ABS begins to decompose at 300C, the major toxic product formed being HCN as well as a smaller amount of nitrogen dioxide (NO^)- These gases are produced from the acrylontrile part of ABS so varying the composition of the ABS may affect the amounts of HCN and NO^ produced its combustion. The toxicities of smokes produced from different materials have been extensively studied and it is apparent that results can be very sensitive to experimental conditions.}, For example when ''time of death is used PVC and ABS $ pyrolysis products are apparently less toxic than wood but when the amount of^ sample which caused 50% of the animals to die was determined ABS and PVC were' much more toxic than wood.^ The relative toxicity of PVC also rises drammatically when air Is drawn over the samples towards the test animals. Physiological and histopathological studies indicate that the major toxicant in PVC pyrolysis gases is HCl.-^ It would also seem evident from the few .experiments that have been done that HCN Is the major toxicant from ABS combustion. Vhen water is used to trap HC1 in smoke toxicity tests, the animals are able to survive five times the amount of PVC pyrolysis products that they can survive without a water trap. This implies that water from sprinkler systems or other sources would be valuable in reducing the HC1. content of the atmosphere during escape or in fire-fighting operations. ' Carbon monoxide, hydrogen cyanide, nitrogen dioxide and hydrogen chloride all interfere with the body's system for uptake, transport or use of oxygen to reduce their capacities either seriously or fatally. Hydrogen cyanide and nitrogen dioxide are about twenty-five times as toxic as carbon monoxide based on the lethal concentration values and hydrogen chloride is Intolerable' at levels of 100 ppm or more with 1000 ppm causing lung edema after a very shor 0000708*1 exposure 'time. The effects of HC1 will not be evident immediately and carbon monoxide can cause death as long as S"15 months after a person apparently has recovered. The situation is further complicated by the fact that Inhalation of a complex mixture of toxic gases and smoke in an actual fire situation will result in additive or possibly synergistic (greater than additive) Responses that are not well studied or understood. Information is available concerning the apparent increase in the toxicity of carbon monoxide when blood alcohol is greater than 0.1% (volume). In actual fire victims the carbon monoxide levels are elevated but very often are not sufficiently high to have caused death indicating that other toxic substances are important factors. .In actual PVC fires, even though there was little smoke In their early T stages and the fires were small, the firefighters involved exhibited symptoms due to inhalation of HC1 and often required medical treatment; The role of cyanide poisoning In fires seems to be less well understood but is nevertheless considered to be serious in terms of its highly toxic effects. Calculations based on experimental data show that if 1.00 pounds of ABS pipe was burned in a 10,000 ft^ apartment it would result in a maximum concen tration of HCN approximately 20 times the lethal amount. The same calculations for 100 pounds of PVC pyrolyzed in the same apartment show that a concentration of HC1 as high as 57*3B5 ppm could be reached, about 57 times the concentration that will cause lung edem a on very short exposure.-S The use of plastic pipe in high-rise buildings is of concern d.ue to the fact that it will melt or burn through thus allowing toxic gases, smoke and fire to penetrate fire partitions. It is evident from this literature T:` search that the use of plastic pipe is not a safe practice in many situations and that metal pipe'would be TessThazardous. : Choice of materials, and development of building practices that will contain any fire which breaks out, will minimize smoke production, smoke toxicity and smoke exposure are clearly desirable. c>p\- oo70$A I. Int roductIon Smoke from smouldering or burning materials is at least as hazardous to life and property a$ uncontrolled fire (1). Indeed, it Is widely recognized that more than half the deaths attributed to fire are caused by .smoke inhalation rather than by heat or burns (l). With the increasing use of plastics In bui1dIngs , Jncluding furnishings, upholstery, piping systems and electrical and thermal insulation, there is increasing concern about the fire- and smoke-producing hazards of these materials. Possible increases ?n danger to fire fighters and rescue workers resulting from the substitution of plastics for more traditional materials is also a concern (2,3,4). Such concerns have been reinforced by a number of recent fires. A good example is the November 1980, fire at the KGM Grand Hotel in Las Vegas. In this fire 679 people were injured and 84 people lost their.lives; Sixty-3 four of the victims were found on the upper floors far-removed from the J site of the actual fire.i The source of ignition was reported to be electrical and 1arge'amounts of foam plastic padding and other plastics were included in the fuels (5). All deaths were attributed to smoke inhalation (6) but the.lethal component or components of the smoke were not specifically identified. The fact that the concentration of carboxyhemoglobin in most of the victims was not high enough to have caused death (7) indicates that other toxic gases or smoke particles must also have been involved. This opens the question as to whether or not the burning of plastics increases the lethal potential of fifes. Although a detailed consIderation of the potential fire hazards of the numerous plastics now in widespread use in beyond the scope of this report, much can be learned about the dangers which can exist from considering two very common plastics, PVC (po1yvlny1chloride) and ABS (acrylonitrilebutadiene-styrene). The largest single use of both PVC and ABS Is for .;i piping systems.*; PVC Is also widely used for electrical conduit, electrical insulation and telephone ducts (8). Lesser amounts are used for wallpaper, window frames, and upholstery. A thorough search of Chemical Abstracts for information on the combustion* and pyrolysis (thermal degradation) of ABS and PVC was* carried out'. The results are presented In this report. ,ftL 0000708*3 * The Hazards of The Py Jol VS s/Co.T.bus t I on Process The fire f>32ard a material js described by: 1. its combustlbi1i;y (how readily ana how rapidly it burns or releases heat) 2. the amount of smoke it produces, and 3. the toxic gases released during heating and combustion (9)- These factors are in turn related to the chemical composition and weight of the material which will determine the total heat, smoke and toxic gases that can be released under specified conditions. The exposed surface area, surface characteristics, thermal exposure and the location of the material within the fire system will also affect the fire hazard associated with it- The combust- ibility can be described by ease of ignition, rate of heat release, and total heat release (9). The ease of ignition and the rate of heat release from * some plastics is very high compared with such traditional materials as wood (9,10,11) but other plastics are less combustible than wood (10). Smoke evolution rs a concern relevant to a significant percentage of the plastics used. In the United States 33% of the li<,791,000 metric tons of 'pi ast i c sold in 1977 were the three types most prone t<? produce smoke: PVC, ABS and polystyrene (12). Smoke is hazardous because: (13) 1. if dense it impedes escape, rescue or fire-fighting by obscuring vision 2. It is irritating and can be destructive to tissues of the eyes, nose, throat and lungs 3. it may contain lethal or incapacitating concentrations of toxic or suffocating gases k. certain of Its constituents particularly acid gases, may damage property. The particulate and gaseous fractions of smoke can be considered separately, and "smoke'* in this report refers to the particulates only, * Combustion Properties of ABS and PVC 1. Smoke Very dense smoke is rapidly produced from both of these plastics and unlike with wood becomes denser under flaming conditions. Indeed for PVC the time until an observer would find It difficult to see an exit sign throush 10 ft. of In . 12.5 *20x1 ft. toon was extlnated to be 2.1 SAL 000070844 -3- minutes under smouldering conditions, and 0.5 minutes under flaming conditions (Hi). The corresponding times for ABS (cycolac) have been reported as 2.98 minutes (smouldering) and 0.57 minutes (flaming) (15). This short time would make escape difficult or impossible in many situations. The corresponding values for various woods ranged from 8-15 minutes (smouldering) and -10 minutes (flaming) (H). 2. Toxic ^ases In addition to carbon monoxide which is often present when any organic substance burns, the major products of concern from ABS and other nitrogencontaining substances such as wool, nylon, orlon, and acrilan are hydrogen cyanide and nitrogen dioxide (16,17)* When PVC is subjected to thermal degradation, under smouldering or combustion conditions, hydrogen chloride gas is produced rapidly and quantitatively somet Imes '"`be fore smoke is evident (18). From one gram of PVC, 0.583 g of hydrogen chloride Is produced. This facile production of large quantities of acid gas in fire situations is perhaps the most striking difference between PVC and more traditional materials. Some benzene is formed at the same time (19,20,21). When acrylonitrile is pyrolyzed or burned, hydrogen cyanide and nitrogen dioxide are.formed. If^ydrogen cyanide^is inhaled, it causes a reflex stimulation of breathing which in turn will lead to a greater concentration of the gas entering the body. It also inactivates certain respiratory enzymes thus preventing the use of oxygen by tissues (22). Concentrations as 4 low as 100 ppm can be lethal,^; Safe concentrations of nitrogen dioxide are below 5 ppm. Nitrogen dioxide is irritating to mucous membranes and when inhaled will cause damage to tissues in the upper respiratory tract. Inhalation of very low concentrations may cause 1'ttle or no damage to the upper respiratory tract but may result in death hours later due to pulmonary edema (abnormal accumulation of serous fluid in the lungs) (23). If inhaled, hydrogen chloride gas dissolves in water to become hydrochloric acid and will severely damage the upper respiratory tract leading first to breathing difficulties , then to pulmonary edema and death. Hydrogen chloride' also acidifies the blood and destroys hemoglobin thereby interfering with : transport of oxygen (2A).':; However, when it is first inhaled it will tend to cause the larynx to close (1 aryngospasm) thus interfering with breathing but SAL 000070845 k but protecting the lungs. While PVC decomposes, benzene Is also formed and it will depress the laryngospasm allowing both solids and aerosols (including * acids) to enter the lungs (22). The main action of carbon monoxide (CO) after ft Is inhaled, even at low- concentrations, is to Bind reyers i hi y- w i tfi hemoglobin (H5l to form carbcrxy- i hemoglobin (COHb). Thus the % COHb of a pers.on'3 blood is related to the concentration of carbon monoxide in the atmosphere and the. time of exposure. Carbon monoxide displaces oxygen in the blood and leads to anoxia and death, if the reaction is not reversed. In general, most persons will not show toxic symptoms below 20% COHb. Death occors at approximately- 6Q.-7Q* C0Kb. (25 1a When carbon monoxide is inhaled there i& also a loss in nerv conduction velocity and a drop in blood pressure which depletes the blc . flow to the brain resulting in confusion and failure to respond to stimui; 22), : however, even after exposure to a potentially lethal or comatose leyel of carbon monoxide, 8D% of individuals will recover immediately or within a few- days. Then perhaps 2-15 months later, 15-20% of those people suddenly develop dementia and the "shakes" dying shortly afterwards^C^ , / The statement that carbon monoxide rs the primary- killer in fires has been disputed (22) but about 53>% of the fire deaths doe to smoke inhalation occur within 12 hours, usually at the fire scene with fairly sirght respiratory* tract, damage. The remainder of the deaths attributed to smoke inhalation occur after the victims are taken to hospital and treated. In these cases the respiratory tract damage continues to develop after they- are removed from the fire and would implicate gases other than carbon monoxide and/or the inhalation of particulates as the cause of death (22), * Carbon dioxide is also present in smoke, but not normally, in sufficientlyhigh concentrations to cause any toxic symptoms. However, inhalation of carbon dioxide will stimulate respiration which in turn will increase lnhalatior of any toxic gases present. Organic aldehydes and acids which are both ir-ritat ing and damaging to mucous membranes are also known to be produced from some materials (26). Human responses to oxygen depletion and various concentrations of gases relevant to this report are found in Appendix 1 (25). 0.0> -5- 3. FI ammab i 1 ? ty In general polymers with an aliphatic backbone such as polyethylene and polypropylene are very flammable, but their tendency.to generate smoke Is minimal. The addition of flame retardants, especially halogen - containing compounds*, wh i 1 e reducing the tendency to burn, increases the evolution of smoke ulOy and introduces strong mineral acid gases into combustion products. Halogen - containing polymers such as PVC are usually relatively non flammable, with high oxygen indices (ko.3% Tor PVC) but display high smoke generation when combustion is supported by the presence of other 'fuels which may include plasticizers. The oxygen index is the percentage of oxygen in an oxygen-nitrogen mixture which will support sustained combustion. The lower the oxygen index, the more flammable is the material. Representative oxygen indices are given in Appendix 2. Polymers with aromatic rings such as polystyrene and A5S not only generate dense smoke (10) but tend to be very flammable, dnfact, in several t studies, ABS was one of the most flammable polymers tested (11,27)- The burning character i stics and "combustibl1ityM of a sample can be described in terms of rate of heat release as well as ease of ignition, and total heat release. The sudden release of heat indicates a rapid spread of flame across the exposed surface. ABS exhibits a very rapid rate of heat release (see Figure is very easily ignited, and burns quickly compared to wood or PVC (9). Factors Affecting Suryiyal An important factor in a fire situation is a person's escape time; \ that Is the time interval Between the person being alerted to the existence of the fire and the point at which escape is no longer possible. The rate of production and distribution of smoke and toxic gases Is therefore very Important (2l, It has Been estimated that a sleeping person needs 12-15 minutes to awaken, react to danger and take appropriate action (2), With the very rapid production of smoke (and toxic gascs^frora ABS and PVC the person will often not have that much time. Judgment may also be Impa'ired on awakening es a result of breathing asphixiants such as carbon monoxide v;hile still*asleep, k 000070947 SA1- 6- Approaches to the Problem The question of the relative hazards and toxicities of smokes from different sources can be approached in two ways. The most obvious is to Study real fires but there are serious difficulties in i dent i f-y i ng sources of individual toxicants in such complex situations. One important study of residential fires in Boston employed a sampling system built into the firefighters' turnout coats to determine the concentrations of various gases in the smoke (26)."' Some autopsy data are also available on fire victims relating to toxic gases. For Instance, the COHb levels and cyanide levels In blood * re n indication of the exposure to carbon monoxide and hydrogen cyanide t the fire scene (2B). Symptoms described by survivors are also* documented Jn the case of PVC fires and provide an indication of whatgales n-iy have been present sal ooo> -7- The importance of the blood alcohol level of fire victims should not be overlooked but often is either not determined or reported. If It is greater than 0.1$ volume, there is probably a strong synergistic response with carbon monoxide that increases the apparent toxicity of carbon monoxide (22) and possibly also hydrogen cyanide to the brain. Indeed in one study of fire deaths In Maryland, }>$>% of the victims had a blood alcohol content of greater than 0.1$ (29). The second approach is to carry out laboratory scale experiments to determine the amount of smoke produced, the concentrations of the toxic gases, and the toxicity to animals of smokes produced from specific materials. There are many papers in the literature on these subjects but findings are often confusing or apparently contradictory and may be difficult to relate to real fire s i tuat ions. *& The wide range of factors involved in a real fire is difficult to reproduce in the laboratory. There are two distinct processes in a real fire: (1) pyrolysis (the thermal decompos11on/vola1I1 Ization of the sample without any flame being present at the immediate pyrolysis site) and (2) combustion (consumption of the sample by burning with a continuous flame). In the laboratory, pyrolysis and ^ombu s t i^o rT)^ r e invest i ga t ed^sepa ra tejjy. Hazards associated with the particulate and toxic gas fractions of smoke can be considered separately. Data are not generally available on .the biological effects due to the inhalation of smoke particulates but a concentration of about 1,000 mg/m^ air will cause immediate respiratory difficulty; much lower concentrations of 20-50 mg./m3 will cause light obscuration and can thereby interfere with escape (26)3^ I I. Smoke Particulates Tests for smoke-producing characteristics of materials employ one of two measurements techniques: gravimetric or optical. That is, some tests are based on determining the weight of smoke particles deposited on a filter under specified conditions; other tests measure the fraction of light absorbed or obstructed by the smoke. Both methods measure the airborne particulate fraction of the smoke and not the gaseous fraction. Results are apparatus dependent and are often reported for commercial products for which the composition is not given. Cross comparisons are 00007084? 8- - difficult but comparisons of materials for each method are valid. The best, known gravimetric methods are the ASTH E162 (30) and the ' Arapahoe smoke tests (31)- The most widely used optical methods are the KBS smoke test (32) and the ASTK 1)28*0 test (also-called Rohm and Haas XP2) * (33) which measure the density of smoke accumulated in an enclosure. In some experiments a modified KBS chamber is used which allows different levels of ventilation. The ASTh E8*i test (3*0 ana the OSU release rate ' test (35) measure, by optical means, the density of smoke flowing past a specific location. 1 I - 1 Results Using Optical Methods (1) KBS Test Specific optical densities (see Appendix 3) which can be measured with this apparatus are independent of exposed area of the specimen, chamber volume, and length of light path, but depend on specimen thickness, chemical and physical properties and exposure conditions. The exposed surface area of the sample is 6.58 square inches; the chamber volume Is 18 cubic feet (1*)`. Maximum speeifrc optical densities are shown |n Table 1 for a number of materials. , Table 1. Maximum Specific Optical Densities (Dm) -for Selected Materials (1*0 Thickness Dm Smolde ring F1 aming Polyethylene (UCC - DXH - 100) PVC (UCC - QYTQ.) ABS (Cycolac) Douglas fir t 1 250 mils. 11 526 315 780 380 780 780 156 Note that for woods is lower under flaming conditions compared to smoldering conditions, but exactly the opposite is true for PVC. The maximum measurable optical density was reached under both smoldering and flaming conditions for ABS. Times at which maximum specific optical Sens1ty- occur red (T \ and at ` fn which the specific optical densities (D^) would be equal to 16 in a 12.5 x 20 x 8 ft. room, the value at which an observer would find it difficult to see an exit sign through ten feet of smoke are shown in Table 2 (1A). Under smouldering conditions the times to obscuration for wood and PVC are very similar but under flaming conditions they are much shorter 0o,, w0 for PVC. It is interesting to note that doubling the thickness of the PVC sample did not change the time to obscuration even though it roughly doubted the time to maximum specific optical density. Note also that wood and -> polyethylene show significantly longer times to reach the specific opticaldensity (Ds = 16) than do the PVC and ASS samples tested, an important matter in terms of escape. Tab 1e 2. Times (in minutes) to Obscuration and Maximum Specific opt i ca 1 Densities (1M > Smolder? ng T m I for D s =18 Fl ami ng T m T for D s =16 Douglas Fir Polyethylene PVC rigid - filled PVC rigid unfilled - 1/8" thick PVC rigid unfilled - 1/V thick ABS *ABS 20 17 30 \k 33 . 11 2.1 5.5 1.6 2.1 2.1 3*0 19 9 n 5 10 6.5 *.6 *.0 0.5 0.5 0.6 0.6 * Data from reference 36 ' Table 3- Effect of Ventilation on Maximum Smoke Dens It i e s f rom Some Smoldering and Burning Materials 0*)- Material Smoke .Densities at Speci flc Ventilation Rates (Air Chances/h ID I 6 I! 20 Smoldering Rigid PVC, filled Douglas Fir 490 380 335 3D0 235 225 160 120 150 90 Fleming Rigid PVC, filled Doug las Fir 530 155 535 65 535 70 *75 60 375 25 000070851 10 The effect of ventilation rate c, the development of maximum smoke density is illustrated in Table' 3* It should be noted from the data that ventilation decreased the maximum smoke densities under smouldering conditions but that there was little difference observed under flaming conditions for PVC (Ik). ' Slmi lar observations were made by other workers^07,1 3) . ^*aA /V1"^ j ^ yt Z t-L- ABS also produced very dense smoke rapidly (27,56) under flaming conditions. At 1.5 minutes after ignition,Dj " 176, already a much denser smoke than that which would cause obscuration of vision. Specific optical densities are dimensionless but the time required 'to reach a given smoke density must depend on material surface area and chamber or room temperature. It is therefore, of interest to note that the ratio of sample surface area to chamber volume In the NBS test corresponds to 13 feet of sealed 3"'nc.h pipe in a k,000 cu.ft. room. -'-Therefore, burning even a short length of ABS or PVC pipe in a room would rapidly produce dense, obscuring smoke. (2) Asm D284Z (Rohm and Baas XP2) This test is limited to flaming conditions. The sample surface-to-chamber volume ratios are similar to the NBS test. It has been.reported that the amount of smoke produced is almost proportional to the weight of material consumed (3B). The amountrof smoke produced Ts~Vcry^dense. for PVC and ABS (in agreement with NBS results) (15). The times to obscuration (D^ = IS) for PVC sheets 0 in, x 1 in. x 0.0.158 In. or 1 in. x 1 In. x 0,Qk2k in.L were 0.03 and 0..0S Kii notes'shj^rter^tfian found In NBS tests 05l, ' Both PVC (YTQ) and ABS (cycolac) reached the maximum specific optical densities measurable with this apparatus. Various polyethylene's had Dm = 10 21k. For PVC (QCA - 2k60) of 15, 20 and kO mils thick, the respective maximum specific optical densities were reported to be 99, 82, and 319 (15). (Z) CSV P.elease Rate Test ' This test measures the density of the smoke flowing out of an exhaust stack under flaming conditions. The sample has 100 sq. in. of exposed surface area (9). Results show that the rate of smoke release and total amount of smoke * released for samples of PVC and ABC are many times greater than for oak (12) (Table k) . SAL 000070852 11 Material Table U. 05U Release Rate Tests Studies (17) Orientation Applied Heat Flux w/cm^ Max. Smoke Release Rate units/min-m^ Oak, 1" - PVC rigid pipe PVC flexible sheet, ABS sheet, 125 mil V 1.0 2.0 2.5 V 1.0 2.6 V 1.0 2.0 H0 1.0 2-5 0.9 5.5 6.9 nk 228 336 27*f 366 366 Total Smoke Release Un i ts/n-i 3 min 1C min 0-9 2.3 1.8 k.G 9.1 n.J1 0.9 91 .k 228 6^0 22.8 ^57 6^0 731 2.3 137 155 457 ^57 5^8 V = Vertical sample H = Horizontal sample 1 smoke unit in 1 m^ air will produce an optical density of 1.0 for a light path of 1 metre. The very large variation in rate of smoke release per ft 2 of exposed surface for different materials Is shown in Figure 2'. While the maximum rate of smoke release for red. oak is less than 200 "part i cl es''/mi n ft 2 the corresponding value fpr ABS at the same heat flux Is over 7900 and for PVC is about 5,500 (9). The use of piloted ignition and excess oxygen assures that essentially all decompositions vapors are burned and would minimize the smoke release'ln the case of the oak. SAL 000070853 12 Figure 2. Rate of Smoke -Release at 2.6 Btu/sec-ft^ (9)^ (4) Other* Ez^peri.r,enis Other workers using different types of apparatus also observed very dense smokes from ABS and PVC compared to wood (35^1,^2,^3) Mass optical density (MOD) (Appendix 3) relates smoke generation to the weight of sample rather than the area of sample exposed. Results are given In Table 5 (^Cl). Table S Mass Ootical Densities of Materials Under Flaming Cohtitions (^0) . Sample MOD cm2 gm AES PVC with 2B% plasticizer PVC PE Hardwood (3 thicknesses) 6900 5600 3^00 2300 300-800 The results from the different experiments and the various calculations all show that much denser smoke is produced under flaming conditions from ABS^S'hd SAL 00007085-1 - 13 - tl-2 Gravimetric Methods (V ASTM Z162 ' In this test flaming conditions are used and the particles are collected on filter paper positioned at the top of the stack. Some results for this test are given in Table 6. It will be noted that, as with optical methods, a~ large difference was observed between wood and PVC (12). Material Red Oak Exterior fir plywood PVC PVC, Fire retardant Table 6. ASTM 162 Results (12) (Flaming Conditions) S i ze 12x18" n ii M Thickness (mils) 750 250 1*7 147 Smoke Depos 0.3 0*3 28.3 10.5 This shows that the optically dense smoke released by these polymers at least partially due. to release of a larger mass of smoke particles. s (2) ^rapahoe Smoke Chamber The sample is exposed to the burner flame for JO seconds with air flowing through a filter at the top of the stack. The burner is then extinguished and air flow continued for a further 30 seconds to give a total collection time of BO seconds (44). Results are reported as percent smoke based on the initial weight of the sample or on the weight loss of the sample (Table 7) (12). Because some celluloslc materials (wood) smoulder for several minutes at the end of the test the calculation based on weight loss for these materials would not be valid and they are best compared to plastics using percent smoke based on * Initial weight (44). The results confirm th-at much more smoke is produced from PVC and ABS than from wood. ** In conclusion it can be stated that both PVC and'ABS produce copious amounts of dense smoke under both smouldering and flaming conditions. Furthermore, in the preceding discussion these plastics were compared with wood which is a traditional building material but JS not used for piping or copduit systems. Traditional metal piping does not produce any smoke under normal fire conditions. * SQL oo?oas5 Material - Table 7. Arapahoe Smoke Test Results (12) (Flaming Conditions) % Smoke based on Initial Weight Weight Los s Cellulose Fibreboard, coreboard Ha rdboa rd PVC flooring PVC rigid PVC, flexible, fire retardant ABS, fire retardant 0.570.06 0.21 1-33 2.36 4.02 0.75 0.08 6.23 10.52 12.74 20.54 11-3 Relative Rates of Smoke and HC1 Release From PVC In the case of a rapid electrical overload of PVC insulated wire, the evolution of HC1 preceding the detection of visible smoke is as shown in FIgure 3 (1B). Figure 3. Comparison of Rates of Formation of HCl and Smoke for Different Heating Rates of PVC Insulated Wire. (A=40eC/min and B=15C/min) When pure PVC film was used the smoke and HCl evolved at the same time regardless of the heating rate used. To complicate matters further, it was found that a commercial sheet of PVC evolved smoke about half a minute before HCl was detected at a heating rate of 20*C/min, and, that at decreased heating rates smoke was detected before HCl. Under some circumstances, particularly in the case of a rapid electrical overload, HCl could be a | significant hazard before a person became alerted to the fire by the presence '>. r r: i n re eKft.dri k* awar^ of the fact that danaerobs acid oases SAL 000070856 can be'present in areas involved with electrical fires even though there may be little visible smoke. 11-4 Toxic Gases Adsorbed on Soot (2) BCl Irritant gases are found to be adsorbed on soot. HC1 adsorbed on soot would gain access to the lungs where, on combination with water, hydrochlocic acid woutd be formed causing a violent inflammatory response, resulting in destruction of lung tissue (2,1*5)' Hydrogen chloride from PVC combustion was found In the gas phase, and both loosely and tightly bound to the soot. About 2% of the total hydrogen ` chloride was found adsorbed on soot. The hydrogen chloride that was loosely ,O bound amounted to 15 mg/g soot on soot particle diameters of 300-1100 A. CO.03"0-11 microns). Such particles would agglomerate rapidly to form larger particle clusters. For rigid PVC the size distribution of particles was found to be 0.1-Q.2 microns and the mean particle size was smaller for flaming than for smouldering conditions (42). The particle sizes ranging from 0.1 to- 2.5 microns diameter (corresponding to soot aged from seconds to gne hour) would be retained in the alveolar sacs to an extent of f romf20-40jof those inhaled (46). ' Assuming there was 1-57 grams of soot/m^ and no HC1 in the gas phase and that the breathing rate of a person is 18 1/min, after one hour of exposure 0.7 grams of soot bearing 13 mg of loosely bound KC1 would be retained in the lower lungs (46). If there was a gas phase hydrogen chloride concentration of 150 mg/m^ with no soot present, at a breathing rate of 18 l/mln and an exposure of one hour about 108 mg of HCl would be retained in a person's body. (46). (It has been estimated that 62* of the hydrogen chloride gas inhaled is retained in the body (47)- X Therefore, it was concluded (47) that gas phase exposure was about eight times as severe as exposure to soot; however the HCl on the soot would cause damage to the lungs. (2) Totyarcrr.atic hydrocarbons Polyaromatfc hydrocarbons have been detected in small amounts from the J combustion of various plastics, including PVC (48,45,50,51). The : production of these compounds was relatively lower under flaming than under i non-flaning conditions (49) (Table 8) and included the potent carcinogens benzo [a] pyrene and 7,12-dI methy1benz [a] anthracene. As the humidity of the ventilating air increased the production of polyaromatic hydrocarbons SAL. 000070857 - lb - Table 8. Amount of Polyaromatic Hydrocarbons Found In PVC Pyrolysis Products under Simulated Fiire Nonflamii and Flaming Conditions (*<9) . ' Amount vg/g of PVC Nonf 1 arn 1 nq Flaming Fluorene Phenanth rene 1-methyl phenanthrene 9-methy1 anthracene 9,10-dimethylanthracene Fluoranthene Pyrene 1,2-benzof1uorene .2,3-benzof 1 uorene Chrysene. 1,2,-benzoanthracene tr phenylene 7,12-dimethylbenzo [a] anthracene Benzo [a] pyrene, benzo [e] pyrene Perylene 3-6 29.1 19.1 15-5 15.6 10.5 11.6 35-3 32.8 16.0 3.5 5-3 7.3 3-6 3-5 . 3-6 *< -7 - 6.1 **-5 5.8 10.5 - l.k decreased (k9). The evolution of benzo la] pyrene generally Increased with increasing temperature but.at high temperatures it decreased drastically when a high air supply rate was used (48). Whilst these compounds are not considered to have acute toxicity they V could be of concern to firefighters who are repeatedly exposed to them?! It i$ difficult to assess the dangers due to the^amounts of polyaromatic hydrocarbons detected Ir> these experiments. I1-5- Smoke Detectors Vith respect' to detectors it is interesting to note three papers in the > l ite'ratu"re'(52 ,53.5*0 Tests showed that ionization detectors are particularly insensitive to the degradation products from PVC, polyurethane foam, "and polyethylene (52). All ionization detectors tested showed a decreasing sensitivity (based on increasing smoke obscuration at alarm) in the order ''punk11 (a standard calibration source) > polyurethane > polyethylene > PVC (53)* PVC cable overloads of 3-5 times the nominal current were detected by ionization' detectors but the alarm was given at 3'10 times the maximum allowable hydrogen /T chloride concent rat ion (5*0. ^ In the case of PVC, evolution of toxic gas is a major threat before the_re is sufficient smoke released to activate whatever detectors that may be in SAL 000070858 17 - place (55). 111-1 Decomposition of PVC 1. Temperature at which deconpos!t!on takes place Dehydroch1 or Ination* of pyc is essentially- a.thermal decomposition. Flaming and combustion conditions are not required (55). Dehydroch1 orination is reported, to begin between 150-190*C (57,58,59,60)_; becomi ng quantitative at about 270C (l8,6l).-: It was also'observed that- py rolys i s .of PVC-at 600lC^ under helium atmosphere resulted in quantitative recovery of HC1 and formation of a chlorine- free ash (52). Wool ley (5^) showed that the rate and extent of dehydrochlorination was essentially independent of the amount of oxygen presentin'the'atmosphere;^ \ Removing HC1 from the reaction zone by evacuation decreases the rate of dehydrochlorlnation PVC but does not change the rate of benzene formation^(6i()^ Until recently the only product reported to be produced during the decomposition * of PVC below 220C was hydrogen chloride (65,56).* Voorhees et al (21) '*#. established the fact that benzene and hydrogen chloride were.'formed simultaneously during the thermal decomposition of'PVC..-; At 275*C a very rapid weight loss occurred accounting for 60^ of the initial weight. The product was about 95% * hydrogen chloride and 5% benzene^(20)^ A second weight loss occurred at higher temperatures (66). In another experiment in which 1.0 g of PVC was burned 583 mg HC1, 779 mg, of carbon dioxide, ^2 mg. of carbon monoxide, and 36 mg. / benzene were formed (66).' Other workers found that burning 3 g PVC in a closed container (0.12 1 air) at A00-800 gave a gaseous mixture containing 14-3% HC1_, 10.6 CO, 10.6 and ^.0% organic materials (67). Burning PVC In air gave 0-^96 9 HC1 , 0.001 g COCl^ (-disputed by others), 0.229 g CO, and 0.^33 g C0^ per gram of PVC (67). Although a very small amount of phosgene had been reported (67) subsequent^ workers have been unable to detect either phosgene or chlorine (68,69). A T mixture of smaller amounts of saturated and unsaturated hydrocarbons is also V formed, in addition to benzene_(70.71,60,20,72,73,7^,75,69). ? At temperatures greater than 300* eighty compounds were formed in relatively small amounts from the combustion of PVC (76). Various i chlorobenzenes (77*78) and formaldehyde (75) have also been detected. At 200*C no hydrocarbons were found (77). Carbon monoxide appeared at about 500*C (79,80) and at higher temperatures was the major product (81)? The higher the pyrolysis temperature the greater the variety of gases produced (82)/? SAL 000070839 - |o t. Rate at which toxic gases are produced Several factors affect the rate of dehydroch1 or 1nation. The rate' Increases-wi th Increasing temperature (59) 'and with Increasing ajr^fjw(^3 72,56). From the rate constants of decomposition the time required for 20, AO and 60* dehydrochlorJnation of PVC in and air between 2D0-300t,C was calculated (72). These results appear in Table 9'. Table S- Calculated Time (min) for Dehydroch1 orination of PVC (72) Temperature *C 200 220 2 A0 260 280 300 20* N2 Ai r A0* N2 Air * 60* N2 Air 251 .A Al.A 7-9 1.69 0.A1 0.11 9 2A.3 5-8 1-55 0.A5 0.1A 619.8 283.3 102.1 60.0 13.A 1^*3 A.16 3-82 1.00 1.12 0.27 0.36 1237-8 585.8 20A.0 119.8 38.7 8.31 2.00 28.6 7-62 2.23 0.53 0.71 The experimental values were found to correlate well with the calculated values (72).7 It should be noted that time for 60* dehydroch1 or 1nation to occt is less than one minute at 3^0C. j The rate of release of hydrogen chloride from 1.5 inch (3-8 cm) PVC condi at different heat fluxes is shown in Figure A 13). Figure A. <T- '* Rate of' Release of Hydrogen Chloride from 1.5" PVC Conduit (9)3 SAL 000070360 19 - The relative rates of smoke and 'oxic gas release is a matter of some concern.' In the case of a rapid electric cable overload the evolution of hydrogen chloride precedes the appearance of a measurable amount of smoke (18). At 3S5*C heat and smoke release from PVC were very low but significant release of HC1 occurred (9). It is of interest to note here that tests with chlorinated PVC water pipe showed that co^p^^l^y^tTTp'fThydro'gen^'.chJpri^de released at about*$8lXIi3fc Heat and stroke release were very small and increased when obvious burning occurred after nearly all the hydrogen chloride had been released (9) 3. Full Scale Fire Tests .% Full scale fire tests have been carried out In a special compartment (3 x 3 x 2.5 m)-corridor (12 m. long x 1.3 m wide x 2.5 m high) facility designed to represent a room attached to a corridor (91). The fire load consisted of wood (12 0-2 ^ 0 Kg) in the form of a crib with thick PVC wall linings (rigid PVC sheet 0.63 KgJ_ In the compartQent or corridor. Eyer^| at `tTie'"corridor end of 'thcutest~rig the temperature;ii:of;:;thefire" gase5_j n_all^teiTt5 exceeded a .bearable temperature, wi thnva ,fewj?inute's^aftec&J.ghji4on.;^iJ The assessment of the hazard arising from the presence of CO and HCl is difficult because of the very high temperatures of the undiluted gases. In practical situations it is often necessary to consider the dilution of gases as would occur during the discharge of fire gases Into the air enclosed within a building. The'jnaxi.muTTconcent rat >ons o^hydfogehTichlor i de and carbon 4 -- *L.` .J' (. .. ^ monoxide formed"when the compartment and corridor gases are di1 uted withaclean aTrsto a'bearable'temperature (120C) are shown 4n-"Table 10 (81*). * Table Id. Production of CO, HCl and Smoke from Full Scale Fire Tests with PVC Wall Linings, After Dilution to a Bearable Temperature (8^).' Fi re Load Wood (kq) PVC r<q) Compa rtmen t CO (ppm) HC) (ppm) Corri' dor CO (ppm) HCl (ppm) V1 s i b (m) 123 123 120 120 21*0 2-^0 0.9 2.63 35.0 115.0* 95.0 115.0* 2,750 232 2,230 526 2.350 6.730 *PVC used as corridor lining 3 79 3,230 360 3,920 1,8oo 4,150 -- 850 -- 566 3,330 8 67 1, 1*60 9,690 1,830 20,500 1.8 1.6 2.1* 1.2 2.1* 2.0 S/U 00070861 'Using a 127 9 ^ood crib and 100 kg PVC wall lining In the same apparatus the amounts of HCl and r~.were measured and compared to a control experiment in which the wood only was present (72). The results are shown in Figure 5. O =Ow 4 O2 ft 10 at ----- CO *"*") ------- Co --- --- HCl (mXtcJ t fvC-) 30 HU ^ UrV, <0 Figure p. Toxic Gas Production from Wood and PVC Fires (Adapted from ref. 72) The rapid and facile release of HCl when PVC is heated suggests that PVC should not be used where there is a possiblity of it becoming overheated. In service corridors, for example, If a f\re should break out, very high concentratio of HCl vapor are to be expected if PVC piping, conduit and wire insultation have been employed. Firefighters need to be aware of these hazards in fighting such f i res. . Effect of Composition of PVC on Decomposition Products The release rate of hydrogen chloride for different PVC materials is fairly uniform however the temperature at which decomposition occurs and the amount of hydrogen chloride released can vary. Cectain^-Tnorg'anic_>iTiers Inf pyeTco'^ourT^ .m3dS'Orberir^durrfrgrrpyToi VS'i^^h~'d,,;cbmbugrTon exampi PVC^7reI]!Jg^L]jXtR^^ stoi ch i orneTr i cfTeq u \ v n^tTjdf7,HC T KerT"b u r rieTT.Tt 8 5) 13 Rigid PVC film containing plasticizer and a small amount of stabilizer completed a major part o`f dehydro chlorination at less than 30DoC, while rigid PVC plate containing about 5% stabilizer evolved maximum concentrations of HCl at ^OO'C (63). P V C^aftTffcta 1 eat her "evol ve'cT^about'"'!/fothe Jamount"of"HC r^compa'fed^t'cT PVC .'taw 69 iS6)- The amounts of aromatic hydrocarbons were found to be dependent on the presence of additivies (78). HeatJ ncpPVC^pl as t i c iIzed;-Wtt d t b u t y 1 ph t h a 1 a t e (87) sal 00070863 * iI I I I -2 p-:CC~pos i t ion of A3S Vhen ABS is pyrolyzed in atmospheres of either nitrogen or air (36) a large weight loss begins to occur at about 300C. The decor,pcsition products which have been reported are hydrogen cyanide (HCN), nitrogen dioxide (iJO^) , methane (CH^), hydrogen and ethylene (C^H^) (33,17,39,70- In 197^ , Chaigneau (17) using a sample of A3S (22% aery 1onitri1e( 19%' butadiene and 595 styrene) subjected to temperatures of 500-1200*C under dynamic conditions In air found the HCN and NO^ production shov.n [n Table 11, Table It. Decompos 11Ion Products from A35 (17) Temp C 500 600 700 Soo 1000 HCN g/lDOg ABS N02 g/lOOg ABS 3-00 0.012 3-56 it.03 4/62 0.015 7.61 1100 4.53 0.01 1200 5.^2 Much less of the n11 rogen was f ound as N0j as compared to HCN. amount of HCN was formed at 1QD0C under these conditions. The maximum "Surni^ancT Js uchTya^/O^)/al so/'K'T n^jJypa^ I.pnT/IlT^ ranging'from^ ^00180DC .fo'urTd~'that"YKe^amounr^of j.HCN'^ro"dUCdTfro'm'ABS pipe ^ ' increased as"t he'7Ve~mpe rat ure'increased rn'"agreerr.en t 'Wi th Cha Igheau. '^They also observed that -the-y ield- of~HCN -was ;highest -in a-'50% ^ r`r'T'^"'505ro'g^er?"| "atmosphere. \ IV Tox I col ogy- Vhen an animal or man. is placed In contact with a chemical agent it can produce an acote toxic effect by acting as .a primary- irritant upon the skin and/or mucous membranes or by being absorbed into the blood stream. .Absorption of very- low' concentrations may affect mental functions. The most common syndromes associated with exposure to combustion products are those resulting from impaired oxygen delivery or transport caused &y impaired pulmonary function, decreased am5Ient cxygen or carbon monoxide b'indlng to hemoglobin. Animal experiments are done in several different ways. Behavioural endpoints, for example, time to inc=pacitation, are sometimes determined. This 'is' considered to be direct ly '"related to'escape capebi'l i ty as ' ^ incapacitation is defined as the onset of staggering /'prestrat ion,"collapse or f convulsions (SOl. Phy s i o 1 09 I ca 1 changes can be monitored by recording SAL 000070863 changes in respiratory rate* heart rate and rhythm (EKG), brain wave activity (EEC) and blood pressure (2*0. The t Ime to death for animals exposed to decomposition products under specified conditions has also been used to '*** determine their toxicity (91 ,92,53,9**55) Th i s'V-does'*r>ot allow for cons I dera ttor of slow-acting toxicants such as HCl. The traditional toxicological approach ?s through determination of the dose required to cause death in 50% of the animals (LD5D). It can be determined.for a single toxicant but combustion y or pyrolysis atmospheres are complex and may contain many varied toxicants y making It impossible to determine a true "dose-response" relationship. The J LC50 (sample weight lethal to 50% of the animals) is sometimes used to assess toxicity (95). It has also been defined in the literature as the concentration of material in the atmosphere inhaled that will produce 50% mortality (96,97). Apparent lethal concentration (ALC50) is defined as that concentration of gaseous pyrolysis products in the atmosphere being inhaled which will produce 50% mortality (Sc hist opa thol og i ca 1 studies have been carried out (98,99). The type and/ extent of damage in the t i ssues of di fferen't^partj:' of., the..animal s is a good indication of the toxic substances that were inhaled before death. According to Hilado (100) 85.66% of the plastics sold in the United States are less toxic "than" wood/'^Uiese results were based on "time to death" data for mice in an unvented chamber, and carbon monoxide and methane were the only gases for which analyses were done. ~I t was noted that, in the case of A3S, the concentration of carbon monoxide was too low to have caused death (100,90,101,102,103). On the basis of these tests PVC was said to be less toxic than wood (100).; These results have been questioned on the `basis that much HC1 probably did not reach the animals due to condensation and the fact that it is not a fast-acting toxicant (24).; The latter point is important because only deaths occurring during exposure were recorded (100). V/hen wood Is exposed to a 2-5 W/cm2 radiant heat flux In a non-flaming mode, animals are Incapac i ta t ed at a carbon monoxide level of 7% (22). This' is likely due to inhalation of a mixture of aldehydes including acrolein, ;j an extremely strong lachrymator which is lethal to humans at concentrations of 10 ppm (see Appendix l). At a higher heat flux (7-5 w/cm^) which is just below the ignition point the animals do not develop symptoms until a much highe carboxyhenoglobin level is present (22). Under these conditions the aldehydes vould form and then be rapidly destroyed. Quite different toxicitics were observed using dynamic air f1ow conditions SAL 000070864 - 23 - and temperatures from 400 - E00*C. Toxicity factors, based on the concentrations fatal to man in 30 minutes, the weight of sample, and the volume of each toxic gas produced were calculated and are shewn in Table 12 (16)' From these data it can be seen that the toxicity of the decom.pos i t ion products is primarily due to HCN and HCl in the case of ABS and PVC, respectively, with carbon monoxide ^ playing a minor role. . Table 12 (16) Calculated Tcxici ty Factors (l/g) Materials Polyscrylonitrile Nylon 6 ABS pipe PVC White Pine CO "2 HCN HCl 7 1 1201 - 17 1 931 - 10 1 267 - 12 1 - 343 47 3 - - A study of 72 residential fires in. Boston (26) in the early 1370's using a sampling system built into the firefighters' turnout coats, showed that acrolein, benzene, hydrogen chloride, hydrogen cyanide, nitrogen dioxide and , carbon dioxide were present at real fires. The carbon monoxide concentration in only 23% of the f i res "exceeded 500 ppnT. At this concentration people would experience hallucinations after 30-120 minutes (Appendix 1). A lethal concentration to man in 30 minutes would be about 4,000 ppm (16). Carbon dioxide at the levels observed in these fires would not have been sufficient to be a significant hazard in contrast to engineered burns where high carbon dioxide V concentrations were observed. In only six fires did the oxygen concentration fall below 18%. A further study in 197^ (26) again showed that low oxygen concentrations were not generally significant. This also is In contrast to results from model fires which consistent1y.showed low oxygen concentrations (26) An investigation of 135 fire injuries and deaths, carried out by paramedics taking blood and breath samples from the victims Tmmediatly after their reir>oval from the fire showed that many had low csrboxyhemog1obin levels (COHb) (22); ` 24% had COHb greater than 50%, 36% had COHB of .11-45% and 11% had COHb of 7~10%J Clearly carbon monoxide alone did not cause a high percentage of these deaths. What did cause them remains unanswered In r.sny cases, f When a mixture of toxic gases is inhaled synergism (meaning more than SAL 000070865 that is not well understood. There appears to be a strong synergistic response between blood alcohol and carbon monoxide. If a person has a blood alcohol content greater than O.lt (volume) his CCHb need not be higher than' for death to occur (22 *22)* It is interesting to note that both alcohol and carbon monoxide interfer with the availability of oxygen to the brain. It is therefore, a reasonable expectation that hydrogen chloride which interfers with breathing and hydrogen cyanide which interfers with use of oxygen by tissues may be members of the same synergistic complex. The rstio of the percentage of carbon monoxide In the blood to the < percentage of carbon monoxide in the atmosphere is always higher with fumesfrom the combustion of materials than it is with carbon monoxide alone (2k). It is possible that this Is due to increased respiration caused by other j gases present such as carbon dioxide or hydrogen cyanide. A s atistical .analysis of data on the combined lethal effects of carbon monoxide, carbon dioxide and oxygen depletion showed that generally the effect of a combination of these factors was additive and even when synergism occurred its contribution v. ds minor (10 k) . An increase in the ambient temperature which is likely to occur during a fire has been reported to lower human resistance to toxic fumes (105)> This Is an area v;here much work remains to be done if we are to understand what is occurring. In time such studies may indicate why people die in atmospheres in which the maximum tolerance levels for various gases known to be present have not been exceeded. 1V-1 PVC Tox1co1ogy 1. Physiological Responses a) . Changes in Respiratory Rate Physiological changes accompanying the decrease in respiratory rate have i been well-documented In laboratory animals and humans (106).* The irritant nature of pyrolysis gases from PVC was assessed using the .decrease in the respiratory rate of mice (58) . The animals were exposed under dynamic air flow conditions. For mice the ^ in ng/l of pyrolysis products were found to be: (106) (RD^ Is the sample weight that caused at 50* reduction in the respiratory rate) SAL 000070866  25 - RD50 Tn9/1 Material pyrolyzed 0.24 0.50 0.13 --< 0.45 (^"l 5 p P "0- Doug las Fir PVC (no plasticizer or fire retardan PVC (piasticizer) HC1 The concentration of chemicals which caused RD50 in mice were found to be intolerable to man. The 0.1 value for mice was uncomfortable but tolerated by man (10?)* b) . Other Physiological Responses Thermal decomposition of polymers can produce chemical species that may contribute little towards sensory Irritation but which would have a significant lethal potential. For example, benzene which has been shown to be produced from PVC at the,same- time as hydrogen chlor ide*T(20,2 1) '} $ a powerful `^5"^ sensitizer of the heart to epinephrine.^'Thus cardiac arrhythmias (irregularity of the heart) and ventricular fibrillation (rapid and erratic contraction of the individual muscle fibres of the ventricular walls of the heart producing weak and irregular heartbeats) could .be inducedpa rt i cul a rl y if a person was also experiencing a deficiency of oxygen. Such effects on the heart during exposure of rats to thermal decomposition products of various polymers have been noted (10&). The maximum rate of decrease in respiratory rate is not as*) f\ Important as the time of onset of irritation and its duration. The total j ^ response was quantitatively related to the total stress Imposed on the animals by the Sensory Irritation Stress Index (S 1 S I),; (38) On this basis * PVC was more toxic than douglas fir and polyurethane.' A comparison of PVC with HC1 suggested that the sensory irritation response was due primarily to HC1 (98).. Rabbits were exposed to PVC pyrolysis products under smouldering (400C) and flaming (8000C) combustion for thirty minutes and the arterial p0^, pCO^, pH, central nervous system {EEG) and cardiovascular system (EKG) were monitored (24). As in the respiratory rate s tud I es ,^,the' i ntoxi cat ion syndrome due to ^ combustion of PVC was found to resemble the results of exposure to HC1. The concentrations of carbon monoxide present were insufficient to have killed ? the animals. The rabbits died during the recovery period, sometimes after* 15-30 days. With carbon monoxide alone, the EEG activity decreased and cardiovascu1 ar modifications- were not laroc (24). On tK? wri =rp ur SAL 0070867 decomposition products caused great decay of the cardiovascular system, lowering of the EEG and rapid appearance of acute pulmonary edema'(abnorma1 accumulation of serous fluid in the -lungs). When a water trap to'Temdve HCl was' present-''*" only the effect of carbon monoxide was observed In the rats and they survived exposure to the pyrolysis products from about five-times as much PVC (2*0. ? With wood fumes the effects were the same as for carbon monoxide for the first fifteen minutes, but Just after this period a dramatic decay of the*'*'''? cardiovascular system occurred. Death followed at about the end of the thirtyminute intoxication period, and acute pulmonary edema was observed. Acrolein and other aldehydes known to be present in wood decomposition products (127)" could be responsible for this effect (2*0. ^ Klshitani (108)- reported that EKG (cardi ovascular) abnormalities in mice exposed to PVC degradation products appeared prior to the generation of large quantities of smoke.. This Is a similar effect to that experienced by firefighters at PVC fires (see Section IV-*0, and is'more evidence that HCT is evolved before detectable amounts of smoke. The COHb of dead mice exposed to PVC degradation products averaged 2.1.25 which is much below the lethal / ar-ount of about 70% (109). 1 Workers acutely Intoxicated by inhalation of the combustion gases from PVC had moderately elevated venous COHb chloride Is known to cause this, whereas carbon monoxide results in high pO^ (2*0 . The results of all of these physiological experiments seem to indicate that the toxicity of P'*C degradation products is mainly due to hydrogen chloride. 2. Horta1ity a). Time to Death and Lethal Concentration Time to death is a* very poor index of toxicity because extremely toxic chemicals are not necessarily fast-acting (111,22), Using time to death as a toxicity index PVC was less toxic than wood (55,112,113). However, when the sample weights lethal to 505 of mice during a 30-minute exposure period and a 10-minute recovery period are determined the values were 12-15 grams of- PVC and 6*i g of douglas fir (11*0. Dynamic conditions were used and PVC is clearly much more toxic than wood in this case. Whether static or dynamic conditions wer used was found to make a significant difference to the toxicities of materials, with irritant gases such as HCl playing a much greater role under the dynamic condi t ions (*<5) . It Is Interesting to note that when HCl, CO and CO^ are removed from PVC pyrolysis products the time to death for mice is about twice as long (2*0. SAL 0070S<SS - 27 - 3. H ? s topathological Studies Based on pathological changes observed in mice PVC is much more ' 9 hazardous than douglas fir or polyurethane J[S8). It must be noted that the mouse is an obligate nose breather and man is a voluntary nose breather. When irritation occurs, man will convert immediately to mouth breathing and the first susceptible epithelium would be the larynx. Damage to this area comparable to that seen in the nose of the mouse exposed to HCl or PVC pyrolysis products would markedly obstruct the airway either killing the victim or necessitating immediate surgical therapy (115)* A comparison; of the damage to tissues from exposure of animals to HCl and PVC degradation products led to the conclusion that HC1/was^'the^principa 1 contributer to the toxicity in the case of PVC (59,2*1,22). After exposure to PVC combustion products, the development of completely abnormal cells was observed In rats (22). If the PVC contains antimony * a massive haemorrhage may occur *i-5 days later (22). / IV--2 ABS Toxicology 1. Behavioural Endpoints and Mortality Nearly all the experiments with ABS have been done using a method developed at the University of San Francisco referred to as the ,'USF3e'sk'1 (93)'A second method, the Federal Aviation Administration-Civil Aeromedical Institute (FAA-CAMl) method has also been used (116, 117)* *The tines to various behavioural endpoints and to death were determined. In these experiments the exposure chamber atmosphere was never analyzed for HCN or NO^, but it was noted that the concentration of cacbon monoxide was insufficient to have caused death (118,90,101,102,103). This is in contrast to the case of polyethylene where the major toxicant is carbon monoxide (116,119). When the "USF'' methods were used the introduction of forced air flow (G,H,l) caused a marked reduction in deaths In the case of polyethylene but it resulted In decreased times to Incapacita11 on and death In the case of ABS. Table 1*4 {120,116,113)* The times to these endpoints also depended on the rate at which the sample was heated, and were shorter when ABS was exposed to a fixed temperature of B00eC than when a rising temperature* program was used^Tablc 1 h) (.12 1 , 122,120, 103) * The rel stive toxieities of the pyrolysis products appeared to be fairly insensitive to-the temperature program used (97). The effect of oxygen depletion was not discussed in any of these papers although in a control experiment using methods B,E, and F T M a 1 tl ^ 'tka n,,ann ^ * a r- ^ * 7 ,, J, . - J . _____ SAL <>0070Q69 Table Results for "USE" Tests on Mice (120,116,119,118,113,55) Method Temp. *C B 200-800 E 600 F 800 G 800 H 800 J 600 J 600 Air F 1 ow (1/min) 0 0 0 1 3 1 3 Sample PE -ABS woods PVC PE ABS PE ABS' woods PE ABS PE ABS PE ABS PE ABS Time to :pac i tat i on (min.) 16.68 13.52 10.31* 5-35 9.95 5.S3 3-57 3-03 3-23 2.91 1.69 5.H 1.1*7 5-31 2.8*1 A. 08 2.80 Time to Death (min) 22.60 17.62 U.72 16-37 16.62 18.52 11.72 9.51 6.16 no deaths 3-80 no deaths 3-*7 **.53 3.69 5.69 Mortality 8/8 20/20 8/8 8/8 8/8 16/16 0/8 8/8 0/8 8/8 1/8 8/8 7/8 8/8 000070870 - 29 - ($6). Using the'apparent lethal cone-ntrat ion values as a toxicity index for ** mice in a sealed chamber ABS and PE appear to be more toxic than wood In contrast to the results using t(n>e Iq dsetb., The ALC^Q yalues in mg/1 were (116.123.36J: ABS,2 PE ABS, 1 Doug las Fir Red Oak 10.^5 11.81 20.32 22.40 64.00 The large discrepancy in results for the two ABS samples probably is dne to their composition. Varying the ratio of acrylonitrile: Butadiene: styrene gives a tremendous variety of ABS products. This results in confusion as many papers.do not state the composition of the ABS used. The lethal dose O-D^q) based on the quantity of material which after combustion caused 50* mortality in mice in 10 minutes was determined and the relative toxicities were ABS > polyethylene > PVC,-under these conditions Table 15 024J. In the case of ABS and other polymers containing nitrogen, as the char yield Increased from 0-20* the time to death increased but at char yields greater than 20* time to death decreased (33). The higher the char yield, theoretically the higher the fraction of the original carbon retained in the char and consequently the lower the concentration of carbon monoxide produced (1011. Thus it would seem that the toxicity due to ABS is related to toxicants other than carbon monoxide as already observed in other experiments. Hydrogen cyanide and nitrogen dioxide, both detected and measured in m ABS pyrolysis gases (17). are, on the Basis of LC^.Q values, about twenty-five times as toxic as carbon monoxide (125). Table 15 Cl2^1 LC50 Values for PI ast i cs ABS 0.034 9 PE 0.052 9 pvc 0.140 9 SAL 000070871 ' ` 1 v-3 Keal Fires Involving PVC In PVC fires a study of the medical histories of over 100 firemen showed , that they became disoriented and that their COHb was usually less-than 20* (22). In another study it was observed that at 17* COHb some subjects had a momentary lapse of attention and failed to respond to all the stimuli presented (2). ^Th.i.siftcould explain the fact that firefighters, having detected the sharp odor of- HCl do not a 1 ways seem capable of escaping from the vapors. Several PVC fires have been Investigated (19). In one .case less than one pound of electrical insulation (plasticized PVC) burned yet five of the eight firefighters experienced shortness of breath, eye irritation, loss of balance, loss of co-ordlnation, numbness and chest pains and had to be treated in emergency. All exhibited a rapid irregular pulse and developed a wheezing condition and coughs during the postexposure period. A second fire involving a small amount of PVC pipe and plasticized PVC, resulted in firefighters experiencing respiratory difficulty immediately upon entering the building although a very 1imited .amount of smoke was observed. After the fire was extinguished they experienced the same symptoms as above. Upon returning to the station these firefighters complained of a burn! sensation of the neck, wrists and elbows. Twenty-four hours after exposure they experience's a sloughing of skin where they had experienced the burning sensation (19)* A third fire involving plasticized PVC electrical insulation also resulted in the Incapacitation of the firemen (19). Several important features of these fires and those reported by Esch and Dyer (2) were that all of them were small and easily extinguished, the level of smoke was described as low to moderate, and the Intoxication syndrome * described by all of the firefighters was essentially the same. On a larger scale, a PVC fire In 1375 in the New York Telephone Company installation generated smoke so dense that it hindered all phases of fire fighting operations and resulted In over 200 people being treated f>r smoke inhalation (A)'J It is clear that smoke and toxic gases from burning or heating PVC are dangerous to people end that the use of PVC In buildings is a significant concern. It is also apparent once again th3t these involved in fighting fires in which plastics are consumed should be extremely cautious. Such fires, depending upon the conditions, may cause relatively little to extremely dense smoke. SAL 000070872 - 31 Both extremes are dangerous. On the one hand, toxic gases may be quite concentrated with little smoke; on the other hand both toxic gases and the effects of dense smoke can be very damaging to the people involved unless proper precautions are taken. IV-^ Real Fires Involving ASS and Plastics Known to Produce Hydrogen Cyanide In 1977 a fire in a Tennessee jail resulted in ^2 deaths. The only thing which burned was the cell padding which was styrene-butadiene rubber covered with neoprene-covered nylon fabric. It had been patched with to 1uene-diIsocysnate polyether-polyurethane covered with PVC-'nylon fabric. In this case, the cyanide could not account for the deaths not already explained by CO in the 10 victims autopsied. In spite of the relative simplicity of this fire, the toxicological significance of elevated HCH in fire fatalities was not resolved (28). In the case of the hGh fire, blood cyanide In one victim was 7"9 pg/ml and COHb was 22.2%. Several other victims'with blood cyanide levels of 1-2 pg/ml had COHb l8.2-k8.2%. One with cyanide levels of 2-3 pg/ml had COHb ^0%. None of these COHb levels is considered high (7^. In fact an analysis of the data In (7) showed that the COHB was below the accepted lethal concentration in all but one case (Table 16). Whether the cyanide levels in conjunction with the CO levels In the victims were sufficient to have caused death is unknown with one exception. Blood alcohol for these victims was^not reported (7), Cyanide toxicity is a difficult problem. Just what the toxic concentrations are Is not agreed upon. Normal blood cyanide levels for humans range from 0 to 0.22 pg/ml, with an average of 0,05 pg/ml^for^nonhstTiokers'' (128) . These higher background levels are attributed to cigarette smoking. The above results were obtained on 32 living subjects and 22 non-fire related deaths .(123). In acute cyanide poisoning, the blood level is likely to be 5 pg/ml. and.;i Inhalation of HCN results In signs and symptoms of acute toxicity at blood concentrations at or above 0.2 pg/ml blood (129). Blood cyanide in fatal cases may be below l^./pg/rnl when HCN gas Is inhaled (130). By contrast Caplan et al, (126) considered 0.26-1.0 pg/ml as being sub-toxic concentrations in a report on cyanide concentrations in 25 fire fatalities. Elevated blood cyanide has generally been found with significantly elevated COHb in fire victims. In contrast to the autopsy results from the HCh fire. 000070973 SAL- - 32 Table . 16 COHb Concentrations in Victims of the MGH Grand Hotel Fire (7) % COHb <10 11-20 21-30 31-*0 *1-50 51-60 > 60 No. of Victims * 9 17 2* 7 9 1 {% of Victims) (5-6) (12.9) (23-9) (33-8) (9-9) 02.7) (1 .b) V-1 Rates of Smoke and Acid Gas Release in Rooms Two examples taken from an article in the literature by E.E. Smith are instruct on this topic (3)* The release rate of HC1 is such that 2.0 ft (60.96 cm) of 1.5 inch (3-51 cm)'PVC conduit when exposed to a temperature of 1,000F (53SC) will release over 0.1 lb (*5.* 9) of HC1 per minute. At this rate the air in a 10 x 10 x 100 ft (3-05 * 3.05 x 30.5 m) corridor in which the combustion occurs would reach an average concentration (assuming rapid mixing)vof 100 ppm HC1 In less than *5 seconds. This concentration of HCl would be intolerable to breathe. The use of PVC in ducts Is also a matter of concern should it suddenly b'ecome exposed to fire or intense heat (S);^ Assume that 100 ft (3.30 m ) of vinyl-covered fibrous glass duct liner is in the concealed space above a *fODD ft3 Cl 13.*9 m3) compartment and that it is suddenly exposed to a 22 heat flux of 2.6 Btu/sec.ft (2,25 watts/cm ), It is assumed that the ventilation system pulls 10? of the compartment's air (*00 ft^ or 11.35 m3) 2 per minute into a corridor. In less than one minute 775 "particles"/ft. x 100 ft^ C8.333 "part 1 cles'Vmetre^ x 9.3 or 77,500 "particles" will be released into the compartment reaching a maximum of IB.5 "particles" per ft3 (660.7/m3). The rate of smoke "particle" emission when there is 90% transmissic of light (O.S.U, Apparatus - Section 11-1). was determined to be 158 "particles" per minute (9). In the first minute following the "flash" fire, over 7,000 smoke "particles" will be discharged into the corridor. If thc-se "particles" were uniformly distributed along a 10 x 10 x 50 ft (3.05 x 3,05 x 15.25 m) or 5,000 f t3 (1*1.86 m3) corridor the concentration would be 7,000/5,000 SAL 000070874 33 pr l.k "particles'Yft3 (7000/1A 1 . 86 = ''particles" per m3). This concentration produces a degree of obscuration which would make it impossible to see an exit sign at a distance of 5.5 feet (1.68 m). The major hazard from the duct materiel would be from the HC1 released, During the first minute of exposure 7.5 g/ft^ x 10Q ft 2 (80.65 g/m9 x 9-3 m^) (9) or 750 g (1.65 lb) of HC1 would be released. Over the next minute, 75 grams (0.1.7 lb) of HCl would be discharged into the corridor where the average concentration could reach 1*00 ppm, making it unsafe as an escape route. If the same surface area of red oak were present in the same concealed space the smoke concentrations reached in the corridor would be very different (9). Because of the larger mass of red oak present the total amount! of smoke could be larger, but, because of the slower release rate, the maximum number of "particles" per minute discharged into the corridor would be less than 25% of the number from the duct liner (3). Using the amounts of HCN and NO^ measured when ABS is pyroly2ed at 800C (17), we can calculate the concentrations of these gases in an average apartment taken*to be 10,000 ft3, assuming that there are 100 lb of DWV* pipe and fittings in that apartment. These calculations' also assume the composition of the ABS to be 22% acrylonitrile, 19% butadiene and 52% styrej^^a^ in (17)- From 100 lbs of this ABS at 80Q'C, assuming that all of j i \ burned^ 1,739 1 of HCN^and 3-3 1 of NO^ (at STP) .would be produced^ Thj^ the average concentration of HCN in the 10,000 ft3 apartment would be ^ 6,lk0 ppm, about 22 times the concentration (280 ppm) that would be immediately fatal (see Appendix l),.T5e concentratIon of NO2 would Be 11.7 ppm, a level which would be mildly Irritating to the eyes, nose, and respiratory tract (see Appendix 1). V-2 Behaviour ofPVC and ABS Pipes in Fire Tests Opposition to the use of plastic pipe in high-rise buildings particularly, / is based on the fact that it will burn through and thus might allow fire gases,' ^(/smoUe, and possibly flames to penetrate fire partitions.' A paper by P.C. Attwood in wh`ch an extensive series of small scale tests are described using a positive pressure of 5 mm within the fire compartment and either a horizontal or vertical penetration of the partitions is quite informative. He discusses several possible situations involving the use of plastic pipe, 'Drain, waste, vent. SAL 000070375 Horizontal Pipes 1. Unprotected The wall was 5/8-in.type X gypsum board mounted on both sides of 2 x 6-in, pine studs. The exposed s-ide of the plumbing consisted of- a 2-in (50.8 mm) lateral with a water-filled P-trap. This lateral penetrated the wall and joined the stack within the wall cavity. The exposed gypsum was backed by_ a sheet of 2^ ga. sheet metal and the PVC wall section was fire-stopped at the top. (lOkl ABS laterals sagged and collapsed within 7 minutes; the pipe burned through in 10 minutes for ABS and 19 minutes for PVC, completely exposing the penetration and igniting the pipe and studs within the wall cavity. 2. St eel-Si eeved Laterals at a Angle With both 1.5-in (38 mm) and 3"in (75 mm) PVC pipe penetrating walls at a ^5 downward angle protection was provided for up to two hours by the formation of a plug due to the intumescent nature of PVC and to char formation, A 3-in diameter pipe would be the largest one that would form such a plug. Pipe above the plugs had been totally consumed. The same test with 1.5"in ABS pipe resulted in the pipe being totally consumed leaving an open path for fire gases. A test with ABS pipe penetrating a wall upwards at a ^5* angle gave similar results. With 1.5-in PVC pipe, penetrating the wall upwards at a ^5* angle, it was found that a barrier against flame and gas propagation was formed due to swelling and charring of the pipe as long as the unexposed end of the assembly was unvented. QqIjJ_ 3- Mechanical Shut-Off Devices Mechanical shut-off devices which relied on the softening behaviour of thermoplastics at elevated temperatures were also tested. To be effective the closure device should shut as the plastic collapses, creating a seal. A variety of single shut-off devices were tested with failure times ranging from 28 minutes to 115 minutes. Such devices were generally unsatisfactory, and the 115 minute duration of one test was only a result of severe blistering of the metal assembly presumably caused by acidic products (HC1) from combustion of PVC. A double shut-off device was more successful and provided protection for up to two hours, although with ABS, combustion products vented through the plumbing system until the second device pinched off the pipe after 6O-7O minutes. SAL 000070876 - 35 - Vertical Pipe Assemblies 1. Unprotected Pipe A 4-inch (10.2 mm) pipe extending seven feet (2.13 m) above a concrete slab and 4 inches below it was used for the tests. A twelve-inch, long steel sleeve was around the pipe. The 4-inch end of the pipe was heated in the furnace. After 14 minutes for ABS and 22 minutes for PVC the pipe had softened sufficiently to collapse in a heap around the sleeve on top of the slab creating a temporary seal. The ABS ignited immediately whereas the PVC burned through after 35 minutes. (104) 2. Stacks Within Vented Chases In each test damage was substantial: a remnant of pipe remained in the top of the chase, the rest of the pipe having collapsed into the bottom of the chase. In one PVC test and the ABS test the pipe in the chase was totally consumed. In two PVC tests the furnace gases had created a path through the PVC ash, thus exposing the penetration. (104) 3. Mechanical Shut-Offs In the time before a seal Is created (30 minutes arid 25 minutes for 3"<nch (75 mm) PVC and ABS and 22 minutes for both 4-inch PVC and ABS) hot combustion gases and smoke are vented through the plumbing system. (104) 4. Unvented Applications Three-inch copper, ABS and PVC drain pipes were connected to water closets with the trap filled wfth water. In the PVC and ABS tests the pipe within the furnace was consumed and a small amount of smoke and fume seepage was .evident around the ungrouted base of the water closet. By the end of two-hour tests all ABS and PVC pipe, flanges and rubber seal rings had been consumed. In the copper tests, the system remained intact except for the seal ring. Severe cracking of the water closet base occurred in each test, but only on surfaces not contacting water. There was no loss of water in any test but smoke seepage occurred through the cracks in the water closet. Considering the rapid rate of dehydrochlorination of PVC at reasonably low there is a possibility that significant amounts of HCl would be vented through the plumbing system before any mechanical shut-offs would have sealed the pipe, or through the cracks In the case of water closet Unprotected plastic pipes, both horizontal and vertical are obviously hazardous (1 SAL 000070877 - 3b It must be concluded on the basis of the above that integrity of fire partitions penetrated by either ABS or PVC pipe is indeed compromised and that the mechanical shut-off devices tested were generally ineffective despite the author's concl us ion (160 'Y^F'pTast Ic^pl pe can penetrate fire separations ' without propagating fire beyond the separation. 000070978 *37- Conc1 us Ions Some conclusions derived from this literature search are the following: 1. The main product of pyrolysis or combustion of PVC is hydrogen chloride vapor which is not only extrepely irritating to "the eyes and nose but causes extensive lung damage when inhaled. 2. ABS is a very flammable plastic which on combustion produces deadly hydrogen cyanide as well as carbon monoxide. 3* The length of time between the initiation of combustion of ABS or PVC in a room and the point at which concentrations of smoke and toxic gases become ove'r power i ng _to^a,yi_ctjnT`4-jsTTshoTtprobab 1 y ' about -one mi nute % ABS and PVC under test conditions produce many times more smoke under flaming conditions than a number of woods that were tested. 5. ionization detectors are reiativeiy insensitive to the products of,^' combustion of PVC sometimes giving a warning after the concent rat ion of hydrogen chloride has built up to several times the tolerable concentration.6. Use of plastic pipe plumbing systems in high rises and mu 11 t - un i t dwelling places can contribute to the rapid product ion -of. dangerous levels of smoke and toxic gases as well as spreading of flames`should the components 7 of such a system catch fire. ,'t0n the basis of experiments described in the literature it is evident that fire proof penetration of fire partitions by plastic pipe has not yet been achieved. SAJ.. ^00070879 -38- Acknowledgements The authors wish to express their grateful appreciation to Dr. E.5. Hall who reviewed and commented on the contents of this document. They also wish to thanks Hisses J. Porter, C.L. Seifert.and D. Bundcaard who typed the manuscript. The work was funded by the Canadian Foundry Association Cast Iron Soil Pipe Division, Edmonton, Alberta. \ 0000 7088 Re ferentes ($) Q 1. Gaskill, J.R., ``Smoke Development. Duri ng Pyrolysis or Combustion'* in Smoke and Products of Combustion, Vol 2. fire and flammability series edited by C.J. Hilado, Technomic Publishing Co. Inc., Westport, Conn. 1973, P- 1 2. Dyer, R.F.. and Esch, V.H., "Polyvinylchloride Toxicity In Fires, Hydrogen Chloride Toxicity in Fire Fighers", J. Am. Med. Assoc. 1976, 235, 393. :" 3# Woolley, W.D., " The Hazard of Building Contents in Fires", Second Symposium on Combustibility and Plastics, Ottawa, Canada, October 30*1 1973, p. 117. Clark, P.R., "Plastics and Fire: A Fire Fighter's View", Second Symposium on Combustibility and Plastics, Ottawa, Oct. 30-1, 1979, P- 218. "Fire at the UGH Grand, a preliminary report". Fire Journal, March 1981, P. 33. Bush, V.R., "MGM Grand Hotel Fire, Las Vegas, Nevada", Building Standards , Jan-Feb. 1981, 6. 7. Clark-County Coroner-Medical Examiner, MGM Grand Hotel Fire Report. .8 Modern Plastics Encyclopedia 19 20 , p. k. 9- Smith, E.E., "Fire Hazard Characteristics of Duct Materials", ASHRAE 1S 7 2, 1M7), 29. 10. Imhof, L.G. and Stueben, K.C., "Evaluation of Smoke and Flammability Characteristics of Polymer Systems", Polym. Eng. Sci . , 1973, 13 (2), 1k6. 11. Kourtldes, D.A. and Parker, J.A., "Flammability Properties of Some Thermo plastic and Thermose-t Resins", SAHPE Q. 1978, 9(3), 36- 12. Hilado, C.J., Cumming, H.J., and Machado, A.H., "Screening Materials for Smoke Evaluation", Modern Plastics 1978, 55(7), 81. 13. Gaskill, J.R., "Smoke Development of Plastics Under Various Fire Parameters" Soc. Plast. Eno., Tech. Pap., 1972, l3(Pt.l), 26k. Ik. Gaskill, J.R. and Vetth, C.R., "Smoke Opacity from Certain W'oods and Plastics", Fire Technol. 1968, k, 185. 15. Hilado, C.J., "The Effect of Chemical and Physical Factors on Smoke Evolution from Polymers" in Flammability of Solid Plastics Vol. 7 fire and flammability series ed. by C.J. Hilado, Technomic Publishing Co. Inc. 197k, 93. 16. Sumi, K. and Tsuchiya, Y. "Toxicity of Decomposition Products - -ko- Polyacrylonitrile, Nylon 6 and ABSM, Build. Res. Note ~ Natl. Res. Counc. Can. Dlv. Bldg, Res.. 1976, 1 ... " ! ~~ 17. Chaigneau, H. and LeMoan, G., "Pyrolysis of Plastic Materials VII. Polyacrylonitrile and Co-polymers", Ann. Pharm. Fr. , 1$7^, 32, ^85. 18. Comeford, J.J. and Birky, M., "Measurement of Smoke and Hydrogen Chloride Evolution from PVC", FI re Techno!. 1372. 8(2), 85. 19- Elnhorn, l.N. and Grunnet, H.L., "The Physiological and Toxicological Aspects of Degradation Products Produced During Combustion of PVC Polymers", Spec. Rep. ~ Electr. Power Res. Inst. (Palo Alto) 1 380, EPRl .EL - 1263, Flammabil ity Solid Polym. Cable Dielectr., 3/1 " 3/^7- 20. O'Kara, H.M., "Combustion of PVC", Pure Appl . them. 1977, ^9(5). 6^9. 21. Voorhees, K.J., Ryan, P.V., Mickelson, R.W., Einhorn.l.N. and:Futrell, J.H., Proceedings 23rd Annual Conference on Mass Spect romet ry and Allied Fields, Houston, Texas, 1375, P- 200. 22. Einhorn, l.N., "Methodology for the Study of Toxicology In Combustion : Application to PVC, J. Macromol. Sci., Chem. 1977, A 11(8), 1519. 23. Deichmann, V.B. and Gerarde, H.W., Toxicology of Drucs and Chemicals, Academic Press, N.Y. and London, 1369. 2k. Boudene, C., Jouany, J.K. and Truhaut, R., "Protective Effect of Water Against Toxicity of Pyrolysis and'Combustion Products of PVC and Wood, J. Macromol, Sci . , Chem., 1977, A 11(8), 1529. 25. Hilado, C.J., Flammability Handbook for Plastics, 2nd edition, Technomlc, Westport, Conn., I37A. 26. Trietman, R.D., Geld, A., and Burgess, W.A., "Air Contaminants Encountered by Firefighters", Second Symposium on Combustibility and Plastics, Ottawa, Canada, October 30"! 1979, p. 28. 27* Kourtldes, D.A., C^ilwee Jr., V.J. and Parker, J.A., "Thermocheml cal Characterization of Some Therm.a 11 y S t abl e Thermopl as t i c and Thermoset . Polymers>ttThernosets High Perform.' Thermoplast. 1977, 113. 28. Birky, K.H., Paabo, H. and Brown, J.E., "Correlation of Autopsy Data and Materials Involved in the Tennessee Jail Fire", Fire Safety J., 1S&0 2(1), 17. 29. Berl, W.G. and Halpin, B.H., "Fi re-Re-Iated Fatalities: An Analysis of Their Demography, Physical Origins and Medical Causes", Fire Standards and Safety. A.F. Robertson, editor, ASTM Symposium, Gaithersburg, Md., April 5-6, 1976. 30. "Standard Test Method for Surface Flammability of -iterials Using a Radiant Energy Source", ASTM E 162-176. ASTM Stanr. -ds. Pert 18, 1977- 31. Hilado, C.J. and Cumming, H.J., "Studies With the Arapahoe Smoke Chamber", SAL 000070882 J . FI rc FI a-.msb i 1 I ty . 1 377, 8, 300. 32. tee, T.G., "Smoke. Dens i ty Chamber Method for Evaluating the Potential Sr.oke Generation of Building Katerials11, N3S Technical 757, Jan. 1973. 33. "Standerd Method for Measuring the Density of Smoke from the Burning or Decomposition of Plastics", AS7M D2Bk3-/0, AS7M Standards, Part 35,0577). 34. "Standard Test Kethod for Surface Burning of Building Katerials", ANSI/ ASTK B4;77, ASTM Standards, Part 1 8 (1577). 35. Smith, E.E., "Measuring Rate of Heat, Sr.oke and Toxic Gas Release", Fire Tech, 1972, 8, 237 35. Kourtides, D.A., Parker, J.A. and Hilado, C.J., "Therrochemi ca 1 Character ization of Some Thermoplastic Materials", J. Fire Flammability, 1577, 0(1), 59. 37- Gasklll, J.R., "How Plastics Smoke", Soc. Plast. Eng. J., 1972, 28(10), 43. 38. Seito, F., Research Institute(Japan), Research Paper No. 33, 1 68. 39. Calcraft, A.M., Green, R.J.S. and HcRcberts, T.S., "Burning of Plastics .1. Smoke Formation", Plast. Po1ym,, 1974, 42(16), 200. 40. Keisters, H.f "More Realistic Testing of Smoke Generation", Plast. Eng. 1378. 32(8), 49, 4l . Bankston, C . P. , Powe 11, E . A. , Cas s a nova , R. A. end Z \ rin , B .T . , "Det a i 1 ed Measurment of Physical Characteristics of Smoke Particu1 ates `Generated by Flaming Materials", J. Fire FIammabi11ty, 1 977, 8(4), 395. 42. Zinn, B.T., Powell, E.A., Cassanova, R.A. and Bankston, C.P., "Investiga tion of Smoke Particulates Generated during the Thermal Degradation of Natural and Synthetic Materials", Fire Res., 1977, 1(1), 23- 43. Christopher, A.J., ''Some Aspects of Smoke end Fume Evolution from-Over heated Non-Ketallic Materials", J. Combust. Toxicol. 1978, 3, 89. 44. Hilado, C.J. and Machado, A.H., "Smoke Studies In the Arapahoe Smoke Chamber", J. Fire Flammability 1978, 3, 240. 45. Cornish, H.H., Hahn, K.J. and Barth, H.L., '`Experimental Toxicology of Pyrolysis and Combustion Hazards", Environ. Health Perspect. 1975, 11, 191. 46. Stone, J.P., Hazlett, R.N., Johnson, J.E. and Carhart, H.V/., "The Transport of Hydrogen Chloride by Soot from Burning PVC", J. Fire Flammability 1973, 4, 42. 4?. Henderson, Y. and Haggard, H.W., Noxious Cases, 2nd ed.. Reinhold Publish ing Corp., N.Y. (1943), P- 71. 48. M.orikawa, T., "Evolution of Soot and Polycyclic Aromatic Hydrocarbons in Combustion", J. Combust. Toxicol. 1578, 5, 349- SAL 000070883 -k2r ij9. Liao, J.C. and Browner, R.R., "Determination of Polynuclear Aromatic Hydrocarbons In PVC Smoke Particulates by High Pressure Liquid. Chromato graphy and Gas Chromatography - P.3SS Spectrometry", Ana 1 . Chen, 1978, 50(12), 1683. 50. KorTkawa, T., "Evolution of Soot and Polycyclic Aromatic Hydrocarbons in Combustion", Shobo Kenkyusho Hckoku 1578, i<5,- 13* 51. Chaigneau, H., '`Formation of Some Polycyclic Hydrocarbons tn the Course of the Thermal Degradation of PVC", C.R. Hebd. Seances Acad. Sci. Ser. C. 1978, 286(8), 257. 52. Wagner, J.P., "Smoke Detector Characteristics", Proc. j nt. Conf. Fire Safety. 1977, 2, A32. 53* Welker, R.W. and Wsoner, J.P., "Particle Size and Hass Distribution of Selected Smokes: Effect on Ionization Detector Response", J Fire F1 a mm. 1977, 8(1). 26. 54. Purt, G., "Fire Protection for Fires With PVC", Ver. Foerder. Deut. Brandschutzes 2. 1 9&9 * 18(M, 158 - 55. Hilado, C.J., Cummings, H.J. and Casey, C.J., "Toxicity of Pyrolysis Gases from Natural and Synthetic Katerials", FT re Techno 1. 19 78, 14(2), I 36. 56. Woolley, W.D., "Dehydrochlor1natTon of PVC in Nitrogen and Air", P1ast. Folym. 1972, ^0(K8), 203. 57. Chaigneau, K., "On the Evolution of Various Pollutants from the Thermal Degradation of PVC", C.R. Hebd. Seances Acad. Sci. Ser. C. 1576, 282(13)* 583. 58. Bradt, P. and Kohler, F.L., "Mass Spectra of Thermal Degradation Products of Polymers", J. Research Natl. Bur. Standards 1555* 55, 323~7 5960. Paullk, J., Paullk, F. and Erdey, L., "Combined Der1vatographic an. Thermal Gas - Analytical Studies", Klkrochlm, Acta. 1966, 886. LeKoan, G. and Chaigneau, M., "Pyrolysis of Katerials in Plastics .1. PVC Characterization of Possible Volatile Toxic Compounds", Ann. Pharm, Fr. 1969* 27, 97. 61. Caret, A.B., "Pyrolysis of PVC and Experimental P(VC) Compounds Using a Thermal Gravimetric Analysis Furnace and Oven Technique with Recovery Studies of Hydrogen Chloride", Proc. Int. Wire Cable Symp. 1978^, 27, 299- 62. O'Kara, H.M., "High Temperature Pyrolysis of PVC : gc-ms Analysis of the Pyrolysis Products from PVC Resins and Plastisols", J. Polym. Sci. Part A-1 1970. 8, 1887. 63. Woolley, W.D., "Decomposition Products of PVC for Studies of Fires", Paper CP 11/7*1 Building Research Establishment, Fire Research Station, Borehamwood WPG 2BC, Great Britain. 6*4. Hainan, K.B., Papko, R.A. and Pudov, R.A., "Thermal Degradation of PVC (0, SAL 000070884 -43- Vysokomcl. Soedln, Ser. A. 1 $68, 1 0, E4 1 . 65- Forstler, H., "Combustion Products of Synthetic Materials", Rev. Tech. Feu. 1975, 16, 24. 56. Autain, J., "Toxicologic Aspects of Flammability and Combustion of Polymeric Materials" in Stroke and Products of Combustion; Vol 2.fire and flammability series, ed. C.J. Hilado, Technomic Publishing Co. fnc.t Westport, Conn., 1573, P- 57. 67- I mo to,. M. , "Products by Pyrolysis of PVC", Setchaku 1574, 18, $40. 68. Michal, J., "Evaluation of the Assumed Toxicity of Some Plastics", Nehorlavost. Polym. Mater. 1576, 125. 65. Ksbayashit , Horl, M. and Murata, H., "Combustion Gases Generated from PVC and its Products. Model Experiments Simulating Fire11,1 Jap. Plast. 1971, 5, 40. 70. Chang, E.P. and Salovey, R., "Pyrolysis of PVC", J. Polym. Sci . , Poly. Chem. Ed. J_974., 12, 2527. 71. Ball, G.L. and Boettner, E.A., "Toxic Gas Evolution from Burning Plastics", Polym. Prepr., Am. Ch&m. Soc. Div. Polym.Chem. 1973, 14, 986. 72. V/oolley, V.D., "Toxic Products from Plastics Materials In Fires", Plast. Polym. 1973, 41,.280. 73. Noffz, D., Benz, V. and Pfab, W., "Pyrolytic Gas Chromatography Study of High Polymers"., Fresenius 2. Anal. Chem. 1968, 235, 121, 74. Hiramatsu, K., "Pyrolysis Products of Polymeric Materia 1s by Mass Spectro metry. IV, Mass Spectrometry of Pyrolysis Products of Poly(vinyl alcohol) and PVC", Shitsuryo Bunseki 1$, 25. 75- Hagen, E., "Composition of Pyrolysis Gases of Plastics", Plaste. Kaut. 1968, 15, 711. 76. Takahashl , T. and Serizawa, M., "Pyrolysis of PVC", Enka . Bini1ru To Porima 1971, 11, 26. 77. Ilda, T., Kakanishl, M. and Goto, K. , "PVC.l. Evolution of Aromatics on Pyrolysis of PVC and Its Mechanism", J. Polym. Sci., Polym. Chem. Ed. 1974, 12, 737. 78. Goto, K. and lida, T., "Pyrolysis of PVC . Formation of Aromatic Compounds", Enka. Biniiru To Porima 1973, 13, 18. 79* Koichi, K. and Nakamura, K., "Toxicities of Combustion Products", J. Fire FI amr.ab i 1 i ty/Comb us t ion Tox i colocy S up pi 1974, 1, 104. 80. Kishitani, K. and Nakamura, K., "Study on Toxicities of Combustion Products of Building Materials at Initial Stage of Fire", J. Fac. Eng., Univ. Tokyo, Scr. 8. 1377, 34, 295. SAL 000070885 -kk- 81. Dotreppc-Giseard, N., "Compounds Obtained by Combust Ion of Plastics'*, Trib. Centre Beige Etude Doc, faux 1958, 21, 2k7. 82. Schriesheim, A., "Method for the Controlled Burning of Combustible Materials and Analyses of the Combustion Gases". J. Research Natl. Bur. Standards 1956. 57, 2k5. S3- Gordon, G.Ya., "Thermal Dehydrochlorinetion of Chlorine Containing High Polymers", PI astTcheskie Massy 155k (k), 6. _ 8k. Woolley, V.D., "Behaviour of PVC in Fires", J. Kacromol. Sci. Chem. A 11. 1977. 1509. 85- O'Kara, H.H., "Pyrolysis Gas Chromatography Analysis of PVC.II. tn Situ Absorption of HCI During Pyrolysis and Combustion of PVC", J. Polym. Sci., Part A-1 1971, 9, 1387. 86. Eitingon, A. I . , Solov'eva, T.V., Gribunova, G. and Naumova, L.S., "Toxi city of Volatile Products Emitted During the Burning of Polymer Materials Synthesized from a PVC Base", Gig. Sanit. 1975. 2, 10k. 87. Antonyuk, O.K. and Aldyreva, M.V., "Substantiation of the Maximum Permis sible Concentration of Dibutyl Phthalate in the Air of Industrial Premises", Gig. Tr. Prof. Zabol . 1573. 8, 26. 88. Chaigneau, H., "Mass Spectrometry Analysis of Compounds Formed by Pyrolysis of Polyacrylonitrile and Copolymers", Ana 1 usis'1977 , 5. 2 23- 89. Chaigneau, M., "Gas Emitted by the Pyrolysis of Different Plastic Materials at 1,00DC.", C . R. Acad. Sci., Ser. C. 197k, 278, 109- 90. Hilado, C.J. and Brauer, D.P., "Concentration-Time Data in Toxicity Tests and Resulting Relationships", J. Combust. Toxicol. 1979, 6, 1-38. 91. Hilado, C.J. and Machado, M., "Toxicity of Pyrolysis Gases from Some Cellular Polymers", J. Combust. Toxicol. 1978, 5, 162. 92. Hilado, C.J., Huttlinger, N.V. and O'Neil 1, B.A., "Effect of Heating Rate on Toxicity of Pyrolysis Gases from. Some Wood Products'* J. Combust. Toxicol. 1978. 5 25. ' .. 93* Hilado, C.J. and Casey, C.J., "Pyrolysis of Polymeric Materials.!. Effect of Chemical Structure, Temperature and Heating Rate and Air Flow on Char Yield and Toxicity", J. fire Flammability 1979, 10, IkO. 9k. Chaigneau, M. and LeHoan, G., "Toxicity of Plastics Combustion Broducts.il.", ' Ann. Pharm. Fr. 1977, 35, 153* 95* Barrow, C.S., Alarie, Y. and Stock, M.F., "Sensory lrrTtstlon and Incapaci tation Evoked by Thermal Decomposition Products of Polymers and Comparison with Known Sensory Irritants", Arch. Envir. Health 1978, 33, 79. 56. Hilado, C.J., Ksrcussen, W.H. and Furst, A., "Apparent Lethal Concentrations of Pyrolysis Products of Some Polymarlc Materials," J. Ccnbust. Toxicol. 1978, 3, 3^5. 000070886 -.45- 07. Hilado, C.J., Solis, A.N., Karcusscn, V.H., and Mschsdo, A.H., "Effect of Temperature and Heating Rate on Apparent Lethal Concentrations of Pyrolysis Products," J. Combust. Toxicol. 1976, 3. 381* 58. Barrow, C.S., Lucia, H., Stock, H.F. and Alarle, Y.C., An, Ind. Hygiene Assoc. J. 1979, 40, 408. 39* Barrow, C.S., Lucia, H. and Alerie, Y.C.,' "A Comparison of the Acute Inhalation Toxicity of Hydrocen Chloride vs the Thermal Decomposition Products of PVC", J. Combust. Toxicol. 1979. 6, 3* 100. Hllado', C.J., Cur.minc, H.J. and Casey, C.J., "TcxIcity'of Pyrolysis Gases from Plastics and Elastomers", J. Elastomers Plast'. 1979, 1 1, 3. 101. Hilado, C.J. and Machado, A.K., "Effect of Char Yield and Specific Toxicants on Toxicity of Pyrolysis Gases From Synthetic Polymers", Techno!. 1979. 15,51* Fire 102. Htlsdo, C.J. end Huttlincer, N.V., "Concentration - Response Data on Toxicity of Pyrolysis Gases from Six Synthetic Polymers", J. Combust. Toxicol. 1978, 5, 81. 103. Hilado, C.J., Soriano, J.A. and Kosola, K.L., "Effect of Heating Rate on Toxicity of Pyrolysis Gases from Some Synthetic Po 1 ym.e rs", J. Combust. Toxicol. 1977, 4, 333- 104. Attwood, P.C., "Penetration of Fire Partitions by Plastic Pipe", Second Symposium on Combustibility and Plastics, Ottawa, October 30-1, 1979 p. 272. 105. Orlggi, P., "Flammability of Plastic Materials", Mater. Plast. Elastomer!. J_976, 120. 106. Barrow, C.5., Alarie, Y.C. and Stock, H.F., "Sensory Irritation and Incapacitation Evoked by Thermal Decomposition Products of Polymers and Comparison with Known Sensory Irritants", Arch. EnvIr. Health 1378, 33, 7$. 107* Kane, L.E., Barrow, C.S. and Alarie, Y.C., "A Short-Term Test to Predict Acceptable Levels of Exposure to Airborne Sensory Irritants", Am. 1nd. Hygiene Assoc. J. 1`9 7 9, 40, 207* 108. Klshitani, K., "Study on Injurious Properties of Combustive Products of Building Materials at the Initial Stage of Fire", J. Faculty of Enaineer- tng, U. Tokyo (3), 1371. 31, 1-35. * 109* Sakai, T. , "Intake of Carbon Monoxide in the Mouse Exposed to a Mixture of Carbon Monoxide and Hydrogen Chloride", loaku To Seibutsuoa ku 1S77, 94, 475* 110. Colardyn, F. van dcr Straeten, H., Lamont, H. and van Peteghem, T., "Acute Inhalation - Intoxication by Combustion of PVC", Int. Arch, Occup. Environ. Health 1976, 37 121. 111. Anderson, R.C. and Alarie, Y.C., "Approaches to the Evaluation of the Toxicity of Decomposition Products of Polymeric Materials Under Thermal SAL 000070887 -46- Stress", J. Combust. Toxicol. 1978, 5 214. 112. Hilado, C.J., Cunming, H.J., Kourtidcs, D.A. and Gilwee Jr., W.J., "Relative Toxicities of the Pyrolysis Products From Some The r nop 1 a s 11 c and Thermoset Polymers", Thermosets High Perform. Thermoplast. 1 977, 150. 113- Kourtides, D.A., Gilwee Jr., W.J. and Hilado, C . J. , "Re 1 ative Toxicity of the Pyrolysis Products from Some Thermoplastic and Thcrmoset Polymers", Folym. Eng. Sci . 1978, 1 8, 674. 114. Alarle, Y.C., "Toxicologic and Acute Lethal Harard Evaluation of Thermal Decomposition Products of Synthetic and h'atural Polymers", presented at Second Symposium on Com.bus tibility of Plastics, Ott awa, October 30-1, 1373, P. S&* 115. Lucia, H.L., Barrow, C.S., Stock, H.F. and Alarie, Y.C., "A Semi-Quantitative Method for Assessing Anatomic Damage Sustained by the Upper Respiratory Tract of the Laboratory Mouse, Mus nusculis", J. Combust. Toxicol. 1377, 4, 472. 116. Hilado, C.J., Gumming, H.J., Machado, A.K. and Schneider, J., "Comparison of Animal Responses to the Combustion Products Generated by Two Test Procedures, the USF/NASA Methodology and the FAA/CAMl System", J. Combust. Toxicol 1377, 4, 325* 117. Hilado, C.J. find Crane, C.R., "Comparison of Results with the USF/NASA and FAA/CAMl Toxicity Screening Test Methods", J. Combust. Toxicol. 1377, 4, 56. 118. Hilado, C.J., Camming, H.J. and Casey, C.J., "Toxicity of Pyrolysis Gases from Plastics and Elastomers", J. Elastomers Plast. 1373. 11, 3- 119. Hilado, C.J. and Cummings, H.J., "The Effect of Test Conditions on Relative Toxicity of the Pyrolysis Products from Some Plastics", Fire Techno1 . 1377, 13, 325. 120. Hilado, C.J. and Cumming H.J., "Relative Toxicity of Pyrolysis Gases from Materials: Effect's of Chemical Composition and Test Conditions", Fire Mater. 1378. 2, 68. 121. Hilado, C.J., Soriano, J.A., Kosola, K.L., Solis, A.N. and Furst, A., "Effect of Heating Rate on Pyrolysis Gas Toxicity of Synthetic Polyrers and Elastomers", Proc. West Pharmacol. Soc. 1378, 21, 171* 122. Hilado, C.J., "Toxicity of Pyrolysis Gases from Materials", Hail. Synp. Exhib. 1378, 23, 325. 123* Hilado, C.J., Gumming, H.J. and Furst, A., "The Effect of Test Conditions on Relative Toxicity Test Results and Rankings", Aerosp. Med. Res. Lab. (Tech. Rep.) AMRL-TR (U.S.) 1977, AKRL-TR - 77-37; Proc. Annu. Conf. Envir. Toxicol. 8th; AD - A05K334, 77-85. 124. Chaigncau, M. and leHosn, G., "Toxicity of Plastic Combustion Products III. Rapid Evaluation Method by Determination of LD50 in Mice", Ann. SAL- 000070888 -1*7rhrm. Fr. 1377, 35, *61 . 125- Hilado, C.J. and Cumming, H.J., "A Review of Available LC50 Data", _J. Combust. Toxi col . 1 977, **, 415. 126. Caplan, Y., Thompson, B. and Altman, R., to be published. Reported in reference 28. 127. Lipska, A.E. and Alvares, N.J., "Chemical Constituents of Smoke and Conjecture as to Their Role in Foam Destruction" in Smoke and Products of Combustion, Vol 2 fire and flammability series ed. C.J. Hilado, Techncmic Publishing Co. Inc., Westport, Conn. 1373, `P*' 171* 128. Caplan, Y. and Altman, R., ".Mi c rode te rml nat ion of Cyanide in Fire Fatalities", 26th Annual fleeting American Academy of Forensic Sciences, Wash. D.C. 1976. 129. Sunshine, 1 and Finkle, B., "The Necessity for Tissue Studies In Fatal Cyanide Poisoning", Int. Arch. Gewerbe pathpl. Gewerbehyg. .1$64, 20, 558. 130. Reiders, F. and Sunshine, !., Methodology for Analytical Toxicology, CRC Press, 1971, p. 115- 131. Sumi, K. and Tsuchiya, K., "Combustion Products of Polymeric Materials Containing Nitrogen in their Chemical Structure", in Smoke and Products of Combustion Vol. 2 fire and flammability series ed. C.J. Hilado, Technonic Publishing Co. I nc. Wes tport, Conn., 1973, P- 97. 132. Isaacs, J.L., "The Oxycen Index Flammability Test", Flammability of Solid Plastics, Vol. 7 fire and flammability series, Tethnomic Publishing Co. Inc., Westport, Conn., 1974, p. 1. OSS'? 00007 -i<8- APPEKD1X 1 HUMAN RESPONSE TO OXYGEN DEPLETION AND TOXIC GASES (25) Oxygen Depletion . Signs and Symptoms of Toxicity of Reduced Levels of'bxygen % Oxygen in Air 20% 12-15% io-m 6-8% . 6% or below 2-3% No symptoms Muscular co-ordination for skilled movements lost Nausea and vomiting, faulty judgment, rapid fatigue Collapse and unconsciousness, rapid treatment can prevent death Death in 6-8'minutes Death in k$ seconds Toxic Gases The combined effects of breathing a mixture of gases is not well under stood. The information presented here applies to each gas as the sole toxicant. Carbon Monoxide Concentration of CO (ppm) 100 200 300 *<00 500 00 1000 1500 2000 3000 8000 12800 Sympt oti5_ No poisoning symptoms even after 8 hours. Headache after 2~3 hours; collapse after *<-5 hours. Headache after 1.5 hours; distinct poisoning after 2-3 hours; collapse after 3 hours. Distinct poisoning, frontal headache and nausea after 1-2 hours; collapse after 2 hours; death after 3"^ hours. Hallucinations felt after 30-120 minutes. Collapse after 1 hour; death after 2 hours. Difficulty in ambulation; death after 2 hours. Death in 1 hour. Death after **5 minutes. Death after 30 minutes. Invnedi ate death Unconsciousness after 2-3 breaths; death in 1-3 minutes. SAL 000070890- .1,3- > CDKb (Carboxyher.sg 1 obin), % in the blood____________ Synptcns 20-30 30-^0 AO-50 50-60 . 60-70 70-80 80-90 *------------ "-- -------------- *--- ------------ .... ---------------------------------------- ------------------ ---------------------- Headache, throbbing in the temples. Severe headache, weakness, dizziness, dimness of vision, nausea, vomiting, collapse.. As above, increase In pulse and breathing rates , greater possibility of asphIxiation, col lapse. As above, coma, intermittent convulsions and Cheyne-Stokes respiration. Coma, intermittent convulsions, depressed heart action and respiratory rate, possible death. Veak pulse, slowing of respiration leading to death within a few hours. Death in less than an hour. Carbon Dioxide Symptoms Concent ration (ppm) 250-350 900-5000 18,000 25,000 1*0,000 Normal concentration in air. No effect. Ventilation increased by 50%. Ventilation increased by 100%. Ventilation increased by 300%, headache, 80,000 100.000 120.000 200.000 ----------------------------------------- ------------------- Dizziness, stupor, unconsciousness, distinct dyspnoea, lowered blood pressure, congestion, death within k hours. Headaches and dizziness. Immediateunconsciousness, death In minutes. Narcosis, immediate unconsciousness, death by suffocation. Hydrogen Chloride Concent ration (ppm) Sympt ems 1 "5 5-10 35 50-100 1,000 ----------------------------------------------------------------------------------------------- Limit of detection by odor. Mild irritation of mucous membranes. Irritation of throat on short exposure. Barely tolerable. Danger of lung edema after short exposure. SAL 000070891 Hydrogen Cyande (23 and 25) Con centra 1I on (ppm) Sympt cms l8-36 -- *----------------- i*5"5^ --------------------- 100 --------------------- 110-135 --------------------- 135 --------------------- 181 ------------------- 280 ------------------- -- Slight symptoms, headache after several hours. Tolerated for 1/2-1 hour without difficulty. Fatal after 1 hour. Fatal after 1/2-1 hour. Fatal after 1/2 hour. Fatal after 10 minutes.' Immediately fatal. Nitrogen Dioxide (25) Concent ration (ppm) 10-20 50 80 90 100-200 250 Symptoms Hlldly irritating to eyes, nose and upper respiratory tract. Distinet irritation. Tightness of chest after 3~5 minutes. Pulmonary edema after 30 minutes. Very dangerous within 30-80 minutes. Death after a few minutes. Acrolein (CHa=CHCH0) (25) Concent ration (ppm) Sympt oms 0.8 1.0 5.5 10+ --------------------- ----------------------------------------.------------------ Laobrymation, irritation of mucous membranes. Irritation Intense irritation. Lethal in a short time. Benzene (25) Concent rat 1 on (ppm) Sympt oms 500 1500-^000 8000 20000' --------------------------------------------------------------------------------- Slight Irritation. Dangerous to life after several Fatal after 30-S0 minutes. Fatal after 5 minutes. hours. Parts per million (com) is defined as the volume of the gas in one miill ion parts air-vapor at 25 0 and 7&0 mm Hg SAL 000070892 APPENDIX 2 Oxygen Index1 (Defined as the Percentage of Oxygen in an Oxygen-Nitrogen Mixture Which Will Just Support Sustained Combustion.)(lo) Polyethylene, high density 17.4 A'SS, Cycolac T, (Marbon) ABS/polyearbonate Alloy (Cycoloy S00) ' 18.2 20.2 PVC, Plaskon 2005 Chlorinated PVC, Geon 101 Polytetrafluoroethylene (Teflon) 95.0 Various Woods 22 - 24.5 (1) More complete Indices are given by Isaacs (132) and by Hilado (25). Effect of Composition of PVC on the Oxygen Index Plastic PVC PVC with S% ABS impact modifier PVC with 41% dioctyl phthalate PVC (5D%)/ABS (50%) PVC (4E%)/ABS (4B%) with 4% $b20i PVC/ABS alloy Cycovin KA Oxygen Index (10) 40.3 35.3 21.6 23-6 33-0 27.0 SAL 000070893 -52- APPENDIX 3 OPTICAL DEFINITIONS Optical Density Optical Density D = logic -j-- Optical density is directly proportional to the length of the light path Vo Specific optical density, Ds = -- logic -- , where V * volume of smoke chamber. A -- area of burning or smouldering material. K = length of the light path- ' l0 = initial light intensity. transmitted light intensity. Ds is dimensionless. Hass Optical Density, HOD V. (100) -- 1d9 --t-- Lm 1 where m mass loss of sample up to T. T - minimum light transmittance {%) (^0) .