Document ypbpkaNqLM2YmvOOmdVDob0oX

bfg technical document staff bcuxgai. ntnci bpokt mc. B. P. Goodrich Chemical Company ^fj A OVtttON Of TH i. OOOORICH COMPANY \K J DEVELOPMENT CENTER / RESULTS Or SB EXPOSURE OP TEST RATS TO THE CMQBTXOD PRODUCTS PROM B.P.C.C.C. PRODUCTS Michael K. O'Hara Dftta Coupletod: October 21, 1973 Deparoaat Ho.: 3026 Data leaned: October 27, 1975 Project Mo.: 2346 Dlatrlbutiop Akron J. H. Powell, Jr. W. C. Bechtel R. V. Straeaburg Brackevllle R. J. Fawcett C. H. Lufter H. Tucker-A. R. Slabcrt *J. A. Glaaa D. E. Up R A Pile (2) E. D. Dlckena-V. J, Eroaokc A. V. Mctowa-D. H. Kurtz m Itc Technical PIlee (2) R. J. Fulton-R. H. Bela 9. E. Wrl^t-M. I. Shamed ALTC P/Untt Ml A.L. Schulte I. M. Ermagar c. a. cum R. A. Yoiaie L. I. Crider Projeet Tech. Ninagara Clareland R. D. Scott R. A. Krueger B. M. C. Zvicker-M. 8. Rohe 0. 1. Thereon 7. J. Donat 8. C. Sctaweegarla E. J. Saha K. Greene J. L. Helson E. B. Oaborne G. S. Raster H. R. Ran D. L Kant M. 0. Priadberg J. D. Tana ill 1 J. P. Malone J. C. Bee Ip R. C. Wllfint J. A. Stahl Modified Report 41481 BFG 14326 Z1483001 Abicrict This report presents a unnsry'bf the background lead Inf up eo our flrat snlaal c<nbuatlon-expoeure axperlnants, tha currant philosophy behind this kind of taaclng and currant Llaluelona with tha taatlng. Twelve key aaeerUli Involving the following product lines (Eats*.-, Abaon, PVC, Hl-Taep) were chooen for thla Initial evaluation. All experlnents were carried out at U. S. Taatlng using a Modification of their taatlng protocol. Za smary, tan out of tha twelve aubaltted Materials perform* worae tha- wood. One SMoke retarded PVC fomulaeloo vaa Much superior to wood. An aoalyala of tha data indicates that 3 out of tha 10 aaterlala ware worse than wood because of tha anount of coabuetloo products produced; the remaining 5 seaplea ware worse than wood bocauee of tha hinds of eonhuaeloo products produced. 21483002 IfbU 9f foBHatf 1. Introduction: Problea Development Paste 1 II. Discussion of Toting Protocols l III. Tho U. S. Testing Protocol................................................... 3 A. Procedure.................................................... ....................................... B. Discussion of Procedure end TestingPhilosophy .... C. Limitations with the U.3. Testing's Protocol .... 3 4 10 IV. Test Results on B.P.Goodrich Materials ........................................... 11 A. Materials' Selection........................................................ 11 B. Specific Testing Procedure...................................... 11 C. Analytical Results............................................................ 11 D. Discussion ............................................................................................ 1** V. Appendix . . VI. Bibliography 21483003 BFG14328 L. Iacroduct Ion: Problem Development / / The need to obtain bioassay date on the combuaeion products fro* BPG plastic materials has been increasing t Lpilflcantly over the peat two years. Federal programs aimed at the toxicity of combustion products from synthetic materials, In general, have all involved both analytical and bloasaay Measure* oents. This activity has Increased very significantly In 1974*75 with federally sponsored progress at University of Utah, University of Pittsburgh, harvard University, the National Bureau of Standards, the University of Michigan and the Federal Aviation Administration. Specific progrnaa at these institutions have already been discussedd"*). The following pertinent information has developed free all of these progress: Cl) toxicity defined In terns of analytical Measure* ante la Msanlaglaaa without aubatantlatlva an las l exposure data and, (2) aninal exposure experiments generally Involve brief exposures (15 minutes 60 minutes) accoMpanled by high gas concentrations (1,000 10,000 ppm). Earlier this year, 1 carried out a survey of pertinent animal exposure cape* bi.liti.es around the country and proposed In-house, In-depth teating(S), Since w do not have tbs la-house resources to carry out such a program, It vaa decided that an outside testing approach ehould be conetderadTM'. One of the facilities surveyed by me^ seemed to fit thla approach, so a program was developed to expose tbs combustion product* from 12 kay BVGCC products to test animals (V *' The purpose of this report la to summarise the results of these first exposure experiments. II. Desired Testing Protocol Currant research involving the exposure of teat animals to combusetoo gases appears to have the following characteristics: (1) smolderlne cactuation * flaming combustion la usually avoided because It invariable leada to hyperventilation (from CO^), anoxia (from O2 depletion) sod thermal stress. Alao, it la recognised by many that the smoldering product* of cabustlon (generated by Intense flaming combustion alaswhere) are gen erally responsible for Ufa loss In a fire* Thla caoeept is still the subject of much currant debate within the fire research community* BFG14329 21483004 -2- (2) sample a lie and exposure volume? It is obvious chat the race and degree of animal intoxicitlon Is very strongly dependent upon conbustlon gas concentration In the exposure experiment. This, In turn, la dependent upon Che amount of staple that la consumed and the voluw Into which the coobustlon products are dispersed. Typically the ratio of mass lost during combustion to the total vol>>-- of exposure is measured. Ratios currently used by combustion toxicologists range from SO to 500 mg/llter. In general, very little animal response is recorded below this range (l.e., 01 response) while extremely intense responses are recorded ebove this range. To put this engineering redo in perspective, It should be noted that the ratio for the NBS Smoke Chamber is 10 - 20 mg/liter. This value indicates the reason why the NBS Smoke Chamber is generally not used as a toxicity chamber. Recently, the University of Utah has extended this mass/voluae ratio In the NBS Chamber by increasing the output of the radiant beater to 5.0 vatts/ea* thereby Increasing the mess loss in a typical sasple* They have observed significant mortality induced by PVC combustion products for a m/v ratio of 30 - 40 mg/llter^9). (3) exposure Clae Experiments described in the literature on the expoeure of test animals to cognation products have ranged in exposure times from 5 minutes to 4 hours. Current research teems to be seeding into the 13 minute eo 60 minute exposure range. Clearly the four hour exposure is not representative of a real fire hasard; in fact, any exposure over L hour may noe be relevant to the h *ard chat ia being modelled. (4) response measured Historically, the end point in a combustion Inhalation experimtat has been animal mortality. Recently research has been directed toward animal incapacitation, which la turn is monitored through "avoidaoca response" experiments. Typically an avoidance response is elicited from the animal thraigh an external stimulus (l.a. alactrlcal shock); ones incapacitation in the animal Is attained, ia this case through combustion gas exposure, the animal then no longer avoids the external stimulus. Philosophically, an avoidance response experiment is Mich preferred to e mortality exoarl^nt since the fundamental haaard in developing fire is the incapacitating syndroms (or syndromes) that precedes death. Unfortunately, the research on avoidance re spaa In combustion toxicology is in its Infancy. Therefore, typically. 21483005 t -3- animal mortality la aonitored la a eonbustlon Inhalation experi* sent* Theae measurement* afv' usually of th following type: (1) tins to SOT aortellty for a fLxcd aata of aaterial or (11) veriable aaaa to induce 301 aortaltty for a fixed exposure tlaa. Economic! uaually decide which expcrlatntal approach will be taken* Expert* mental approach #2 la aore definitive but auch acre costly. Ao laproveaeot on approach #2 van made at the University of Michigan recently la which the aesa-of-aetarlal range for iaduclng a 0 1001 aortallty range (fined expoeure ciae) wea determined^). ni,_ The 0. S. Ttatina Protocol A-s__ Prpadmt le la obvious froa the above diecueeioa that aa we get into ehia eree of testing end establish data on SVG products, the following Information would be aoet dee treble in order of descending priority: (1) 1neapedtat Ion/biologleal exealnetlona (2) aortellty (e) multiple done (aeaa range) aultiple response (aortellty range) curve, (b) eniltlple doaa (aass range) - single response (301 aortellty) point, (c) eingle dose single response point. The coee, associated with chase levels of easting, ranges from $9,000 - 913,000 for (1) to $230 for (2e). Obviously the knowledge obtained froa any easting protocol La more or leas proportional to the amount of money spent. la an attest to eiafaisa coat and yet establish a baseline that la representative of the testing that la now going on around the country, u. S. Testing Co., Inc. was chosen for our first animal exposure experlneota. In the 0. t. Tenting protocol, the following procedures are carried out: (1) 10 test rets are pieced in e 40 liter eolaal exposure choker (glass). 21483006 -4 U> tha UK latpU tr exposed to radiant heat in the absence of en igniting flame In a 20 Hear combustion chamber, (3) the time of exposure it variable; the test is stopped when one bell of tbs animals ere deed or one hour whichever occurs first, (4) The test he* been designed so thet wood induces 501 mortality for sons period of tine under 40 minutes, (5) combustion geses formed in the combustion chember ere circulated through the animal chaster at a rate of 8 litars/alnute (4 liters ^minute raw combustion gases + 4 llters/alnute outside air), (6) materials are evaluated with rsspact to tha time to SOI mortality, (7) U. S. Testing rscoemends an exposure takersture of 27S*C and that matarlala be evaluated on an equal volume heals. A schematic of the tf. S. Tasting procedure la shown in Figure L along with pertinent parameters relating to tha test* Photographs of the combustion chamber with radiant penal (Figure 2) and tha animal exposure chamber (Figure 3) are also shown. B. Discussion of Procedure. Limitations and Taatlnn Philosophy Before discussing tha V. S. Tasting procedure and limitations ^ ,,*eof (aa viewed by tha author), It must be s^haalxed that a "standard teat eethod" for combustion toxicological tasting does ggg anise. Indeed further modiflea cions of tha procedure described above will be eade aa the entire science of combustion toxicology grows and aaCures. Thus tha procedure described above should not be considered secromance. In aa effort to discuss the U. S. Tasting procedure, lea relevancy to other tasting procedures, and its limitations, 1 poem tha following quest ions which have been directed to me by a number of people: (1) Sines fires Involve flaming combustion, why doas the procedure call for smoldering combustion? As noted before, flaming combustion leads to e^erlaental prob lane (beat stress, anoxia, hyperventilation) with the test animals. Secondly, aa Intense firs will ersate a thareal front or wave that will create significant pyrolysis la aatarlals cloaaby. BFG14332 214S3007 t U. S. TESTING PROTOCOL EXPOSURE TEMPERATURE: 400*C MASS MATERIAL EXPOSED: --lSOg BFG14333 600G 8W ' BFG14334 - 8- Another question arise* with respect to the fact that heat stress, anoxia and hyperveotilstlon are real problem* in a firs and prob ably should be modelled. At this point we can only puses at the laportence of these three effects. Certainly hyperventilation caused by COj Is auch aore l^ortant than heat stress (a statis tically significant group does not die froa bums) or anoxia (Frlstroa's work at Johns Hopkins showed that in a full-scale fire, oxygen depletion Is not an laportant hazard except In at^ very near to the fire rooa). (2) Why it the expoeure teaperaCure 27VC? In ay opinion, thla la the weakest part of the procedure. U. S. Teetlng feele thet thla la a good nodal for a 1m Intensity fire or the early stagaa of a fire and thus describee the Initial gas ha tarda In a fire. Frankly, Z don't faal that thla arpoamt Is entirely vetId end Z strongly suspect thac an exposure temper ature of 275*C will be rejected by aoet in the fire comnity. Historically, Inhalation coabuatloo experiments have usually involved exposure Ccaperetures in the 450*C - 550*C region. The WS Smoke Density Chamber is baeed on en exposure flux of 2.S vatts/ca2 or approximately SgO*C. (3) How sensitive are the test results to exposure ce^erature? Z feel that this aay be the aoet l^ortant variable In an Inhalation experiment. For example with respect to saoke, which is only one "product of combustion'*, it has bean shown chat La changing the flux from 2.5 to 5.0 watts/cm2, the ranking of aatarlals will change significantly. Recently, Eiahora baa stated (though Z have not yet seen the data) that the combustion products *ron wood are aore lethal whan generated at low fluxes (1.0 - 2.0 latts/cm2) than at high fluxas (2.5 5.0 vatts/ca2). (4) How relevant is the U. S. Tasting aodelto the current state-ofthe-art? Baaed on the following attributes of the U. S. Teetlng procedure, 1 believe thet this protocol le ae good (l.a. relevant) as aay of tha others: (a) coabuatloo la baaed on both a radiant heater and a significant mass of notarial (as opposad to a bunsen burnsr aad quarts tube), (b) Oxygen depletion is rigorously avoided, <e) the aaee loss/volume recto (100 - 100 ag/lltar) te la lias with other procedures, (d) exposure times are very reasonable. 21483011 -9- () the experiment U based oa sisable number of animals (5 male > 5 female rats), (f) Che experimentalise (K. Hohrmana) is very capable In texts of understanding the response of test animals to combustion products. (5) How significant la this particular modal or any animal exposure model to a real fire hasardt Probably not very tlpjif leant because (l) people lo a fire situation are not forced to remain in a cage and (2) fires involve s mixture of materials sod tbe interaction of materials la a fire may be more Important chan tbe performance of single materials. However, tbe political reality of Chla problem mjse be faced. First, It is obvious Chat a number of regulations are 'oesed on animal experiments chat nay or may not ralata to mn. Clearly tbs VCM problem relates to both yet the eyclaneta ben may be (l) baaed on inaccurate animal experiments, (2) is not based on sny actual human cancers. Secondly, there la obviously e historical precedence in using small scale experiments to regulate materials. The MS Smoke Density Chamber has bean used in regulations yet the same quest loos of relevancy exist with this test. (6) U. S. Testing Judges performance on an "equal voliam of material" basis. Wouldn't ants or surface acme be more relevant? This decision by U. S. Testlog in currently based upon recent i 111111111 a r 1 mu between U. S* Tasting sod tbe International Code of building Officials (ICBO) la tbelr (ICBO) effort to establish a testing protocol and thereby enforce the toxic gas requirement that is currently on tbs hooka. Our company feedback to and from ICBO haa bean vary minimal so I cannot Judge why this performance basis was chosen. Historically, the precedent, again relative to tbe MBS Smoke Chamber for material evaluation. Is baaed upon constant surface area and end-use thickness (up to 1/2 inch). Anotbsr complication with respect to tectiog must be brought up. In our smoke retardant research work within the company, research.baaed testing U dona on an equal surface area and equal mass basis (i.a. Om/g) while performance-baaed tasting Is dona only on an equal surface area basis. The mass criterion in this case la a function of tho particular and-use application. To make a long story short, we really have 3 basaa upoo which to Judge materials in an anInn1 exposure experiment: (1) equal area/cod-use thickness (11) equal area/conatant volume (ill) equal aree/conatanc mesa tb QC $ ic 10 - Fran a performance standpoint, #1 would be mote reasonable but frea a research standpoint (what la causing animal mortality, why and hew co correct) #3 would be desirable. Our experiments at U. S. Testing were all carried out on an equal erea/eonataat wsa basis; It is obvious that if ttw performance' criterion la ultimately baaed upon an equal volume basis, then our current experiments will be of little value in ascertaining performance. Since wood has a aieh lower density than noat of the plastic Materials we investigated, our expcrlatnts at eon* scant naea will have bean too al^d if an equal volvne criterion la called for. It is obvious thae the yet-to-be eatabllabed ground rules will play e very slpiflcant role in the comparison teat involving our materials and wood. __ Ualtatlone with the tf. S. Testine Procedure There ere e nunber of limitations inherent with the V. S. Testing procedure. These ere listed below end discussed in depth. (1) beaie for performance-evaluation: This hat been discussed above bue it oeede the attention of thoec who ere interacting with the code groups. (2) tternel exposure conditions: Rather then expose the notarial to e constant te^ereture in which energy la increased or decreased during the experiment in order to maintain e constant ta^arature directly in front of -a ea^La, a flxad ensrgy input along t^a llnea used 1st tbs KBS Snoka Chamber should ha usad. There are indlcetiona that 0. S. Testing is moving in this direction; fixed energy inputs at 1.5 watts/cm* sod 3 vatts/cm* (or related values) would be highly desirable. (3) animal'a body wastes problem: During exposure, tbs teat rats constantly release their body wastes and these remain In the cage during exposure. This is s very important parameter; Cornish (Qnlwrslcy of Michigan) allowed in 1964 that animal urine la a very efficient hydrogen chloride scrubber. 1 recoamanded to U. S. Testing that this problem be corrected. X don't believe we went inhalecloo combustion data that la based on experimental artifacts as described above. Un fortunately, X did not realise the al^lflcanee of this problem until we were half way Into our tasting program at U. S. Testing. BFG14338 21483013 11 ftut* all data In tbla raport la baaed upon the preaenca of the animal waste artifact. This artifact will tend to positively Influence the par forma nee ofthose materials that produce acid gases during combustion. I cannot, at this tljw, ascertain the magnitude of this artifact on the test results. IV. Tese Results on B.F.Coodrlch Materials A. Materials* Selection The objective of this study at U. S. Testing was to sereen key BFC products (coenerclal formulations) with respect to fire retarded and nonfire retarded formulations. The choice of aatarlala was more or leas based on those product lines that would be suacaptlbls to toxic gas regulations. For example, while our analytical studies Indiesta that Bycar may exhibit a problem with respect to hydrogen cyanide avolution during smoldering combustlon(lO), this material was not chosen for evaluation because the signi ficant market hare la la automotive under-the-hood applications; this market will not be subjccead to toxic gas reflations. The materials chosen sod cosmante relating to those choices are sumnarlted In Table 1. In weary; 12 key produets involving the Abeon, Hl-Teap, PVC, end Katana product lines were chosen for evelustloo. B. Spectre Tgeglfla Procgdy^ For all materials, except wood, eppraxlwtaly 140 - 130 grama of material was placed in the combustion chamber sad exposed to 400*C In the absence of an Igniting flams. Tha experiments were continued uneil 5OX of the entomls died (by visual observation) or 1 hour whlchaver occurred first. The soimsis were then removed fre-j the exposure chamber, placed In wire cages, sod postobserved for two weeks. All materials were evaluated relative to white plot and the baa la of ehls evaluation wee the time to 50X mortality (tu^g). C. Analytical Kaaulte Tha following analytical maaeunemats were made during the exposure experiments: mass, mm lose, minimum Oj recorded in animal chamber during experiment and the time of death for eaeb animal. In this sectIon, this death data la suHsrized In terms of an average tlma to death (tlAjg) for a 501 population and ehe total death incidence (X mortality). It should be eophaelsed that It la impossible to carry out an e^erlmeat where an exact 501 mortality la recorded. Typically, the mortality la higher than this because soma of the aalmels that survive tha exposure ere so Intoxicated that recovery la not possible. Tha tlma of each animal's death for all experiments la recorded la tha Appendix. 41 481A lumtry of all analytical data la 21483014 - 12 - JL S T O f.S b T ? . Material PVC/CPVC Ceon 8750 8750 + 35 phr Al. hydrate + 6 phr B/N<1> 8750 + 35 phr Ai. hydrate 8750 + 1.5 F/8.5 M (2) 8804 Blk 288 8737 81k 2S9<3> 3010 85721 Nat. 020 A as 89129(4> 820X16 + lubricant Control Currant Iw faoki (near commrclallzatlon) PTC compound Another low awoke coag>ound aearlag field teeting Par D. Dickana reeoanendatloo Non*fIra retarded flexible Jacketing compound _____ A representative fire retarded flexible formulael n Hi-Tenp cc pound Expended formulation Currant i e retarded Abson compound Identic . :o 89129 except does not coataln fire scardencs; A:B:S ratio la identical to th.t In 89129 Estane X430 X430 + drlp/flra retardant*5* Theie cwo co^ounda are a result of new fire retardant technology; polymer modification baa beao carried out to Improve drip reaiataoca; theae are near cowrclalliatlon* Noo-putlc Control a pine wood wool fabric Aa per U. S. Teat tag procedure Thla hea been Included ea an example of a nitrogen containing natural product; recent MBS raoka chafer atudiaa auggeat very high level# of h^rogen cyanide during anoldertng conbeetloo. (1) Refer* to 3 phr hleauth aubcavhonata > 3 phr nickel oxide (2) 1*5 phr Iron oxide + S.S phr Iron oxide. <3>Antimony oxide retardant. (4) Pire retardant la baaed on PTC + antimony oxide co^oaltlon. ^ Baaed on decfeloraaa, antimony oxide, chlorinated polyethylene BFG14340 - 1J . srmatT or ALL daia rum u, . P9T11C AKOlAL exposvtt exftAtWlftS Nnli rla 1 Ah^.-n A.'iKtl*. Ali *,'KY{*i [ . r . ......... nni*. Aik ,,>aa i . A/17 lU 289(S* 14 in T. m * l.t. i- .m A/Vl u >>n H /Si* * l) pbr hydrated aluutna )) phr ll/Nl CM c.Mt nimi + j) phr hydrated .1 tumlmi a/mi * V> phr r*/nt CM ^ HV.'I Nat. <no w.i (nHtiri'l) W...I <c>aitr<*l) Naaa, a ibu TUa. Oj(lJ luaa, g la CbMbar 'LD10. 149 14 7. ) 14 7 ISO 14) 142 144 144 147 144 2 14.) 21 S7 42 77 48 J4 11.3 24 19.0 19.) 17.) 19. S 1S.0 17.0 17.0 to.) 19.0 18.0 4.1 9.1 13.8 8.1 14.9 10.1 IJ 41.4 tipoaure 1J.9 1*9. ,14) ,, 14 5 37 141 24 )0 10 20.) 19.3 l. 19.0 ll.1 10.9 J9.0, )*.4<n js.st> v. s. t.- l NurtaUty^^ Bank 1m loot loot 70T loot loot tom 5<71 80t l 1 10 4 9 ) 2 12 14 .(4> *71 9 9171 4471 4<*t 4Jt ? 4 ll 1J 11 ) TIi I la h" vlnli amn l*wl thac waa racardad In ch* anlaal caga during aaposur*. data nmcatnad tn Appandla. ll)-nv-w tlracba uurrrd daring cba Mac or toaadtoMly altar. *"**t-wrc: |o*Woc ('V (irc-rptaiM tlrilktt (urwlltioi <MTV *( aatortal to chid ns mi coo bL0u bouarer, atoca wa aro toco a "tbarvally tblcb" region, reducing ehi- aau e* 14)g will probably not affict cba oaaa loaa ilpKUaattr; tbia nacorlal will ba 1 i.a wait* obcatood by V. I. Ttactog at cbalr own coat. <a> f,,r WT unreality. 21483016 BFG14341 14 - D. Discussion Of Che 12 BFC produces Submitted by us, U. S. Testing has ranked then In che following decreasing order (see Table 2) of hazard: Absoo > f.r Estane > f.r. Absoa > Geao 8804 > Cseane > Geon 83721 > Geon 8750 + 10 phr Fe/Ni > Geon 8750 + 35 phr hydraeed alumina > Ceoo 8737 > Hl-Temp wood > Ceoo 8750 > Ceoo 8750 * 35 phr hydrated aliaslna + 3 phr Bi/Ni CPA Thus ten out of the twelve aaterlals are worse than wood while one Mterlal Is superior to wood and one Material la far superior to wood* The worse material was Absoo 820X16* This Material literally exploded, (observed by U. C. Bechtel) and resulted lathe generation of a rapid, highly cooceaerated dose of combustion gases* The situation la the animal exposure cage after 7 ainutes Into this experiment is shown In Figure 4; not* the brown, heavy snake - ell eainels were dead or near death (totally incapacitated) at this point. A content on the wool experiment Is in order. It will be noted in Table 2 that the amount of material tsstsd in the experiment with wool was significantly lower than all other experiments* This was done so thee soother "1001 deed, short time to death'* date point was not obtained. Thus, le sbsolutely csn not be concluded thst wool is safer than wood because the evaluation was not dome on an equal mesa basis* If It had been, there is no doubt in this author's mind that wool would have been one of the worse omterials. However, this decision to reduce the ness of wool In the exp* nent was made on purely analytical grounds. In an attempt to analyse these results, s brief review of the factors thst lead to animal mortality Is la order. There are t*o significant factors that control anisml mortality in a combustion-inhalation experiment: the kinds of combustion gases and tha amounts of combustion gases. If, for example, ehers Is evidence that a larga amount of combustion gases Is generated sad animal mortality is low then one must conclude thst the toxlelty of those com bustion gases is low (Case I). On the ocher hand, if a small amount of com bustion gases are generated and animal mortality Is high* then one mist con clude that tha toxicity of those combustion gases la high (Case II)* finally, tha third situation la tha esse where a larga eonceatratlon of coafeustloo gases are released and animal mortality is high (Case III). In this situation, one cannot conclude anything about tha tomlelty of the combuetioo gases because tha detector (animal) has bean overwhelmed by either a high concentration of moderately comic geeoo gj a tow concentration of highly toxic gas la the presence 21483017 15 Ttipn * Animal Exposure Chamber After 7 Minute* Into Experiment With Abeon >20X16 ______ ____ I 41481 W cc cc o (X BFG14343 ttepioja 21483019 9*9 rot re 6*91 8*8 8*01 9*19 rtt e*u 0*6C 6*CT pop 00 1*8 S*S 03007' 8 ii 99 9 XC K 82 92 92 n S*8I S*91 01 f **90\ MUI 91X028 *9V (91) 0C9X powpI (1) *X*i + 0C9X P3*X (21) IU9 *0 (11) 9088 w>9 (oi) 122*8 oopo (6) 0g oo*s (9) 9dD JMd 01 + 0S28 *9 (X> d*i-7B (9) pooa (fi) *i **q + osx8 o <9) W + 0528 f> (C) Ootqy '9`i (2) IOOA (x) XP7*3m --------- - .. uotq anoqt rf 8073011 tpu *poqopu oat 00070*10000 807 -3p*03O7 jo 2qm v '07009 *(Tl3 o no pMPdooo u*qa m poo ox i *7Pqa oa taxpaesov poa*xx 9*o otPtaoapo JI (mat 99 - sbvjS oi) *! *,,i 1 *on *P7a * 37473x0 prp p3**3 um aotp oxo?*apo *qa Xx*aoana*oj *p7P *700700 pqa XqA pot taanpoad 00730*9000 pqa JO XaT7*3 qa anoq* px* *q oro 9nrqaapoo *f*>73tnqooo 9o7*np pool * ajpqs jo aq*Tt Pt*of ** TP7* nw JX 'onq ox > oqa *7 oaonpoad 00730*91*00 oqa jo TStSWKE *qa jo jaaiiMM e* omxx* aoqa aoMOinoooa tool3*1*0* *a*pavaoa *v*i + o8 0009 rf **33pi *qa 70 pftepxo op J9X3038 oo*qy 07 **m*oj oqa jo x4bw* oy *ao*q pqa ooaj 1*7*03^ 071*74 8o7Xi*ppoi pqa oaooaoad a pqa o*j*n p pampoad poo aoqo 03 paa oaaqao ottq* oinpodxp pqa toT*np ppoxdx* Ixi*9*3!! oaonpoad wmos PtP7*pao 70 Xaxxxqn* tKaqa 807X1pa pqa 70 oonpapq *xqt**odB7 7 *743 #*apop *f7PPq H*aonpo*d oo73nqoo J 00730*30*0000,, lonbo o* 00 fin*3o oapfeoo 03 rqn p|noA pa Xn*pl *p*7P oxpot* oqa X^ popao**pun oa 807X33 pop tfnapol *s *Q 3* oainoo* ano 807*074 07 aopaaodoi P7 nr XP07} rjqa jo oovroxjxatxa pqj *p*f 97x03-000 go 00730*30*0003 qlxq * go - 91 - 17 a analyzing chi* li*t and in light of the three classlfIcatloo* discussed above, 'It la apparent that materials #10 - #14 (a** Hat, above) fall Into a Clasa 111 category* That la, the a* eatarlele are hazardous, not because their combustion products are especially toxic, but rather because a high concentration of combustion products vere formed* As with any Clasa 111 material, we can say nothing about the degree of toxlelty of the combustion produces* It Is interesting to note that the average ness loes to volume ratio for aaterlala #10 #14 la approximately 700ng/lltar* whereas it Is only 120mg/llter* for wood* Cleerly the low thermal stability of these materials, and not any unusual set of combustion products, is responsible for their poor performance In the test. Materials #4, 5, 6 end 7 all exhibit about the sane mass loss yet the three plastic materials (#4, 6, 7) are siptificaatly worse than wood (#5). inis la, therefore, a Gaea 21 situation in which the toxicity of the _ equation products from sample a #4, #4, #7 are wore* than those from the wood control. Comparing material #2 to wood (#5), the combustion products tr<m this material are alenlflcantlv more toxle than those from wood. Along the same lines of reasoning, one must conclude then that the toxicity of the combustion products from sample #6 (Geon 8750) is lees than that from the wood control. Sample #9 (expended vinyl) also seems to be a Case 11 situation* Comparing this aa^le to aenpla #8 (rigid 8750), it can be seen that the combustion products fron #9 asm more toxic (significantly) than those from sample #8. This co^erison of sample #9 with Geon 8750 rather than with wood is necessary because of the similarity in anee losses between eae^l #9 end Geon 8750* Finally, MterUls #1 and #3 (wool and Goon 8750 + CPA) present an Interesting case. Material #3 exhibited one of the lowest mass losses end subsequently none of tla animals died during the exposure* Wool fabric (#1) on the ocher head exhibited the lowest mass loss yat 40X of the animal* died. Either the wool fabric la vary bad and the modified Geon 8750 is good or the wool fabric la moderately bad and the modified Geon 8750 la vary good. *Thi* value wee obtained by the following treatments M/V + *2 + *JJ wh*r Vt sod V2 at. tte cluabar valuata, fj t* ch* clt*n *lr flw lata th* xp*rlatnt (Utara/ala.) .a* tj 1* HAjq <1b adnata*). BFG14345 21483020 In lutMry, eta* above treataent Indlcatee that there arc two cUimi of materials chat are bad but for different reasons. Ona clan of notarial* .(#10 - #14) exhibits a high degree of eoxlelty of combustion products because a vary high concentration of combustion gases are produced. This in turn la duo to Chase materials' low thermal stability la a high temperature environ* ant. Another class of materials (#2, #4, #6, #7, #9 (perhaps)] exhibits a high degree of toxicity of combustion products bacause their combustion products ere more toxic than tteoee from wood* In the final evaluation though (regulations), it really doesn't natter why a notarial la worse than wood, only that it la. Yet this distinction is important to ua since solutlona to ona problan (or class) aay not ba solutions to another problem. It muit again ba emphasised that these experiments are in essence only a jingle experiment. He know very little about the reproduelblllty of the teat (it appears to ba reproducible with respect to wood) sod the test will undergo modifications as the science of combustion toxicology matures. 8w ever, I believe these results, whan viewed in light of current research in this field, are reasonable and suggest that a continuing and sustained effort la this area la not only Justified but important to our future grewth In the market that is affected by this kind of legislation. This itedM coQUiaJ a ion thorough lifting of th aolail t*e data than it coquload 1a Tabla 2 Llatad bl<*f arts (1) HUrUli eaatad (2) individual anlaal daath tlmi (3) pose axpoaura daatha and tlaaa and (4) two-vaak survival. BFG14349 21483024 f Death (m inute*) Poc-Expo*ure Dech* S urvival - 22 VI. Bibliography (1) M. H. O'Hara, '"trip Report: Parc 1 Aoiael Tatting at tha University cf Utah**, 7/15/73, 1.0.C. (2) H. M. O'Hara, "Currant Federally Funded Studies on Toxicity of PVC Coobustion Product a", BFGCC Heating Report, 8/22/75. O) H. M. O'Hara, "Exposure of Kata to tha Comb melon Products fro* PVC" (University of Michigan Work), BFGCC Technical Report, 12/274. <4) M. M. O'Hara, "FAA-SWRI Statue Report", BFGCC Technical Report, 10/8/74. (5) H. H. O'Hara, "The Use of Anlaal Tasting a Kev Prohe in the BTC Placability Progran", I.O.C., 3/27/75. 9l (6) R. W. Strasaburg to 8. M. G. Zvleker, "Anlaal Tasting for Flaselc Combustion Products", 6/75. (7) M. M. O'Hara, "Animal Tasting at U. S. Tatting Company, lac." (Part 1) BFGCC Technical Report, 4/21/75. (8) M. M. O'Hara, "Anlaal Testing at U. S. Tasting Company, lac." (Part 2) BFGCC Technical Raport, 6/7/75* i (9) Technical leport on this Utah prograa in praparation ,1 (10) H. H. O'Hara, l. S. ShU, "FlaMbillty of Hycar 1061 Part 2", Staff *4 Technical Raport #328. BFG14350 S DlitrlNtlo* >*OM _ " ----------------------------i'JuuS'WWaSi Wdf i ido so ' ' ---- _____________ M. M. O'Nsra ubjCT Avon Lalta Technical Canter ^October i.9, 1975 -- . The Interrelationship Between Bioessay Testing and Analytical Combustion Studies. Part II; Analysis of Tonic Cases Introduction In Part I, I attempted to show the Interplay between bloassey testing and analytical chemistry that should take placa in ordar to keep outside bloassey testing coats within limits iaft to bring a more fundamental under standing to anlael oxporlonato. la thie report the discussion win revolve around the problaua of tootle gee aacourenoato and the status of our progrsn at AUC to provide a sggfglggg effort in thie area. It noet ha reco^lxed that one of thn kay conponanta to the rapid growth of our Copsay'i anoha retardation technology waa the existence of an accepted teat eatbod. The MS Sasha Density Cheater wee essentially "on-line" at the inception of the early anoha noth at Bracks*ilia and Avon Inha. THenha to the foreeight of t. Ihjeti the rhidior waa purchased, tested and put through an in-houas anoha onesorenset progran. Thus, we hod testing facillciaa that were available and nun or lata accepted by thnts who were considerleg future snake legislation. In addition, our in heuas progrmaa were la signal to provide a thorough, basic understanding of chnhbar dynamics so that future develapneutal programs, which ware based on the chaahar results wonld ha on a firm tbooratical grand'1'. Thua wa warn in an excellent poeltion analytically to exploit anoha retardant technology. Unfortunately, wa m not at thin state with respect to "low uals gee technology", them U no aeeepted itinl tasting prooedura and than are no "acoaptad** analytical aathoda of eonhaation analysis. This problem la anon farther r.ia^Hnamd by the feat that enohe retardant tnetaology U baaed on a single nananransat of con product of eo^ustloa ttet in knoani Mk gga tarhnol ngj meet bo baaed ipm multiple neasurenanta of an MWH varietyj( eeshnetloa products (at Uat count PfC had over ft na^namm ggadneta12') that sen in neat annas mkmmm. Not only arc mmf of Mi pcedusto mhanwi from a qualitative analye it standpoint but they nan M oMsan from aa acutaTM' tonicity standpoint. With this level of oa^Ioalty of the problem prsnent, it neat be obvioua that rapid nlutloaa to all of our tonic gas problems will sot be forthcoming. In fast, mush of hi driving foroc babied progreat la thin area lias in aedical idleness in defining combustion toxicology, Onfortuoataly, the political arena sad regnlatlans will not wait for this !! grinding of medical <l>*. D. M (2)I. Sainsr, Ptagran for US e private aonnualcatlon. BFG14351 Chamber Studies', 12/14/71 arras p.opposed to ohronia tonicity (nonthe. 21484001  October 29, 1979 Fes* Two Ivon In light of theta coo#Id*re Clone, the problem is manageable. For specific plestic*, cho me Jot combustion toxicological hazard can be approximated and, therefore, can be approached scientifically. While pvc ay produce 60 combustloa/degradation products, three of these probably account for 99*T of the toxicological response in test animats: hydrogen chloride, carbon monoxide and benzene. Medical research may eventually shot# that aromatic hydrocarbons pley e role in transporting hydrogen chloride into the biological system. Thus, analytical work on PVC products which is geared toward hydrogen chloride, carbon monoxide a total hydrocarbon analyses* trill go a long way in establishing cause and effect in animal experiments. In nitrogen containing polymers (Byear, Abeon, latmoa), there are specific cognation products again that probably can tribute significantly to toxicology. Specifically hydrogaa eyemlda, hydrogen halides (from fire retardants), nitrile compounds, nitrogen amides and carbon monoxide ere of greatest concern. Well designed animal exposure experiments coupled with analytical data will show which of than* products are of tht greatest concern, from omr analytical studies alone, we know that hydrogam cyanide generation from Bycar la significant'*) hot la negligible from aoe-fir* retarded Katanav^) under smoldering comdltlcee. Omr the peat 4 ymere mo Ism ilody bdlt t* omr capabilities in the area of commotion gaa mnml racing, An M development cook place, a problem in data hand! lag developed. VsrbnaMly, amtllar this yamr we amend Into omr now OnagbUlty lab aad amdtsd Ha problem of handling the massive smnmat of data that cam ceamlt from combostloa gaa axparlmaata. 6. Bnltk has beam given tha assignment at interfacing six of our outputs to a data handling ayecon. As of 10A/79, this project was 951 cooplet*. A SMtry of tha coabnatlom gases that m can annlyao aad methods of analysis and data handling are summarised in Table 1. Currently we ere developing a aam antbab of oanlyala tor hydrogen cyenido based on olactron rapture ^g ekramtogpoglqrand wa namd to further develop tbs gpa . itemitsimhlmvus mans trie natbmd of epeeif ic hydrocarbon analyses'*'. V total hydrocarbon oanlyoia, 1 naan a quantitative emalyois of the total fcgdiauartima not an analysis of each hydrocarbon In the mixture. <4>* M. Olfcrn, Staff ttebnUial lapert #32*, 1/22/79. <5)L K. Olbfa, papar praaeated at 1*79 teirlma IndustrUl Hygiene Aaaee. Maeting. M. O'Hsra, "A Mithod for Trapping Volatile Organic Combustion Products from tha HM Smoke Charter for Subsequent Msas Spectromstrlc Identification", Staff Technical It*port #333, March 10, 1973. BFG14352 214S4002 BFG14353 Hi H friai&fU(f) of isft*r4i hrcMto*rt*hj flM AM0|rifev flM yiMirHv tw llllttlrflt Mt flllft* H4SMMtaM| titrilM, h|lri Mrt iw, u. iatra*n4 AM Amto^afkr MU fUtCIMU/ eoQtfftTZ cmcImui or btuk coaCifluoua or Meek tauk botch botch cootiououo botch botch cootiououo cocttououc botch October 2% Hu Four thar^r 0r the put year Z hm vithdtm from the iru of coUmcioa product analyse* (aoro or lu) cad wo have devoted our raokc chaabcr to saofce rotardcoc itudUi la support o lias group activity. To reestablish ooroolvee la till needed croc of 0 rheology, Bob Yount bit beta assigned to the notability croc* A SSMBMMHI attained effort can non b carried out la the cnabuitioa pi iim. Za additioa to till, I hm ccuaitted sppconfaarst j 90S of ay ttm to chic orao ao that both support program (davnlopaaat) cad oaa aethoda taobaplogy (roaaarch) caa bo carried out slaaitaacously. Oar laaadiata objectlveo la Ola araa are the following: a> co a) uric es. la (4) data that hoc sitoady collactod lltlvoa la rigid FTC. thin. t oar aaalytiaol ibdlu be celled to ia-houee eh this paobloa aroa. Thereforo, our loag with Corporate haeoareh, Cheaieal Cragriny daoalopaoat pvagraao la the aost affloadoua U. H. 0*Mtra 21484004 BFG14354 Crldtr letelu iMkBtl ItnHkort Tivcct FrMtorg liTlt T ttafcl Mmtt 0 tiliNr IfclCM n--im in 21464005 ti.'' . '4 BFG14355