Document dD9NLMqDV0o8bK2N8xXaLgM6

MonsantoS O .C I E T E TOXICITY OF FIRE RESISTANT FLUIDS USED IN COAL MINES GENERAL Fire resistant fluids currently used are classified in 4 categories called A, B, C, D. Liquids A are oil water emulsions containing a maximum of 20% oil. They are made of hydrocarbons and additives and are used in hydraulic pushers and props. Liquids B are water-oil emulsions containing a minimum off 40% water. They are not currently used in the CEE mines because none of them have been able to meet the fire resistance spe cifications. Liquids C are water glycol containing additives and minimum water content is 40% ; they are used in mine car pushers. Liquids D are synthetic based on chlorinated diphenyl and aryl-phosphates esters. Fluids composition can vary, but roost of fluids we have analyzed are about of the same chemical composition when examined by infra-redspectroscopy. As of june 1st, 1971, 274 liquids have been submitted to CEMM. Today, only 14 are being used (3A, 4C, 7Df. .../... DSW 586330 STLCOPCB4091664 Monsanto ** 2 * These fluids can causa Injuries at different levels either in normal use or during incident or accident, such as leakages, hose breaks, smelting of coupling fuses, etc... Consequently, the E.C.C. proposed in successive reports a list of toxicological tests. The last one has been Issued on March 26th, 1971. These tests Include oral toxicity or irritation value, on toxicity of aerosols at roots temperature or at 1509C. and on thermal decomposition products toxicity. Each test results are marked from 0 to 10, following a precise scale. Final mark is obtained by adding up all marks multiplied by a particular pondaration coefficient for each test. If this amount is below 50, the fluid meets the specification except however if one of particular mark reaches 10. C.E.M.M,(Centre d'Etudes Medlcales MiniOres) equivalent t Mining Medical study Center, has all equipment needed to carry these tests i - infra-red spectrography for fluids identification (A, C, D). This test is necessary to find out if no change in formulation has bean introduced by the manufacturer without changing the product brand-name in adding a low quantity of a new component to modify the final result. - Oral toxicity (A, C and D). This teat la a determination on white mice of the lethal dose by ingestion. To carry out this test, we would need about 250 mice for each fluid. For this reason, we do not run this test because it does not reproduce a normal incident. It could only happen by a volontary Ingestion, and quantity would be then defined. .../ DSW 586331 STLCOPCB4091665 Monsanto Ponderation cofficient equal 1. Total toxicityof soluble oils and emulsions (Aand D) We carry out this test on a fish called "carassius auratus". Survival of fish in an acqueous solution of liquid at different concentration is marked. We know fish breathing and ingesting water is very sensitive to toxic produsts. Ponderation coefficient is 2. Irritation value (for A, C and Df. Irritating value on skin and eyes of rabbit are determined by contact with the fluid at room temperature. Result rating is vast, but though more severe in the last report than in the previous one, it would be not severe enough for an opthtalmologist. Ponderation coefficient is higher and equal to 5. Aerosol toxicity We use a full-grown white rat from wlfctar head. This one is kept for 3 hours in a close cabinet where spray concentration is defined. These sprays are at room temperature for fluid of "A"form, at 70*C for fluids of "C "form and at 50*C and 150*C for the "D "products. Ponderation coefficients are 4 for A and C, and 2 times 2 for D. High temperature decomposition products toxicity Fluids to be tested are sprayed to a heated plate using a diesel pump and injector system. Time of exposure is 3 hours like in qSW 586332 STLCOPCB4091666 Monsanto the preceding test) all animals going through this test are then kept under observation for 14 days. Unfortunately observation methods are not sufficiently defined in case of sub-poisoning and practically only the death of one or several animals during the test or while observation period and ponderal curve irregularities allowed us to rate this test. To summarise toxicological tests, in the way they are carried out today, can determine which fluids are hazardous. But some of them even if the total mark is acceptable, can create a false security. It is important to keep in mind the partial marks and sometimes to emphasize their value by a particular comment when this one is high. In another hand, sometimes, tests result determination is difficult, and following laboratories carrying out these tests, interpretation can differ. Today only 3 labs are entitled i they are Pharmakologisches Institut Harabourg, Piturages and CEMM. For example, when Pr. MALORNY examined a product called FYRQUEL NF (D) on rabbit eye he ascertained an erythema, leaving off after 2 days. Be gave to this test a mark 2 in conformity to report N* 4 specification. Inflanaoatory reaction according to coming out, rapidity, extent and duration t 1 to 5. But inconsistent to those mentioned in report N* 2 which specified the following rating from 1 to 5 : Conjonctive erythema and watering of eyes i /... DSW 586333 STLCOPCB4091667 S 0 C I E T 'Monsanto 5 leaving off within 10 minutes ............ " 1 hour......... 6 hours................. " 24 hours ....... " 5 days..................... 1 2 3 4 5 This rating would give at least the mark 4. As the ponderation coefficient is equal to 5, we get a difference on result total of 10 1 Consequently, we have narked the eye irritation test in using this second scale. Unfortunately, some other tests are ambiguous too. . TOXICOLOGICAL TESTS CARRIED OUT ON PRESENT FLUIDS USED IN COAL MINES OF NORTH OF FRANCE. Tested fluids t 1* ) Type A : 3 fluids - CASTROL S 4157 - LABO INDUSTRIE S 2021 C - SHELL DROMUS B 2* ) Type C i 4 fluids - NAPHTACEIMIE NAFIC 402 H - CASTPOL HYSPIN AF/1 - NAPBTACHIMIE NAFIC H 454 - SHELL S 6694 ) Type D i 7 fluids - 5P SHF 0200 ( Pydraul A 200) - CASTROL B 460 - PUEFINA HYDRAN FR 2 - SHELL S 7702 - SHELL S 7014 - SHELL S 7704 DSW 586334 /... 1 STLCOPCB4091668 Monsanto "6" He are still waiting for an other type "D", manufactured by ELF, and called E.S.T.C 724. Equipment and test methods. The report N*4 regarding specifications and test conditions for fire resistant fluids used in power transmission (Luxemburg, Marclif, 26th 1971, annexe XVIII for fluids "D") define tests method! and equipment to be used. Up to now, qe have carried out all the tests except oral toxicity and thermal decomposition. In order to test the 14 fluids presently used in the coal mines of the North of France, we have installed a thermal decomposition apparatus in conformity with that described in report N 4 able to spray the fluid to be tested through a standardized injector to a hot plate kept at a fixed temperature. One cm3 of fluid is sprayed or decomposed every minute, then, cooled down to the room temperature to condensate oil vapors and decomposition gas. Rats used in this experience breath this mixture for 3 hours and are kept under observation during the test and while a 14 days period. A draft of this equipment is enclosed. All parameters, such as temperature, fluid flow, and air flow carrying along decomposed products are easily precisely measurable. In addition, the condensation system is particularly sophisticated. This one includes a first condenser "E", a glass flask "F" where gas temperature is cooled down to about 50*Cand a condenser "G" where expanded air is injected through ejector"H". Mixture of gas coming in the cabinet are near room temperature. However, it is not possible to. condensate the whole fluid vapor. Classical safety measures are taken in order to avoid laboratory pollution : the test cabinet or cage "K" is imder a slight depression and the hot plate "D" is put under a ventilated hood. /... DSW 586335 STLCOPCB4091669 Monsanto I5SI-B1SPLIS -7 Results are rated following EEC recommendation (see covering letter). Particular narks assigned to each test after ponderatlon are listed In chart 1 with their total. These figures obtained for each test after ponderatlon, for none of tested fluid, goes over 50. But result of thermal decomposition at 700*C. for all type "D", and 1 type "C", is equal to 10. According to EEC recommendation, they cannot be approved. For this reason, the thermal decomposition test set a particular problem having to be more fully examined. .../... DSW 586336 STLCOPCB4091670 STLCOPCB4091671 Ta b le a u -1 R e s u lta ts d 'e s s a is de 14 liq u id e s d if f ic ile m e n t in fla m m a b le s u t ilis e s h a b itu e lle m e n t dans le s B o u illc re s du B assin du Nord e t du P as-de-C alais. DSW 58633E STLCOPCB4091672 Monsanto 8 TOXICITY OF DECOMPOSITION PRODUCTS OBTAINED DURING THE TEST CALLED " THERMAL DECOMPOSITION" Firstly, let us take the case of product "C", N14, made by SHELL and called S 6694 ; it is a water glycol product with unknown additive. During the test, the animals are dead from oxicarbonyl's intoxication. The post-mortem examination did not show any macroscopic alteration and besides carbon oxide, concentration in the test cage reaches 1000 ppm,though in same conditions for the other "C" fluids N* 11, 12 and 13, this concentration was only 170, 160 and 200 ppm. To check this order of magnitude, we had to take back these 4 fluids for a second experience and find out that the N* 14 incompletely burnt when in contact with the 700* C. hot plate. Consequently, the fire resistance of this fluid must be border line. Fluids of type D are made of polychlorinated diphenyl, sometimes blended with aromatic phosphates esters (arylphosphates). When the fluid is sprayed to the hot plate, there is a calefaction wich vaporize the fluid immediately followed by a condensation giving a mist whose bigger drops are about 2.5 micron size. The turbulent medium condensation system stops the bigger drops. Animals, then, had to breath a very stable mist where the size of droplets are below 0.5 micron. The carbon oxide concentration is very low {10 ppm), and there is no phosgen (less then O.lppm). Consequently, it is difficult to talk about thermal decompositior or combustion. In addition, if the mist is cooled down to minus 20*C., the condensed product obtained gives exactly the same infra-red spectrum than this one obtained on nex fluid. We can conclude it is the mist coming from vaporization and condensatior which poisoned animals ; we can say, consequently, it is a remake of the test called "toxicity of aerosols", but with a higher concentration (about 20g/m3). .../... DSW 586339 STLCOPCB4091673 S 0 C I E T E Monsanto 9 In another hand, we have tried to decompose the fumes at high temperature by circulation through a coil heated up to 700C. We have found in these conditions only few carbon ox^de and phosgen traces. These fluids of type D are particularly stable, and their toxicity either in mist or vapor is due to their components : chlorinated diphenyl, arylphosphates, and additives. 1) - Chlorinated diphenyl General formula of this product is the following : Cl Cl Cl C H Cl 12 10-n n They can be mono, di, ... decachlorSs. They are more or less viscous liquid at room temperature, except derivatives octo and deca wich are cristallized solids. They have a low vapor pressure and are used as plasticizers, fire proofing and high temperature1 lubricants. They are also able to transfer important heat quantities. Their toxicity has to be compared to other chlorinated aromatic derivatives and particularly toxicity of chlorinated naphtalene. The main result of PCB action is a liver attack. More the molecule of aromatic derivative contains chlorine, more the action on the liver is important. We must point out the synergic action of ethylic alcohol or carbon tetrachloride rapidly causing a liver necrosis. Consequently to exposure to a mist at 150 C for 3 hour the hepatic function showed evident problems. After few minutes PCB is accumulated in liver fats. They are acting about in the same ways that DDT, whose formula is similar. / DSW 586340 STLCOPCB4091674 5 0 c 1E T E Monsanto 10 The post-mortsnjexamination of animals done by the medical dept, of cemm shows in case of death a liver volume increase and in the same time a red blackish coloration and the variegated lungs show oedema symptoms and haemorrhage appearance areas. These phenomenons are compatible with the rise of transaminases found by MALORNY demonstrating an infarctual and nearotic state of the liver. The main preoccupation is the fixation of PCB's by liver fats which is a cumulative phenomenon able to lead to severe trouble even with low amounts or brief time of exposure mainly in the case of synergic action from ethylic alcohol. Besides it could be possible that some D fluids contain also polyphenyl ethers used in the States as high temperature lubricants and whose action on liver and kidneys is vallknown by toxicologs. The KaxiauB allowed doae defined by USA and USSR for PCB containing loss than 10 % of chlorine is 1 o/m3. ' "'o have already noticed a i.ighor concentration of cover a I grams per m3 in our test cages. This demonstrates the unrealistic character of the tost called "thermal decomposition". 2} Arylo nos > hates The current formular is the following : 0; / 0X DSW 586341 STLCOPCB4091675 Monsanto 11 Phenyl radicals can be substituted. For example t paratrlcresyl phosphate 0= P used about 15 years as lubricant ana hydraulic fluid in aviation. This product is probably the most hazardous of all phosphate esters. Its antlcholinesterasic action can be compared to that of insecticides. In addition it provoques polyneuritis by motory degeneration and frontal callosities of spinal cord, accompagned by various haemorrahes, fatty degeneration of liver, rate, pancreas and kidneys. 3*)- ADDITIVES We do know which products are used and of course, they can be toxic. Ke must point out that most of the manufacturers of fluid; do not talk very much about and it is very difficult even for a specialist to analyze from an infra-red spectrum all the ccmpone; of fluids type D mainly when the concentration is very low. We must also notice that oifferent fluid components used in typd' are skin and lung tissue irritating. The thermal decomposition test as defined by CCE subject animals to a very heavy and stable mist. Consequently, they support the toxic effec^fef fluid component. In the particular case of fluid this action is severe and brines animals to death. However, it scene there is no risk that fluid used in coupling .../ DSW 586342 STLCOPCB4091676 Monsanto 12 could be sprayed on to a hot plata 7 even in case of fire, it ia likely that this sort of fluid will only produce carbon oxide as phosgen is decomposed above 900* C. to give hydrochloric acid. But, if the fuse smelt between 140 and 200*C. , il could be possible to produce enough heavy mist to create haxardeous conditions, and moreover in normal conditions continuous leakage could maintain in the atmosphere a low but toxic and continuous concentration causing effect on sensibilised people and in the same time creating a chronic pathology. It is only from this sole standpoint we have to consider toxicity of type D fluids. And if we must follow EEC rectmsoendation all these products we have tested should not be approved. SIN-le NOBLE, June 29th 1971 E. QUINOT GM/dc 1.9.1971 Translated by Mr. G. MITREAU DSW 586343 STLCOPCB4091677 Monsanto COVERING LETTER 13 TOXICITY DETERMINATION - RATING OF RESULTS Extract from raport N* 4 regarding specification* and teat conditions related to fire resistant fluids used in power transmission. Luxemburg, March, 26th, 1971. - Global toxicity (A And C) All the animals are alive Animals subjected to a 1.10 * concentration dead after one hour dead within one hour Animals subjected to a 1.10 -2 concentration dead after one hour dead within one hour :0 t1 :2 >3 i4 Animals subjected to a 1.10 dead after one hour dead within one hour concentration t5 :6 Animals subjected to a 1.10 dead after one hour dead within one hour concentration t7 :8 Animals subjected to a 1.10 dead after one hour dead within one hour concentration i9 tlO DSW 586344 STLCOPCB4091678 Monsanto 14 Irritating value test for rabbit eye Irritation Aside from all infection t - no reaction observed :0 - inflammation observed according to rate appearance, extent and duration : 1 to 5 - permanent lesion without loss of vision : 6 to 10 - loss of vision t 10 Test for rabbit skin irritation Aside from all infection : - no reaction observed - erythema following extent and duration - skin lesion depending frdm extent and duration death of animals tested :0 : 1 to 3 : 5 to 10 : 10 Mist or thermal decomposition 1- No animal is dead either during the experience or while the observation period t - no reaction observed t0 - irritation symptom like >perturbation of blood circulation, nervous shock leaving after 1 hour :1 " "6 hours i2 " "5 days i3 - loss or inderIncrease of body weight 2- Some of animals are dead during the experiment or while the observation period x dS\N 586345 STLCOPCB4091679 Monsanto During the experiment 15 0 123 05 1 -- 5 26 8 9 10 9 10 10 37 Each test result is given a mark from 0 to 10, multiplied by ponderation coefficient listed herebelow : Test Forms Coefficient Oral toxicity Global toxicity Irritating value on eye Irritating value on skin Cold aerosol Cold Hot Thermal decomposition 200 700 A, C, D A, C A, C, D A, C, D A, C D D A, C, D A, C, D 1 2 5 5 4 2 2 1 1 A product obtaining before ponderation mark 10 in any these tests cannot be accepted. A product, whose total marls, after ponderation reaching 50 is not accepted either. <34/ dc 1.9.1971 DSW 586346 STLCOPCB4091680