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08/12/98 15 :47 FAX 804 2743055 PHILIP MORRIS 1pj001 kkkiik###kkk###kk#ki# xaa TX REPORT xkx xa#axkasaki#aaakksaaa TRANSMISSION OK TX/RX NO 0589 CONNECTION TEL 93208274 SUBADDRESS CONNECTION ID ST. TIME 08/12 15 :39 USAGE T 07'23 PGS. SENT 10 RESULT OK DRAI''T Component Safety Assessment for Benzyl Alcohol (CAS No. 100-51-6)

Component Safety Assessment for Benzyl Alcohol (CAS No. 100-51-6) DOC CODE : 0622

Description of Use : The primary use of benzyl alcohol (BA) is as a co-additive in the textile dyeing industry. The chemical is also used in the manufacture of other benzyl compounds and as a solvent for gelatin, casein, cellulose acetate, and shellac. It is an ingredient in perfumes and food flavorings, mostly in the form of aliphatic esters and is also used as an embedding material in microscopy and bacteriostat in pharmaceuticals (NTP Technical Report No. 343, 1989). Other reported uses include dairy foods, candy, baked goods, puddings, chewing gums, virucidal in lotions, as an industrial solvent. Benzyl alcohol is a natural component of tobacco, jasmine, hyacinth, ylang-ylang oils and at least 2 dozen other essential oils (Opdyke, 1973). In the manufacturing of cigarettes, benzyl alcohol is found in flavors and in flavor/plasticizer. Manufacturer's Disclosure : Vendor-supplied confidential disclosures for cigarette components containing benzyl alcohol are maintained in PM product integrity files. Benzyl alcohol is found as a component in flavors and flavor/plasticizer. Worldwide Regulatory Status of the Component : Benzyl alcohol is a Flavoring and Extract Manufacturer Association (FEMA) GRASlisted ingredient (#2137). It is an FDA-approved food additive (21CFR172.515) for direct addition to food for human consumption as long as the amount added to food does not exceed the amount reasonably expected to accomplish its intended physical, nutritive, or other technical effect in food, and when it is used as an appropriate food grade chemical, prepared and handled as a food ingredient. Benzyl alcohol may be used as an "indirect" food additive only as a component of adhesives. Containers with sealing gaskets containing benzyl alcohol may be used safely for packaging, manufacturing, packing, processing, preparing, treating, transporting and holding food. The Food Additives and Contaminants Committee has recommended that benzyl alcohol be temporarily permitted for use as a solvent in food and recommended the maximum concentration of use in consumed food as 500 ppm (Reynolds, 1982). The Council of Europe has established an Acceptable Daily Intake (ADI) of 0-5 mg/kg (Opdyke, 1973). Occupational exposure guidelines for benzyl alcohol have not been established by OSHA, NIOSH, and ACGIH in the United States or by Deutsche Forschungsgemeinschaft (Germany), most likely due to it's low vapor pressure and therefore relatively low potential for exposure in the workplace. A short-term exposure limit of 5 mg/m3 has been established i in Russia (RTECS, 1995). ~ N 0 V Uf i ~ co ~ N DOC CODE: 0622 3

Safety Review Results of PM Safety Studies : INBIFO, PM Central and Product Integrity files were searched for toxicology study data generated by PM. No toxicology studies were found ; this evaluation was generated from a review of the scientific literature contained in Product Integrity files. Scientific Literature Review : Introduction : Benzyl alcohol is a colorless alcohol with a faint aromatic odor and a sharp, burning taste. The chemical has a vapor pressure of 1 mm of mercury, is sparingly soluble in water, and freely soluble in 50% ethanol. It is miscible with alcohol, ether, and chloroform. Synonyms for benzyl alcohol include hydroxytoluene, phenylmethanol, phenylcarbinol, phenyl methyl alcohol, benzenemethanol, and alpha-toluenol. Acute Toxicity : The LD5o in the rat was reported as 50-441 mg/kg when administered by routes allowing rapid absorption and distribution of the chemical (ip, iv, ia). Clinical signs associated with benzyl alcohol treatment included chronic pulmonary edema and dyspnea. The oral LD50 in the rat was approximately 1230 mg/kg ; this dose produced somnolence and general depressed activity, excitement, and coma. The Lclo in the rat was 1000 ppm/8 hours when administered by the inhalation route. Acutely toxic/lethal doses in the mouse were slightly higher than toxic doses in the rat. In the dog, an iv dose of 50 mg/kg produced mortality (LDIo) and produced clinical signs of dyspnea, hypermotility and diarrhea before death. A parenteral dose of 9 mg/kg produced tremors and respiratory effects. Toxicity in the cat was produced at much higher doses than the dog when administered by the iv route (LDIo - 625 mg/kg). Dermal and Ocular Irritation : Benzyl alcohol produced a mild skin reaction in man, and moderate irritation responses in the rabbit and domestic swine upon dermal application. Non-occluded application of 10 mg to the skin of the rabbit for 24 hours produced mild irritation. Instillation of 750 µl benzyl alcohol in the eyes of rabbits caused severe eye irritation (RTECS, 1995). Sensitization : Sensitization reactions were produced in some humans (1%) tested with 5-10% BA in petrolatum (BIBRA Toxicity Profile, 1991). However, under conditions of the Kligman maximization test no human volunteers responded with a positive allergic response on day 10-14 following a 10-day induction period. The induction procedure consisted of a 48-hour closed patch application with 10% BA administered 5 times over a 10 day interval. Using the guinea pig and 30% BA in solvent, 2 of 35 animals responded with a DOC CODE: 0622 4

positive test response when challenged with 10% BA on days 21 and 35 after induction (BIBRA Toxicity Profile, 1991). Mutagenicity : Benzyl alcohol was evaluated for mutagenic activity using several standard mutation assays. Results of assays in bacteria were uniformly negative. Benzyl alcohol did not induce growth inhibition due to DNA damage in Escherichia coli or Bacillus subtilis nor was it mutagenic in any of several strains of Salmonella typhimurium when tested in the presence or absence of exogenous metabolic activation. NTP studies with benzyl alcohol showed no increase in revertant colonies in a preincubation protocol with Salmonella TA98, TA100, TA1535, TA1537 with or without Aroclor 1254-induced male Sprague Dawley rat or Syrian hamster liver S9. In the NTP mouse lymphoma assay, benzyl alcohol induced trifluorothymidine resistance in the absence but not the presence of Aroclor 1254-induced male F344 rat liver S9. Exposures of human cell cultures to an unspecified amount of the chemical did not result in single-strand chromosomal breaks or chromosomal aberrations. NTP cytogenic analyses in the CHO assay with and without addition of the S9 fraction showed an equivocal increase in sister chromatid exchanges with a weakly positive response at the highest doses tested (1250-4000 µg/ml). In hamster cells, chromosomal damage was induced in the presence of S9, but not in the absence of metabolic activation. A weakly positive result was found for sister chromatid exchanges with and without the S9 fraction (BIBRA Toxicity Profile, 1991). Reproductive Toxicity : Benzyl alcohol was evaluated for developmental toxicity on days 6-13 during the organogenesis phase of gestation. Pregnant dams were treated by gavage with up to 750 mg/kg/day of benzyl alcohol in water. A decrease in the birth weight of the pups and an increase in the rate of weight gain was observed for the pups. There were no toxic effect upon the pregnant dams or upon pup viability. Repeated Dose Toxicity : NTP Sixteen Day Studies : Male and female F-344 rats were gavage-dosed at 0-2000 mg/kg benzyl alcohol in corn oil in 12 doses over 16 days. All animals in the high dose group died. Five of 10 animal in the 1000 mg/kg group died. Mean body weight in the 1000 mg/kg group was 18% lower than controls. Lethargy was observed at the 2 highest doses. No dose-related histopathology was found in any animals at any dose level. Male and female mice wer exposed to benzyl alcohol using the same treatment regimen. All animals died in the hi h dose group and 3 of 10 animals in the 1000 mg/kg group died. Lethargy and rough hair coat was observed in animals from the 500-2000 mg/kg groups. The 2 highest dose DOC CODE: 0622 5

group animals had blood in the urinary bladder at necropsy. No compound-related histopathology was observed. 1 NTP Thirteen Week Studies : Male and female rats and mice were dosed by gavage with 0-800 mg/kg benzyl alcohol 5 days/week for 13 weeks. Some rats in the 2 highest dose groups died but these deaths were attributed to gavage error. Rats in the 800 mg/kg group had signs of neurotoxicity with staggering, labored breathing and lethargy. Mean body weights in the high dose group was 5-7% lower than controls. Compound-related histopathology included necrosis of the dentate gyrus of the hippocampus, skeletal muscle necrosis, thymic congestion and hemorrhage and kidney nephrosis in 50% or more of animals. Kidney lesions were believed to be age-related. Mice had 5-8% reductions in body weight at the 2 highest dose levels. These animals also had staggering during the first 2 weeks of dosing. No compound-related histopathology was observed. In the human, a small number of workers exposed to a mixture of 10% benzyl alcohol and 5% benzene and other solvents for 1.5 to 2 months developed headache, nausea, vertigo, gastrointestinal symptoms and weight loss. Investigators attributed these effects to exposure to benzene and benzyl alcohol. In preterm infants, iv injection of saline solutions containing 0.9% benzyl alcohol developed "gasping baby syndrome" which was attributed to benzyl alcohol. Estimated intake of 99-403 mg/kg/day BA for 2-28 days caused a shift in the baby's acid-base balance producing severe metabolic acidosis. This change resulted in gasping, neurological deterioration, blood abnormalities, skin breakdown, liver and kidney failure, lowered blood pressure, heart failure and death in some cases. The gasping syndrome was not reported for doses of 27-99 mg/kg/day in the infants. In the rat, gavage treatment with 125 mg/kg/day for 12 doses over a 16 day period produced no effects upon growth and survival. At 200 mg/kg/day 5 days/week for 2 years, a reduction in survival was observed in females although there were no microscopic changes of tissues and organs observed in a comprehensive examination. Doses of 400 mg/kg/day, 5 days/week for up to 2 years caused reduced survival in both sexes but no treatment-related tissue anomalies (NTP, 1989). Doses of 800 mg/kg/day for 90 days caused some deaths, staggering, reduced growth, breathing difficulties, lethargy, and tissue changes of the brain, thymus, skeletal muscle and kidney. When 2000 mg/kg/day was administered for 12 days, all rats died. Repeated dose studies conducted in the mouse at similar doses and treatment regimens produced similar toxicologic signs in the mouse, and reduced survival at at the highest doses. DOC CODE: 0622 6

Carcinogenicity : Groups of 50 rats (F-344) of each sex were treated with 0, 200, or 400 mg/kg benzyl alcohol in corn oil by gavage, 5 days/week for 103 weeks. Mice (B6C3F1) were treated with 0, 100, 200 mg/kg according to the same schedule. No treatment-related clinical signs were observed in rats during the study. Survival of rats in the dose groups was significantly lower than controls after 50-103 weeks. In rats, forestomach hyperplasia was observed infrequently in some males and females from the treatment groups. Anterior pituitary gland adenomas or carcinomas were observed in some female rats, however, the incidence of these lesions was lower than controls. Effects on the male rat respiratory tract were seen at increased incidence including nasal tract inflammation, hemorrhage of the larynx, edema, hemorrhage and foreign material in the lungs. (These effects were likely related to gavage-treatment, and/or reflux and aspiration of test material and debris-this author's conclusion). In the mouse, no clinical signs were observed during the study. Body weights were comparable to controls. Females controls had reduced survival compared to high dose group females after week 74. A spontaneous lesion of the brain was noted in animafs of all groups and was not treatment-related. A slight increase in adrenal tumors in high dose group males was not considered to be treatment-related. Harderian gland tumors were observed at low frequency in all groups. Lung congestion and foreign material in the lung was observed in all groups and was not treatment-related. The conclusions of the NTP technical report review panel was "no evidence of carcinogenic activity in male and female rats and mice". Metabolism : Benzyl alcohol is rapidly absorbed from the gastrointestinal tract and oxidized in the liver by alcohol dehydrogenase to form benzoic acid. Benzoic acid is conjugated with glycine, producing hippuric acid, which is eliminated in the urine. If formation of benzoic acid exceeds the formation of hippuric acid some of the benzoic acid is excreted as benzoylglucuronide. In the human 75-85% of the administered dose is eliminated as hippuric acid within 6 hours. The plasma half-life of benzyl alcohol was found to be approximately 1.5 hours in the dog (HSDB, from Micromedix, Inc., 1998). Epidemiological Data : No epidemiological data on benzyl alcohol were found. Description of Analytical Methods : Purge and Trap : Purge and trap analyses have been performed on flavors used on tobacco to identify and quantitate volatile components. The purge and trap analysis method consists of DOC CODE: 0622 7

volatilization of a known amount of the component at 100 or 300 C for 5 minutes. Evolved volatiles from the component mixture are conducted into a GC-MS for identification and quantification. For each component peak of the chromatogram, analysis results are presented for chemical identity, retention time, area percentage and CAS number. In some cases, the identity of a component peak may remain unknown since only the structural backbone of the molecule or its substituents could be identified without complete identification of the molecular structure. Pyrolysis : Pyrolysis analysis is conducted using a known amount of test sample which is heated from 300-600 C in a quartz tube furnace in a helium atmosphere. The volatiles are condensed onto an initial section of a fused silica capillary column held at a low temperature. The GC oven and column temperature is then raised at a preprogrammed rate to attain a final elevated temperature (usually 600 C). This temperature is maintained for at least 30 minutes. Analysis of the pyrolysate is accomplished using GC-MS for identification and quantification of each component. For each component peak of the chromatogram analysis results are presented for chemical identity, retention time, area percentage and CAS number. In some cases, the identity of a component peak may remain unknown since only the structural backbone of the molecule or its substituents could be identified without complete identification of the molecular structure. Purge and TrapJPyrolysis Results Purge and trap analyses have been performed on numerous flavors used on tobacco to identify and quantitate volatile components. In general, the analyte was detected at concentrations ranging from (data not yet available on database). Pyrolysis of flavors to detect the presence of benzyl alcohol has not been performed. Smoke Chemistry Results Smoke chemistry studies to detect the presence of benzyl alcohol in pyrolyzed cigarettes have not been performed. DOC CODE: 0622 8

Safety Assessment : From an NTP carcinogenicity study in the mouse and the rat, the NOEL for the rat was 400 mg/kg/day. The following safety factors will be used to calculate the "permissible daily exposure" (PDE) to benzyl alcohol : Safety Factor Source of Each Factor 5 rat to human extrapolation 10 human variability factor 5 dose route factor 1 lifetime exposure duration in the rat Permissible Daily Exposure (PDE) : PDE = NOEL(mg/kg/day) X (50 kg body weight)/ Safety Factor PDE in mg/day = (400 mg/kg/day X 50kg)/ 250 = 80 mg/day in the human Average Acceptable Use Level (AAUL) : AAUL = PDE/16.7 cigarettes/day = mg/cigarette _(8 mg/day) X (16.7 cigarettes/day) = 4.8 mg/cigarette Upper Limit Acceptable Use Level (ULAUL) : ULAUL = PDE140 cigarettes/day = mg/cigarette _(80 mg/day) X (40 cigarettes/day) = 2.0 mg/cigarette DOC CODE: 0622 9

REFERENCES BIBRA toxicity profile on Benzyl Alcohol, reference number.acn-3600,1990. HSDB, from Micromedix, Inc., 1998. Reynolds, J.E.F., Prasad, A.B., (eds.), The Extra Pharmacopoeia, 28s' edition, THe Pharmaceutical Press, p. 40, 1982. National Toxicology Program, Technical Report Series, Report No. 343. "Toxicology and Carcinogenesis Studies of Benzyl Alcohol in F34-0IN Rats and B6C3Fj Mice", NIH Publication No. 89-2599, June, 1989. Opdyke, D.L.J., Mongraphs on Fragrance Raw Materials (Benzyl Alcohol) published in Fd Cosmet. Toxicol., Vol. 11, pp 1011-1081, 1973. Taylor, S. E., Scientific Literature Survey for Benzyl Alcohol, Unpublished internal report on benzyl alcohol, 1991. ea FX ~,<,j DOC CODE: 0622 10

Table of Contents Description of Use......................................................... 3 Manufacturer Disclosure................................................. 3 Worldwide Regulatory Status of the Component...................... 3--J Safety Review.............................................................. 4 Results of PM Safety Studies.......................................... 4 Scientific Literature Review............................................. 4 Introduction...................................................... 4 Acute Toxicity................................................... 4 Mutagenicity..................................................... 5 Reproductive Toxicity.......................................... 5 Repeated Dose Toxicity........................................ 7 Carcinogenicity.................................................. 7 Metabolism...................................................... 7 Epidemiological Data....................................................................................... 7 Description of Analytical Methods 7 Purge and Trap/Pyrolysis Results........................................8 Smoke Chemistry Results................................................ 8 Safety Assessment......................................................... 9 References.................................................................. 10 N 0 ~ Of i V ~to W 0 DOC CODE: 0622 2