SAFETY CONSIDERATIONS OF FRAGRANCE

Steve Herman WHAT IS FRAGRANCE?.

A mixture of chemicals with all the attendant concerns-flash points, MSDSs, toxicology, environmental fate etc. THE BLACK BOX

Without patent or copyright protection, the fragrance industry maintains confidentiality of formulae. ASPECTS OF SAFETY

• As a chemical • As fragrance • In a candle OUTLINE

• Physical considerations • Physiological considerations • Upper airways initiative • Candles/ air fresheners PHYSICAL CONSIDERATIONS

• Shipping-Flash Points • Right to know • Quality control • Water •MSDS RIGHT TO KNOW Every American has the right to know the chemicals to which they may be exposed in their daily living. Information is usually given in general terms (top five ingredients, % ranges, RIFM compliance), with more detailed disclosure usually covered by confidentiality agreements. CONFORMANCE LETTERS

• RIFM/IFRA • Vapor pressure • Proposition 65 • Canadian DSL •EPA • Kosher MSDS On November 25, 1983, OSHA issued its final regulations. Under this ruling, MSDSs were required for all shipments of hazardous chemicals leaving the manufacturers work place . Material Safety Data Sheet Manufacturer: AFF International 1265 Kennestone Circle Marietta, GA 30066 1-770-427-8177 EMERGENCY NUMBER: 1-800-123-4567 SECTION 1 - PRODUCT INFORMATION

PRODUCT NAME AND NUMBER: Candle Fragrance NCA 2003 CUSTOMER: NCA Meeting SECTION 2 - PHYSICAL DATA

APPEARANCE: Light yellow BOILING PT: N/A liquid

ODOR: Almond odor MELTING POINT N/A SPECIFIC GRAVITY: 1.047-1.067 VAPOR DENSITY N/A

H O SOLUBILITY: insoluble VAPOR N/A 2 PRESSURE FIRE HAZARD

• Flammable • Combustible FLAMMABLE "Flammable liquid" means any liquid having a flashpoint below 100° F. (37.8° C.)… COMBUSTIBLE Class II FP greater than 100° F, less than 140°F Class IIIA FP≥ 100° F but less than 140°F Class IIIB FP≥ 140° F but less than 200°F Class IIIB FP≥ 200 °F

Regulations (Standards - 29 CFR) Flammable and combustible liquids. - 1910.106 DOT CHANGE

Raised flammable liquid definition to 141 °F (60.5 °C) to conform to UN definitions. (1997)

49 CFR Parts 171-178 http://hazmat.dot.gov/rules/hm215bf.htm EXTRACTS, AROMATIC, LIQUID

UN1169

49CFR 172.101 Hazardous Materials Table FLASH POINTS

Flashpoint by ASTM D56 – Flash point is defined as the temperature to which a fuel must be heated to produce an ignitable vapor-air mixture above the liquid fuel when exposed to an open flame. ASTM D-56

ASTM D-93

International Air Transport Association’s (IATA)

Flash point 141°F and above to ship by air NFPA DIAMOND

National Fire Prevention Association HMIS LABELS

Hazardous Materials Information System VOCs

Any compound containing at least one carbon atom, with a vapor pressure greater than 0.1 mm Hg at 20° C

The vapor pressure of a mixture is the sum of the vapor pressure contributions of all the ingredients VOC FORMULA Vapor pressure contribution= Vapor pressure X concentration X correction factor • 1 MW 120 or greater • 1.33 MW 100-120 • 1.66 MW 80-120 • 2 MW 60-80 • 3 MW less than 60 WATER

• Transport • Storm water • Environmental fate-fish AQUATIC RISK RIFM Environmental Framework Calculator Kd (L/kg) Influent Conc. (ug/L) Primary Effluent Conc. (ug/L) Secondary Effluent Conc. (ug/L) River Water (ug/L) BCF Fish (mg/kg) LC50 (mg/L) PNEC (ug/L) PEC/PNEC

Environ Toxicol Chem (2002) 21 (6) 1301-1308 CANADA • DSL – Domestic Substances List • NDSL- Non-domestic Substances List • The Canadian Environmental Protection Act, 1999 (CEPA, 1999) • Canadian Centre for Occupational Health and Safety (CCOHS) PERSONAL SAFETY

A six year old boy had to leave a minor league ballgame because of chemicals in the air. The team found the problem and set aside a separate area of seats… THE PROBLEM

Peanuts… and the boy was also allergic to milk and soy RIFM/IFRA

For thirty years, the fragrance industry has had a continuous program of safety testing, and the process has no end in sight. HISTORY

FMA- Fragrance Materials Association the US trade organization successor to EOA in 1979

RIFM- Research Institute for Fragrance Materials established 1966 to independently study fragrance safety

IFRA- International Fragrance Association (1973) sets standards based on RIFM reports RIFM: MISSION 1. Engage in research and evaluation of fragrance materials through an independent Expert Panel 2. Determine safety in use 3. Gather, analyze and publish scientific information 4. Distribute scientific data and safety assessment judgments to RIFM members, industry associations and other interested parties 5. Maintain an active dialogue with official international agencies September 2002 PHYSIOLOGICAL CONSIDERATIONS • Skin irritation • Phototoxicity • Carcinogens • Allergens NON-SKIN CONTACT

• Solid air fresheners • Plug-in air fresheners • Insecticides • Toilet blocks • Joss sticks • Candles • Plastic articles SKIN CONTACT

• Aerosols • Detergents • Potpourri • Carpet powders • Household cleaning products • Liquid refills for air fresheners Hydroxycitronellal (Laurine, Hydronal, Phixia, Laurinal) Last Amendment April 28, 2000 First Issued March 01, 1987 CAS # Recommendation Skin Contact Non-Skin Contact 107-75-5 Restricted 1% 10%

Hydroxycitronellal should not be used such that the level in consumer products exceeds 1%. This is equivalent to 5% in a fragrance compound used at 20% in the consumer product. This recommendation is based on a no-effect level of 10% in diethyl phthalate and on a no-effect level of 2.5% in ethanol/diethyl phthalate in standard Human Repeated Insult Patch Tests (R.A. Ford and A.M. Api, Fd. Chem. Toxic. Vol. 26, p. 921-926, 1988). The RIFM Expert Panel reviewed these data in September 1999 and concluded that no further actions were required. UPPER AIRWAYS

• What are the effects of inhalation exposure to fragrances? • What are the public perceptions that need to be addressed, and what have we learned from earlier public health-related and environmental issues that will help us?

• RESPIRATORY SAFETY PROJECT • Exposure – 3 product forms – Aerosol air freshener – highest exposure in the shortest time span – Plug-in air freshener – sustained exposure – Fine fragrance – product form most commonly associated with fragrance use

Candles coming next? RESPIRATORY SAFETY • Selected fragrance ingredients – Benzyl acetate – Eugenol – α-Hexyl cinnamic aldehyde (HCA) – HHCB – Hydroxycitronellal – β-ionone – d-limonene – Linalool – Methyl dihydrojasmonate PRIORITIES

• Chemical structure reviewed for structural alerts • Exposure – Volume of use CHEMICAL GROUPINGS

• A means to defend structurally related materials, without having to test every material in the group – ~ 2,000 chemically defined fragrance ingredients – 22 Groups (e.g. Acids, Acetals, Alcohols) – > 60 Subgroups (e.g. Straight chain saturated, straight chain unsaturated etc.) AEROSOL EXPOSURE

• Exaggerated (conservative) exposure conditions to an aerosol air freshener – Single-use, 8 ft3 simulated bathroom (14.5 m3) – Emulsifier, propellant, stabilizer, water – Five-second spray – Adult and child sampling height collections – Particle size analysis AEROSOL STUDY

• Formulation: 0.06% each benzyl acetate, eugenol, HCA, HHCB, hydroxycitronellal, β-ionone, d-limonene, linalool, methyl dihydrojasmonate; 0.20% BHA; 0.50% emulsifier, 29.00% propellant, 69.76% water • Sampling locations: Adult/child breathing zone (5/1.5ft height, 3 ft from spray origin • 5 second spray. INITIAL REPORTS

R.E. Rogers, D.A. Isola, and L.W. Smith. (2003). Characterization of potential human exposure to fragrances during consumer product use. J Allergy Clin Immunol. Supp. 111(2): S239. #683. D.A. Isola, L.W. Smith, R. Ansari, D.R. Cortes, and M.S. Black. (2003). Exposure characterization from a fragranced plug-in air freshener. The Toxicologist. 72(S-1): 291. #1416. BURNING CANDLE

• Exposure calculation • Structure/combustion correlation EXPOSURE

Assume:

10% fragrance in candle, Fragrance contains 0.13% methyleugenol (ME). Burn 5 gm/hr for 4 hours: 10% X 0.0013 X 20 gm = 0.0026 gm ME In 8’ X 8’ X 10’ room = 640 ft3 2.6 mg/640 ft3 = 4.06 µgm/ ft3= 0.14 µgm/l ME EXPOSURE

Respiratory rate of 1000l/hr X 4 hours = 4000l 0.14 µgm/l X 4000l = 0.56 µgm ME For 60 kg body wt: 0.56 µgm/60 kg = 0.93 µgm/kg ME = 1000 X less than no effect level from animal toxicity studies of ME Thanks to Dr. William Troy Avon/Firmenich SOOT

Soot emissions from scented candles were significantly higher than those from non- scented candles. Soot production from non- scented candles, that produced soot, ranged from 20-175 µg/min/wick.Soot production from scented candles, that produced soot, ranged from 20-3100 µg/min/wick.

http://www.lead.org.au/lanv7n4/L74-9.html SOOT COMBUSTION CHEMISTRY BEST WORST alkanes alkenes alkynes aromatics C-C C=C C C

branching and presence of oxygen helps

Burns well AROMA CHEMICALS Good burners O

O FP 69°C Cyclopidene O Ethyl methyl-2-butyrate Methyl n-amyl ketone O FP 39°C O FP 26°C AROMA CHEMICALS Bad burners CHO Vanillin FP 153°C

OCH3 O OH Coumarin O FP 150°C

Oranger crystals FP 168°C QUANDRY Esters (a great burning group) have low flash points (not good!). Bulk of aroma chemicals are aromatics, cyclics, etc--not good for combustion. Most of the aroma chemicals should evaporate from the melted pool, but those that don’t can be expected to combust poorly as a group. GEL CANDLES

• Perfect solubility in mineral oil • Flash point over 170 °F

Combination of fragrance concentration and low flash point can cause flare DEP-FACTS VS RUMORS

Many phthlates, for example DBP (dibutyl phthalate) and DEHP (diethylhexyl phthlate) can cause reproductive problems. But DEP (diethyl phthalate) given clean safety record from CIR, FDA, EPA, RIFM, COLIPA, Health Canada, etc WEB SITES

• www.ifraorg.org • www.iata.org • www.nfpa.org • http://rifm.org (members) • www.osha.gov • www.epa.gov • www.dot.gov JOIN THE GROUP RIFM membership is open for "supporting members" who use fragrances.

See Dan Isola here or call 201-689-8089 CONCLUSIONS Safety is a continuous process of refinement. RIFM leads the initiative to make fragrances as safe as possible. Fragrance suppliers make every effort to conform to all the regulatory and consumer requirements of a global industry. QUESTIONS & COMMENTS