SAFETYCONSIDERATIONS

OF FRAGRANCE

Steve Herman

WHAT ISFRAGRANCE?.

A mixture of chemicals with all theattendant concerns-flash points, MSDSs, toxicology, environmental fate etc.

THE BLACK BOX

Without patent orcopyright protection,the fragrance industrymaintains confidentialityof 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

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.

RIGHT TO KNOW

CONFORMANCE LETTERS

• RIFM/IFRA• Vapor pressure• Proposition 65• Canadian DSL• EPA• Kosher

MSDSOn 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 SheetManufacturer: AFF International

1265 Kennestone CircleMarietta, GA 300661-770-427-8177

EMERGENCY NUMBER: 1-800-123-4567SECTION 1 - PRODUCT INFORMATION

PRODUCT NAME AND NUMBER: Candle Fragrance NCA 2003CUSTOMER: NCA Meeting

SECTION 2 - PHYSICAL DATA

APPEARANCE: Light yellow liquid

BOILING PT: N/A

ODOR: Almond odor MELTING POINT N/A

SPECIFIC GRAVITY: 1.047-1.067 VAPOR DENSITY N/A

H2O SOLUBILITY: insoluble VAPOR PRESSUREN/A

FIRE HAZARD

• Flammable• Combustible

FLAMMABLE"Flammable liquid" means any liquid having a flashpoint below 100° F. (37.8° C.)…

COMBUSTIBLEClass II FP greater than 100° F, less than 140°FClass IIIA FP≥ 100° F but less than 140°FClass IIIB FP≥ 140° F but less than 200°FClass IIIB FP≥ 200 °F

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

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

http://hazmat.dot.gov/rules/hm215bf.htm49 CFR Parts 171-178

EXTRACTS, AROMATIC, LIQUID

UN1169

49CFR 172.101 Hazardous Materials Table

FLASH POINTSFlashpoint 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 aboveto ship by air

NFPA DIAMOND

National Fire Prevention Association

HMIS LABELS

HazardousMaterialsInformation System

VOCsAny compound containingat 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 sumof the vapor pressure contributions ofall the ingredients

VOC FORMULAVapor 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)BCFFish (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)

PERSONALSAFETY

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 continuousprogram 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 Materialsestablished 1966 to independently study fragrance safety

IFRA- International Fragrance Association (1973)sets standards based on RIFM reports

RIFM: MISSION1. Engage in research and evaluation of

fragrance materials through an independent Expert Panel

2. Determine safety in use3. Gather, analyze and publish scientific

information4. 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)

107-75-5 10%1%

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% inthe 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.

First IssuedLast Amendment April 28, 2000

March 01, 1987

RestrictedCAS # Recommendation Skin Contact Non-Skin Contact

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 structurereviewed 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 REPORTSR.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

EXPOSUREAssume:

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 MEIn 8’ X 8’ X 10’ room = 640 ft32.6 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 MEFor 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 METhanks to Dr. William TroyAvon/Firmenich

Soot emissions from scented candles were significantly higher than those from non-

SOOT

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 CHEMISTRYBEST WORSTalkanes alkenes alkynes aromatics

C-C C=C C C

branching andpresence ofoxygen helps

Burns well

AROMA CHEMICALSGood burners O

OCyclopidene

FP 69°C

O

Ethyl methyl-2-butyrate

Methyl n-amyl ketoneFP 39°C

FP 26°C

O

O

AROMA CHEMICALSBad burners

OCH3

CHO

OH

Vanillin

OCoumarin O

Oranger crystals

FP 153°C

FP 150°C

FP 168°C

QUANDRYEsters (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 shouldevaporate from the melted pool,but those that don’t can be expectedto combust poorly as a group.

GEL CANDLES

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

Combination offragrance concentrationand low flash point can cause flare

DEP-FACTS VS RUMORS

Many phthlates, for exampleDBP (dibutyl phthalate) and DEHP (diethylhexyl phthlate) can cause reproductive problems.But DEP (diethyl phthalate) given cleansafety 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 GROUPRIFM membership is open for "supporting members" who use fragrances.

See Dan Isola hereor call 201-689-8089

CONCLUSIONSSafety is a continuous processof 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

THE BLACK BOXASPECTS OF SAFETYOUTLINEPHYSICAL CONSIDERATIONSRIGHT TO KNOWCONFORMANCE LETTERSMSDSFIRE HAZARDFLAMMABLEDOT CHANGEEXTRACTS, AROMATIC, LIQUIDFLASH POINTSASTM D-56ASTM D-93International Air Transport Association’s (IATA)NFPA DIAMONDHMIS LABELSVOCsVOC FORMULAWATERAQUATIC RISKRIFM Environmental Framework CalculatorCANADAPERSONALSAFETYRIFM/IFRAHISTORYRIFM: MISSIONPHYSIOLOGICAL CONSIDERATIONSNON-SKIN CONTACTSKIN CONTACTUPPER AIRWAYSRESPIRATORY SAFETY PROJECTRESPIRATORY SAFETYPRIORITIESCHEMICAL GROUPINGSAEROSOL EXPOSUREAEROSOL STUDYINITIAL REPORTSBURNING CANDLEEXPOSUREEXPOSURESOOTSOOTCOMBUSTION CHEMISTRYAROMA CHEMICALSAROMA CHEMICALSQUANDRYGEL CANDLESDEP-FACTS VS RUMORSWEB SITESJOIN THE GROUPCONCLUSIONS