Fragrances, RIFM, and their Environmental Assessment

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Fragrances, RIFM, and their Environmental
Assessment

• Daniel Salvito, PhD
• Director, Environmental Sciences
• Farleigh Dickinson University
• 28 October 2008

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Objectives

• From an environmental perspective, what are
  fragrance chemicals and are they of concern?
• What can environmental chemistry tell us?
• How do we assess chemicals for risk?
• Background on RIFMs and IFRAs environmental
  programs

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What Are Fragrance Materials?

• Discrete organic compounds, enantiomeric
  mixtures, and natural oils
• Structurally diverse
• Physical-chemical properties cover a wide range
• Presently over 2600 materials listed as fragrance
  materials

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Chemical Classes for FMs

• Organic Acids 42
• Acetals 63
• Alcohols/Phenols 342
• Aldehydes 186
• Esters 684
• Ethers 100
• Hydrocarbons 82
• Ketones 345
• Other 344

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Chemical Classes - Examples
b-Pinene
Diphenyl Ether
Geraniol
Terpineol
Eugenol
Methyl Salicylate
d-limonene
Methyl Dihydrojasmonate
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Environmental Organic Chemistry, Schwarzenbach et
al, 1993. page 4
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Marine food web for the Arctic. Phytoplankton
generate organic carbon through photosynthetic
reactions. Phytoplankton are eaten by the
zooplankton, who are in turn eaten by fish, on up
to large marine mammals. Organic carbon that
settles to the sea floor is usually consumed by
marine organisms there. (Credit Christopher
Krembs, NOAA, US Department of Commerce)
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Environmental Organic Chemistry, Schwarzenbach et
al, 1993. page 6
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Fragrance Industry Approach to Environmental
Issues

• Risk based approach
• Publication of human health and environmental
  approach in 4 research papers
• Voluntary confidential volume of use surveys
• Conducted by IFRA
• Program transparency
• Peer reviewed publications and presentations at
  scientific meetings
• Establishment of an external advisory panel
• Provide scientific advocacy

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Chemicals Legislation

• REACH
• TSCA
• CHAMP
• GHS
• UNEP POPs
• Canada DSL Program

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RIFM FrameworkProblem Formulation

• The RIFM/FEMA Database of Materials consists of
  over 2100 chemically defined organic compounds
• Testing all 2100 materials is neither practical
  nor cost effective
• A screening tool is needed to assess if a
  potential for environmental risk from these
  materials exists and to effectively allocate
  resources on higher priority materials

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Distribution Pathways
Atmosphere
SURFACE WATERS
Down the Drain Disposal
SEDIMENTS
FOOD CHAIN
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Application To Fragrance Materials

• First Tier Using only volume of use, molecular
  weight, and log Kow, PEC/PNEC ratios are
  determined
• Second Tier For all those materials with
  PEC/PNEC gt1
• ECOSAR was used as an alternate QSAR
• PEC/PNEC ratio re-determined

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Exposure Characterization
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Exposure Characterization PEC

• Model assumptions
• All the fragrance usage volume is discharged down
  the drain
• No volatilization occurs
• Both 1 and 2 treatment occurs
• Material removal during treatment is only the
  result of sorption (no biodegradation or
  biotransformation)
• Minimal dilution (a factor of 3) occurs at the
  mixing zone

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Ecological Effects Characterization PNEC

• Assumption All the fragrance is considered
  bioavailable
• QSAR Equation (Könemann, 1981)log 1/LC50
  (mmol/L)
• 0.871 log Kow
  4.87
• Assessment Factor of 106 used

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Assessment Factors
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Data Refinement

• PEC
• Model allows for the use of biodegradation data
• Input of measured WTP or in-stream data
• PNEC
• Use of alternate QSARS
• Collection of ecotoxicity data
• Method Validation
• Assess the ability of the model to overestimate
  aquatic risk
• No false negatives

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Initial Framework Results

• In the First Tier screening, 1563 (73) of the
  materials had PEC/PNEC ratios lt1 and have been
  removed for further consideration at this time
• The Second Tier assessment has reduced the total
  number of materials requiring further refinement
  to 171 (8) of those studied
• The Framework is useful for screening large sets
  of organic chemicals for prioritization

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Decision Tree Role of the Panel Paper
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Application of the Framework

• High volume, high priority materials
• Three tier assessment
• Collection and use of measured data

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Acetyl CedreneStructures and Properties

• CAS 32388-55-9

• Molecular Weight 246.39
• Log Kow for 3 isomers 5.6, 5.8, 5.9
• Alicyclic ketone

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Risk Screening

• Acetyl cedrene considered not readily
  biodegradable
• ECOSAR used to calculate PNEC
• Assessment Factor changed to 10000 for Tier 2
• PEC/PNEC gt1
• Measured ecotoxicological endpoints and
  environmental concentrations needed for further
  risk assessment refinement

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Problems with Kow based QSARS

• Data sets used to build many commonly used QSARs
  are
• Small
• Not structurally diverse
• Are limited to log Kow lt5-6

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Degradation

• Aschman et al. (2001) found acetyl cedrene
  reactive with OH radical, O3 and NO3 radicals
• Calculated atmospheric lifetimes
• OH 1.8 hr (12 h daytime conc. 2 x 106 mol/cm3)
• NO3 11 d (12 h daytime conc. 5 x 108 mol/cm3)
• O3 gt7.5 d (24 h conc. 7 x 1011 mol/cm3)
• Not readily biodegradable in standard tests
• Undergoes biotransformation
• t1/2 of parent in activated sludge ranged from
  lt10 minutes to 1.2 h
• Log Kow of metabolites 0

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ECOTOXICOLOGICAL DATA
All values in mg/L unless otherwise noted AF 50
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US Treatment Plants (Simonich et al., 2002)

• All values in ug/L

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European Treatment Plants (Simonich et al., 2002)

• All values in ug/L

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Hazard Assessment and Fragrance Materials

• RIFM Framework
• Focused on risk
• Prioritizes testing
• Supported by risk based assessment approaches
• European Union
• US EPA
• PBT Assessments
• Hazard Based
• Driven by Precautionary Principle
• Persistence in the environment, Bioaccumulation
  in organisms, Toxic to organisms

Hazard Exposure
Budgetary efficiency
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Table of EU and US PBT Criteria
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Design for the Environment

• EPA Ecolabel
• Fragrance Technical Advisory Group (including
  industry members and RIFM) worked towards
  establishing human health and environmental
  attributes
• Criteria recommended for evaluating chemicals
  used in fragrances for persistence,
  bioaccumulation and toxicity

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Model Limitations

• Persistence
• Fragment based model/expert judgement assigns
  half-life
• Selected fragments may not adequately represent
  the behavior of the molecule
• Half-life in soil and sediment inferred from
  half-life in water
• Bioaccumulation
• Log Kow based QSAR with factors for certain
  structural components, if present
• Does not take metabolism or other removal
  mechanisms into account

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Model Limitations

• Toxicity
• Log Kow based QSARs for different structural
  groups
• Training set for some QSARs very limited
• In General
• These models can both underpredict and
  overpredict the environmental behavior of organic
  chemicals

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Problems with Hazard Based Ecolabels

• Assumes that PBTs or other high hazard materials
  cannot be risk assessed
• No safe use
• Implies substitutes may exist
• Socio-economic impacts are not considered
• Infers that all risks are equal, for PBTs, when
  discounting exposure
• Example a non-PBT with half the toxicity of a
  PBT may need to be used at 3 times the strength
  because of efficacy concerns
• Therefore, increasing environmental risk

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Emerging Issue?
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Program Activities

• Research
• Sediment research at Roskilde University
• HESI BCF Program
• Changing how B is assessed in regulatory
  settings and animal testing issues
• OECD Toolbox development
• SETAC Global Partner
• Bioaccumulation (Co-Chair) and Animal
  Alternatives SAGs
• SAICM Steering Committee

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Distribution Pathways
Atmosphere
RIFM Framework and Biotransformation
SURFACE WATERS
Down the Drain Disposal
Roskilde Univ
SEDIMENTS
Univ of Delaware
FOOD CHAIN
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Program Activities

• ECETOC
• Scientific Committee
• PBT Task Force Methodology developed to assess
  PBTs andmaterials of equivalent concern.
  Methods useful in chemical categorization.
• USEPA Design for Environment Fragrance Technical
  Advisory Committee
• Providing guidance to develop environmental
  attributes for ecolabeled industrial and
  institutional cleaners
• UK DEFRA
• Resulted in the de-listing of 5 fragrance
  materials
• as potential chemicals of concern- no regulatory
  action

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Summary

• RIFM environmental program provides a risk based
  approach to assessing the impact of fragrance
  materials to the environment
• Research and testing are focused on high priority
  areas
• Program is designed to be transparent to
  industry, regulatory authorities, academic
  scientists and the public