And the Accuracy of theHERA Environmental Risk Assessment

Kay FoxSEAC Environment, Unilever

Chair - HERA Environment Task Force

Claudia Poelloth - AISEC. Arregui Petresa C. Stevens Dow CorningG. Boeije P&G R. van Egmond UnileverH. Certa Condea Chemie R. van Wijk Akzo NobelR. Elsmore McBride T. Wind HenkelK. Fox Unilever A. Aarts SolutiaP. Masscheleyn P&G A. Berends SolvayP. Richner CIBA D. Calcinai Condea AugustaW. Schul BASF E. Cerbelaud RhodiaJ. Steber Henkel V. Koch Clariant

R. Toy Shell Chemicals

Environment Task Force

Initiatives on High Production Volume (HPV*) Chemicals

Collect and generate hazard data Produce hazard assessments

• ICCA Global Initiative, 1998 - 2004• US initiative on HPV (EPA, 1998)

* Defined as greater than 1,000 tons/year in Europe and 1 million pounds / year in the U.S.

Hazard data only is NOT sufficient to provide

reassurance about the SAFETY of chemicals to the Authorities

and the public

Sensible Risk Management...

...can only be done within a framework of risk assessment, taking into account both

– the hazards of the material AND–the consumer and environmental

exposure

EU Risk Assessments

Available for only a very small number of substances

lengthy, complex process

increase the pace through focussed risk assessments for certain sectors, e.g. household detergents and cleaning products

Joint European initiative between – suppliers of detergent raw materials

(CEFIC) and– the manufacturers of detergents (AISE)

to perform targeted - or focussed - risk assessments on substances of interest to the detergents industry

Risk Assessment

focus on chemicals that are used primarily in household detergents and cleaning products

focus on “consumer / private use” focus on intended use but also consider foreseeable

misuse and accidental use

focus on environmental compartments potentially at risk through “household use” of detergent & cleaning products

Phase I

• Develop methodology for HERA risk assessments

• Objective : rapid & efficient, but still good, sound science

• Work on example substances

• Objective : demonstrate feasibility for

Regulators Industry All interested

parties

Phase II - Apply to a wider range of substances

Phase 1

Selection for “developing” the methodology:

– Alkyl sulphates

– Zeolites

– Optical brightener FWA-5

O

S

O

O

OO

- Na +Alkyl Sulphate (AS)

an example - linear C12

CH=CH CH=CH

OSO2Na NaO2SO

FWA -5

Methodology - Environment

1. Collect Hazard, Exposure, and Physical and Chemical data from

ProducersFormulators

2. Using the Detergent Scenario Spreadsheet, enter the data into EUSES (based on TGD for European Risk Assessment), with modified (AISE) exposure scenario

3. Use a tiered approach to evaluate safety, or identify further data needs

Collect Hazard, Exposure, and Physical and Chemical data from Producers and Formulators

Chemical characterisation - What is the chemical?- Distribution of components

(e. g. chainlengths, isomers?)- Uncertainty?

Tonnage of the chemical - How much is released to the environment?- Uncertainty?

Chemical characterisation

Optical brightener FWA-5One chemical structure, one CAS number, no problem!

Zeolites Several types, but one type has the majority of the detergent market

Alkyl sulphates16 CAS numbers! (Selected from 46!)AS used in detergent products are mixtures of several homologues

Tonnage Released

Optical brightener FWA-5One producer, participant, no problem! Recent range 500 - 900 tonnes per year (600 in RA)

Zeolites Several producers - main use - detergentsProduction data from ZEODET

Alkyl sulphates European production data from several sources

Formulator dataTonnes product sold per year% chemical in product

Detergent ingredient usage data - Zeolites

European Zeolite Production in the 1990s

0

100

200

300

400

500

600

700

1986 1988 1990 1992 1994 1996 1998 2000 2002

Year

ton

nes

/yea

r X

1000

650 000 tonnes taken for HERA RA. Uncertainty - 10%.

Preliminary industry estimates indicate the total Alcohol Sulphate tonnage is around 120,000 tonnes/year in Europe - preliminary validation of these data indicate a probable over estimation of volumes.

It is estimated that 100,000 t/y is used in household detergents and cleaning products, whereas the remaining 20,000 t/y is used in personal care and other applications.

Detergent ingredient usage data - AS

Detergent ingredient usage data - Uncertainties

+15 000 tonnes per annum?

AS is a significant component in AES – 20% to 40% AS in AES, depending on

product grade– AES tonnage exceeds AS tonnage

AS in AES must be included in the AES risk assessment (definition of a substance). Thus it is not included in the AS risk assessment.

Uncertainties

Chemical Characterisation and Tonnage

Uncertainties must be addressed for each HERA substance in the HERA Risk Assessment Report.

Annual tonnage uncertainties can be better than + 15% for high volume chemicals. Lower tonnage chemicals with a very specificuse may have larger annual tonnage fluctuations.

How good is 1998? Is 1992 similar to 1998?

I will NOT discuss:

Hazard Data How good are the experimental data?How appropriate are the application

factors?EUSES

Sensitivity Analysis (RIVM , esp. Kow)Agreement of predicted and measured environmental data (Schwartz,

Northrhine-Westphalia)

Detergent exposure scenario for EUSES

Wide dispersive use, Detergents (5, 9) 100% of chemical to sewer (Local Use

model) Tiered Methodology

– EUSES Defaults– Replace selected defaults if necessary

• Removal values in STP• Measured Kd values• Biodegradation rates in rivers, soil, etc.

STD. EURegion

Local treatment plants

The standard EU region has 10% of the EUdetergent consumption - for 5.4% of the EU population.

Region Population Area, km2 # EU Regions Pop. DensityEntire EU 370000000 3560000 89 104Switzerland 7325000 39550 0.99 185Belgium 10213000 32820 0.82 311Paris, Picardie, U. Normandie 14500000 43000 1.08 337

The Netherlands 15739000 33920 0.85 464

EUSES Standard Region 20000000 40000 1.00 500

London and SE +E 20452000 39794 0.99 514Northrhine-Westphalia 17800000 34071 0.85 522

0

2

4

6

8

10

12

14

g/p

ers

on

/da

y

Detergent consumption per person in eighteen European countries in 1998, compared with the average European detergent consumption (Europe 18)

STD. EURegion

Local treatment plants

4TGD - Local plant

Modified Exposure Scenario - HERA

TGD - A reasonable worst case treatment plant will receive 4 times the average load

012

3456

78

0 0.4 0.8 1.2 1.6 2 2.4

Boron measured / Boron calculated

Fre

qu

ency

0%

20%

40%

60%

80%

100%

120%

Frequency

Cumulative %

B (representative detergent ingredient)

90th %ile < 1.5 times the average.

Modified Exposure Scenario - AISE

TGD - Worst case (4) times worst case (~2) gives almost 8 times the average ingredient loading to a local sewagetreatment plant.

AISE Scenario - Data backed “worst case” (1.5) times “worst case” (~2) shows three times the average ingredient loading to a local sewage treatment plant.

Paper on the 1.5 factor submitted for publication in Chemosphere, and for the TGD revision, via ECETOC.

Grouping - Alkyl Sulphate

C12 C13 C14 C15 C16 C18

33% 2% 18% 4% 22% 22%

Preliminary European Industry EstimatesData to be validated.

Much, but not all, experimental data has been obtained from tests on commercial grade materials.

Linear 35 15 25 25LinearandMono-branched

15 15 3535Some 2 branching

QSAR and Measured dataAS - Phys Chem properties Na salts

C12 C14 C16 C18 unitsM.W. 288.4 316.4 344.5 372.5 g/molM.P. 205

(204-7)265 276 287 0C

B.P. 588 612 635 658 0CV.P. 6e-11 9e-14 2e-14 3e-15 PalogKow 1.6 2.67 3.66 4.46 log10

Aq. Sol. 150000 51 5 .5 mg/l

Illustrative Example

Detergent scenario for EUSES

Phys Chem properties -– Is EUSES sensitive to property being

represented by QSAR?• If not, use QSAR!

– If EUSES is sensitive, then how good is the QSAR?

• logKow among the better QSARs

• uncertainty often within factor of 3

• different uses of logKow in EUSES - check out each!

QSAR and interpolated (extrapolated?) data

Grouping

Any grouping used in an individual HERA risk assessment must be fully explained in the risk assessment documentation.

Sensitivity to predicted parameters, and the uncertainty in the risk assessment due to their use, must be fully documented.

HERA - Methodology Must:

Involve all producers and formulators Identify all relevant sources of chemical Consider Uncertainty

– Tonnage data– Measured data– QSARs and inter/extrapolations– methodology (EUSES)

Be acceptable to scientists and regulators