Developing REACH Exposure Scenarios for Methanol

1
Developing REACH Exposure Scenarios for Methanol

• WS on REACH Exposure Scenarios (Human Health)
• Authority, ECHA and Industry Perspectives
• 22 23 October, 2008, Copenhagen
• Riitta Viinanen, RV Chem Oy
• r.viinanen_at_gmail.com

2
Project introductionDeveloping REACH Exposure
Scenarios for Methanol

• Participants TTL, 5 companies importing and
  using methanol (idea of consortium, agreement on
  confidentiality made)
• Management group had members from SYKE, STTV,
  VTT, KTry, 2 workers unions, TSR
• Finance TSR (90.000 ), STM (10.000 ),
  companies (43.000 ) and TTL (114.000 ) sum
  total about 247.000
• A two year collaboration project (2006-2007)
• Worker exposure, e.g.
• Use of methanol in various chemical processes
• Use of methanol as solvent in processes and
  technical products
• Use of methanol as washing solvent (windshield
  washer fluids)
• Consumer Exposure to methanol, Report in 2006
• Windshield washer fluids
• Use in hobbies (automotive fuel)
• Effects to the environment were assessed in two
  scenarios

3
1. Assessment of hazardspreliminary DNEL for
methanol worker long-term exposure

• Based on summary reports (not enough in REACH,
  original sources must be listed)
• Acute toxicity
• Headache in workers gt200 ppm
• Or developmental toxicity
• Animal tests NOAEL 1000 ppm (7 h everyday
  exposure) , assessment factor 4 x rat to human
  and human variation 5x workers
• gtDNEL 1000/4x5 50 ppm
• Assessment factors and interpretiation of
  toxicological test results need often "expert
  judgement, there is no "one true answer"
• The derived DNEL should try to protect from all
  these effects (precautionary principle).

4
1. Assessment of hazards preliminary PNEC
values for methanol

• Based on limited data (not enough in REACH)
• PNECaquatic predicted no-effect concentration
  for aquatic organisms
• chronic toxicity test to fish NOAC value 23, 75
  mg/l and assessment factor is assumed to be 10
  (this should be justified in REACH, results of at
  least 3 chronic tests with different species are
  needed)
• gtPNECaquatic 2,4 mg/l
• With calculation (Equilibrium partitioning)
• Sediment
• gtPNECsediment 1,96 mg/kg (wwt "wet weight")
• Soil
• gt PNECsoil 0,348 mg/kg (wwt "wet weight")

5
2. Collection of information and data of uses and
ways of uses

• GENERAL
• REACH-principle communication up and down the
  supply chain
• Information from the customer (chemical buyers
  and ja suppliers)
• Good cooperation gives the best information of
  the use and known exposure
• Information is also
• Business information, litterature, internet,
  information sercives
• Occupational health services, authorities
• Experts, specialists (TTL, consultants)
• IN THE METHANOL PROJECT
• Information and data from the companies and their
  customers, litterature information (KTry),
  Internet (google), KETU, hobby clubs, Databank of
  TTL, information from the new measurement targets
  were collected with a special form

6
2. Collection of information and data about the
amount of methanol from the KETU register

• The manufactures or importer send data to STTV
  annually about the chemical, STMp 337/98
• The data is registered to the National chemicals
  product register (KETU)
• The Finnish authorities are allowed to use the
  register
• About 470 products containing methanol was found
• A special service was used to achieve information
  about the amounts

7
2. Collection of information and data, the
customs statistics. Import of methanol to Finland
8
2. Collection of information and data
Questionary to downstream user RIP 3.2-2
Chemical safety report 05/2007 (draft)

• Annex A-2
• The amount of used raw material /end product
• Who uses industry, professional use, consumer
• Physical form of the substance liquid, solid,
  powder, gas
• The use of the product in industry and
  professional use use categories and substance
  in the product
• Consumer use type of the product and substance
  in the product
• Data about exposure Way of use, frequency and
  duration (list of choises)
• Risk management measures currently used workers,
  consumers, environment
• Measured exposure concentrations, if available
• RIP Reach Implementation Project

9
3. Use of methanol, applications

• 55 applications were in worker use
• 31 applications were found from the measurement
  register of TTL (1994-2006)
• 21 branches, 475 measurements
• In the project measurements were made in 12 new
  applications
• 5 branches, about 200 measurements
• No information from 12 applications
• The scenarios cover the applications where
  methanol is actually sold and loading and
  unloading tasks , i.e. together 33 applications
• Not included in this project manufacturing and
  use of products including methanol, because there
  was so little information (except manufacturing
  of windshield washer fluid )
• 7 applications in consumer use were found, 2 were
  taken in exposure scenarios
• Information about amounts was achieved from KETU
  as additional service

10
4. Use of methanol, chart 1

• Loading, unloading and packing in vessels

Methanol About 150 000 t (customs
statistics) (transportation is outside REACH)
1.1 Import harbours Unloading ships
1.2 Import by rail Unloading railcars
1.3 Loading in containers and railcars
and Unloading railcars
Transportation by road
1.4 Packing in barrels
11
4. Use of methanol, chart 2a

• 2 a Manufacturing of chemical products
  formaldehyde and chlorine dioxide and slime
  preventing agent

METHANOL, 2a2b2c together about 130 000 t (KETU
2006)
2.1 Manufacturing of formaldehyde About 60 000
t/a MeOH, (in formalin MeOH stabilizer max 10)
5.4 Solvent
2.2 Manufacturing of chlorine dioxide for
bleaching
5.3 Washing solvent
4.2 Manufacturing of resins gt 90 of
formaldehyde production in Finland is used, in
all gt 380 000 t/a(? MeOH in resins)
Slime preventing agent
From wood?
4.2.3 Phenol formaldehyde resins (4 producers)
4.2.1 Resorsinol resins
4.2.2 Urea and melamine resins
6.1 Manufacturing of paper mass
6.3 Plywood, chipwood, wood fiber
products Glueing and finishing (resins lt0,8
MeOH)
6.1 Paper manufacturing (no MeOH residues)
6.6 Mineral and glass fiber industry (0,5 in
fixing agents)
6.7 Foundry industry In foundry resins lt0,4 MeOH
6.1 Paper industry Impregnated paper (in resins
max. 5 MeOH)
6.4 Coating Wood, laminates etc.
6.5 Manufacturing of abrasives Fixing agent
12
4. Use of methanol, chart 2b

• 2 b Manufacturing of chemical products

METHANOL, 2a2b2c together about 130 000 t (KETU
2006)
2.4 Formic acid (no MeOH in the final product)
2.5 Methyl formate (ca. 3 MeOH)
2.6 Potassium methacrylate (68-70 MeOH
2.7 Sodium boron hydride (lt 0,2 MeOH)
2.8 Tri-methyl borate (27 -30 MeOH)
6.11 Resins for foundries, chemical processes
6.12 6.13 Manufacturing of silanes, catalyst in
esterification (perfumes, cosmetic products and
pigments)
6.14 Additive in welding (In soldering fluid 60
MeOH)
13
4. Use of methanol, chart 2c

• 2 c Manufacturing of chemical products

METHANOL, 2a2b2c together about 130 000 t (KETU
2006)
2.9 Manufacturing of biodiesel (esterification
process)
2.10 Manufacturing of MTBE and TAME (Gasoline
oxygenates)
8. Use of MTBE ? (lt 1 MeOH in final product)
8.2 Use of biodiesel ? (lt0,2 MeOH in final
product)
14
4. Use of methanol, chart 3

• Use as a process chemical

METHANOL 4 000 t/a (growing)
3.1 Methanol as carbon source in wastewater
treatment (in Finland 7 -10 units use)
15
4. Use of methanol, chart 4

• Manufacturing of products containing methanol as
  a solvent

METHANOL manufacturing and use of windshield
washer fluids about 1 700 t (KETU 2006)
4.1 Manufacturing of paints and pigments and
paint removing products
5.4 Solvent
4.3 Manufacturing of windshield washing
fluids (max. 60 MeOH)
4.4 Manufacturing of automotive fuels (lt 10
MeOH)
6.8 Printing and textile industry (silk
printing) and other industry, wood industry (in
printing colours, solvent and cleaning agent, in
washing solvents)
8.1 Use of windshield washing fluids
6.15 Use of marking colours and paint removing
products
16
4. Use of methanol, chart 5

• Use of methanol as solvent in industry

METHANOL, KETU (2006) ABOUT 30 000 t
5.1 Medicine and pharmaceutical products
5.3 Paper industry
5.6 Repairing Removing of putty and paint
5.8 Natural gas pipelines (inhibitor)
6.8 Printing and textile industry (silk
printing) and other industry (in printing
colours, solvent and cleaning agent, in washing
solvents)
5.5 Manufacturing of sitosterol
5.7 Electronic industry, manufacturing of
instruments
5.2 Manufacturing of resins
17
4. Use of methanol, chart 6

• Use of methanol and products containing methanol
  in industry and workplaces (this includes
  products having methanol as solvent)

METHANOL
6.15 Use of marking colours and paint removing
products
6.8 Printing and textile industry (silk
printing) and other industry (in printing
colours, solvent and cleaning agent, in washing
solvents
6.10 Use of glossy additive in galvanization
basins
18
4. Use of methanol, chart 7

• Laboratory use of methanol

METHANOL about 50 t/a (KETU 2006)
7.1 preparation of reagents, purification of
methanol 7.2 manufacturing mediciinal products
at the chemists 7.3 various analysis (like
ocratoxines, ligniine, PAH-analysis, fatty acid,
vitamines) 7.4 use as cooling agent 7.5
colouring of tissues 7.6 HPLC-analysis (high
pessure liquid chromatography) 7.7 cleaning
agent in glue removing 7.8 tasks in mass
spectrometry
19
4. Use of methanol, chart 8

• Use of products containint methanol in
  professional traffic

METHANOL in manufacturing and use of windshield
washer fluids about 1 700 t (KETU 2006)
8.1 Use of windshield washer fluids
20
4. Use of methanol, chart 9

• Consumer exposure to products containing methanol

PRODUCTS CONTAINING METHANOL
10.1 Dilution and use of windshield washer
fluids (max 60 MeOH in retail products)
10.2 Manufacturing and use of automotive
fuels Model aeroplanes, model cars, speeding
race, speedway motorbikes (in fuels 60 - 100
MeOH)
10.3 Use of fuels in camping cookers (lt 10 MeOH)
10.4 Use of paint and colours removing
products (in paint removing products max 20
MeOH)
21
5. Exposure categories (EC) and exposure
scenarios (ES) in the project

• 1. Transportation of methanol (work during
  loading and unloading) (EC)
• 2. Methanol as the raw material in manufacturing
  of chemical products the process itself,
  maintenance, process sampling, packing, waste
  treatment, regeneration of methanol (EC)
• - Formaldehyde, Chlorine dioxide
• - Formic acid, Methyl formate
• - Potassium methylate, Sodium methylate
• - Sodium boron hydride, Trimethyl borate
• - MTBE, TAME
• - Bio diesel (RME etc.)
• 3. Methanol as carbon source in wastewater
  treatment (ES)
• 4. Manufacturing of products containing methanol
  as solvent
• -production of windshield washer fluids (ES)

22
5. Exposure categories (EC) and exposure
scenarios (ES) in the project

• 5. Use of methanol as an industrial solvent in
  extraction processes (e.g. medicins) (EC)
• 6. Use of methanol as solvent in different fields
  of industry (EC)
• 7. Laboratory use of methanol (EC)
• 8. Use of products containing methanol in
  professional traffic (ES)
• Use of windshield washer fluids
• 9. Consumer use of products containing methanol
  (ES)
• Use of windshield washer fluids
• 10. Consumer use of products containing methanol
  (ES)
• Use of methanol as automotive fuel

23
6. Routes of exposure in various scenarios and
categories for methanol
24
6. Routes of exposure in various scenarios and
categories for methanol
25
6. Relevant short-time preliminary DNEL values in
the methanol project
26
6. Relevant long-term preliminary DNEL values in
the methanol project
27
7. Models for exposure assessment

• It is also possible to assess the worker exposure
  with the models
• Ecetoc Tra (the internet version doesnt function
  yet, the paper version is available from the
  net), Riskofderm (a model for dermal exposure,
  the internet version under testing)
• EUSES 2.0.3, ConsExpo (are available and are
  functioning)
• The user must have sufficient basic information
  of the chemical and know the conditions of use
• The user must know where the models are suitable
• In the project were applied EUSES worker,
  consumer and environment assessment, Ecetoc Tra
  worker, ConsExpo (consumer)
• RIP version of October 2007 also mentions
• Stoffenmanager-exposure model, new version of
  EASE and COSSH and Easy-to use wokplace control
  scheme for hazardous substances
• The models are under development(revised versions
  in use in the end of 2008?)

28
8. Example Laboratory use of methanol, risk
characterisation
29
8. Example Laboratory use of methanol,
preliminary exposure scenario (only worker
exposure)
30
8. Example Laboratory use of methanol,
preliminary exposure scenario (only worker
exposure) (cont.)
31
8. Example Laboratory use of methanol,
preliminary exposure scenario (only worker
exposure) (cont.)
32
9. In the project measured / collected exposure
levels to methanol / industrial use / laboratory
use

• In closed industrial use manufacturing of
  chemical products exposure was generally
  controlled and exposure low. (9 applications of
  33)
• If methanol was in open vessels or there was
  othervise direct contact to the air, exposure of
  the workers exceeded the Finnish OEL or was near
  it (TWA 200 ppm/270 mg/m3 , STEL 250 ppm/330
  mg/m3. (8 applications)
• short-term loading and unloading of methanol
  (ships, railcars),
• maintenance work at wastewater plants,
• manufacturing of windshield washer fluids,
• short-term maintenance of reactors,
• use as solvent in extraction processes,
• washing of cylinders in paper industry and
• laboratory use of methanol in glue removing

33
9. In the project measured / collected exposure
levels to methanol / industrial use / laboratory
use

• If methanol is in industrial solvent use as part
  of the mixture
• Concentrations are generally low (4 applications)
• In laboratory applications
• Concentrations were below 28 OEL (7
  applications)
• Risk management measures were recommended in
  scenarios of industrial use to reduce the
  exposure to level which does not create health
  hazards

34
9. In the project measured / collected exposure
levels to methanol / consumer use

• In use of windshield washer fluid worker exposure
  and consumer exposure overlap (2 applications)
• To both the same RMM recommendations. i.e.
  lowering of the concentration of methanol in the
  windshield washer fluids. RMM in consumer use
  include primarily measures which are connected to
  the product
• Consumer use as automotive fuels (1 application)
• Exposure is very low

35
9. In the project measured /collected exposure
levels to methanol / biomonitorig

• Limited data
• 56 U-formia (formic acid in urin) samples 28
  persons
• 38 U-MeOH (methanol in urin) samples 19 persons
• U-Formia results were below the action level and
  the reference value of nonexposed was exceeded
  only in manufacturing of windshield washer fluids
  and some laboratory applications
• U-MeOH results were all below the reference limit
  of nonexposed
• Additional value of biomonitoring in this project
  was mainly in assessing of skin exposure and the
  ensurance of the level of protection in situation
  where respiratory protection was used.

36
10. Conclusions and recommendations

• The project succeeded with the main applications
  of methanol use
• Work was time consuming and demanding!
• In reality the registrant collects the
  information from the downstream users and must
  reserve a lot of time for it
• Grouping the applications to categories
• Can be done also in other ways than was done in
  the project. REACH gives freedom for it.
• The most relevant guidance for risk management in
  each scenario or category is however the goal is
  (e.g. the tasks with the highest exposure to the
  same scenario, like maintenance in various
  branches ).
• Exposure scenarios were no made to all
  applications
• Manufacturing of products containing methanol
  (other than windshield washer fluids)
• Use of products containing methanol in industry
  and workplaces
• -gt exposure scenario for a product (ECHA
  "Guidance for downstream users" )

37
10. Conclusions and recommendations

• Modelling programs gave higher exposure estimates
  to inhalation exposure than the measurement
  results.
• Skin exposure and modelling the results were
  overestimated, althouhg also underestimates were
  suspected (methanol in laboratory use)
• Environmental hazard assessment during use in
  wastewater treatment or in windshield washer
  fluids no excessive emissions to the environment
  (assessment was not carried out in other
  scenarios)
• The exposure scenarios are preliminary in nature,
  the final DNEL and PNEC values may differ from
  those presented in this project.

38
Additional information of the project

• The final report (in Finnish, incl. summary in
  English)
• Alustavien REACH-altistumisskenaarioiden
  kehittäminen metanolille
• can be loaded from the FIOH address
• http//www.ttl.fi/NR/rdonlyres/C9BD79E2-79D6-4F17-
  B733-0E33912D3509/0/REACH_altistumisskenaariot_met
  anoli.pdf
• or
• FIOH homepage http//www.ttl.fi/internet/english
  
• and search metanoli and select further from the
  list
• REACH_altistumisskenaariot_metanoli.pdf
• E-mail addresses of the writers are

39
Abbreviations used in the presentation

• AKT Transport Workers'
  Union AKT r.a. (Auto- ja Kuljetusalan
  työntekijäliitto ry)
• EcetocTra European Centre for Ecotoxicology and
  Toxicology of Chemicals,
• 
  Targeted Risk Assessment
• EUSES the European Union
  System for the Evaluation of Substances
• FIOH, TTL Finnish Institute of Occupational
  Health (Työterveyslaitos)
• Kemianliitto Union of Chemical Workers
  (Kemianliitto)
• KETU National chemicals
  product register (Kemikaalirekisterin
  tuoterekisteri)
• KTry Finnish Chemical
  Industry Association (Kemianteollisuus ry)
• MTBE, TAME Methyl tert-butyl ether, tert-amyl
  methyl ether
• RME Methyl ester of
  rapeseed oil, biodiesel
• STM Ministry of Social
  Affairs and Health (Sosiaali- ja
  terveysministeriö)
• STTV National Product
  Control Agency for Welfare and Health
• (Sosiaali-
  ja terveydenhuollon tuotevalvontakeskus)
• SYKE Finnish Environment
  Institute (Suomen ympäristökeskus)
• TSR The Finnish Work
  Environment Fund (Työsuojelurahasto)
• VTT Technical Reserch
  Centre of Finland (Valtion tutkimuskeskus)

40
Thanks !

• Special thanks to occupational hygienist Sanni
  Uuksulainen from FIOH for letting me use her
  excellent material while preparing this
  presentation! Sanni was the leading researcher in
  this project.