fds methanol eng vers.3.0

S.C. VIROMET S.A.

SAFETY DATA SHEET

according to (EC) Regulation no.1907/2006 (REACH) / (EC) Regulation no.1272/2008 (CLP) / (EC) Regulation no.453/2010

METHANOL Version 3.0 / date : 29.03.2012

Code PS-MI-14-F09 / 26 pag.1 / 25

1. Identification of the substance / mixture and the company / undertaking

1.1. Product identifier Trade name : Methanol Substance name : Methanol IUPAC name : Methanol Index no. : 603-001-00-X CAS no. : 67-56-1 CE no. : 200-659-6 Synonyms : Methyl alcohol,Methyl hydroxide,Monohydroxymethane,Wood alcohol, Carbinol

REACH REGISTRATION NUMBER : 01 – 2119433307 – 44 – 0062 ; 01 - 2119433307-44-xxxx

1.2. Relevant identified uses of the substance or mixture and uses advised against

Note: The following uses are compliant with the identified uses in the Chemical Safety Report (CSR) and in the Exposure Scenarios (ES) of the CSR, annexed to the Safety DataSheet.

Identified uses : Industrial uses : Manufacture of the substance/Use as an intermediate/Use as an process chemical ; Distribution of the substance; Formulation and (re)packing of substance and mixtures; Use as a fuel in industrial settings ; Industrial use in cleaning agents; Use as a laboratory reagent in industrial settings; Industrial use as wastewater treatment chemical; Professional uses : Use as a fuel in professional settings; Use as a laboratory reagent in professional settings ; Professional use in oilfield drilling and production operations; Consumer uses : Consumer use of cleaning agents and de-icers (liquid products); Consumer use of cleaning agents and de-icers (spray products); Consumer use of fuels indoors (Domestic/hobby use e.g in model engines, fuel cells, etc); Consumer use of fuels outdoors (gasoline additive).

Most common technical function of the substance : solvent

Uses advised against : no data

1.3. Details of the supplier of the safety data sheet

Manufacturer and / or distributor:

Company : S.C. VIROMET S.A. , VICTORIA town, zip code 5050700, Aleea Uzinei Str. no. 8, Brasov County , ROMANIA Telephone : 0040 / 268 / 241 120 Fax : 0040 / 268 / 242 484 e-mail : [email protected]; [email protected]

1.4. Emergency telephone number: S.C. VIROMET S.A.-Working team REACH-- 0040 – 268241120 / interior 1395/ 1241 Schedule: Monday - Friday (workdays) hours: 8-16

National Institute of Public Health, Office of International Health Regulations and Toxicologic Information –0040-21 318 36 06/ Schedule: Monday - Friday (workdays) hours: 8-16

2. Hazards identification

2.1. Classification of the substance

Classification and labeling information of the substance

Substance name : Methanol

Classification according to (CE) Regulation no. 1272 / 2008 (CLP) :

(CE) Regulation no. 1272 / 2008 (CLP) Hazard Class / code Hazard category Hazard

statements Obs.

Flammable liquids / Flam. Liq. Cat. 2 H225 -

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SAFETY DATA SHEET



Code PS-MI-14-F09 / 26 pag.2 / 25

Acute toxicity / Acute tox. Cat. 3 H301 oral Acute toxicity / Acute tox. Cat. 3 H311 dermal Acute toxicity / Acute tox. Cat. 3 H331 inhalation Specific target organ toxicity – single exposure / STOT SE

Cat. 1 H370 Target organs : optic nerve (nervus opticus), central nervous system

Specific concentration limits:

Concentration Classification C ≥ 10 % STOT, SE, cat. 1, H370 3 % ≤ C < 10 % STOT, SE, cat. 2, H371

Classification according to Directive D 67 / 548 / CEE :

Directive D 67 / 548 / CEE Classification Danger

symbol Risk phrases Safety phrases

Highly flammable

F R11

Toxic

T R23/24/25

Toxic

T R39/23/24/25

S1/2 S7 S16 S36/37 S45

Indication of danger : F- Highly flammable ; T- Toxic

Concentration limits: Concentration Classification

C ≥ 20 % T ; R23/24/25 3 % ≤ C < 20 % Xn; R20/21/22 C ≥ 10 % T ; R39/23/24/25 3 % ≤ C < 10 % Xn; R68/20/21/22

For R and S phrases text see section 16.

The most important adverse physico-chemical human health effects

Toxic if swallowed, by skin contact and if inhaled. Causes damage to organs. Target organs : optic nerve, central nervous system.

The most important adverse physico-chemical environmental effects

Methanol is not classified dangerous for environment ( see 12.5).

2.2. Label elements

Label elements according to (CE) Regulation no. 1272 / 2008 (CLP)

Substance name : Methanol

Signal word : Danger

Hazard pictograms:

GHS02 : flame

GHS06 : skull and crossbones

GHS08 : health hazard

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SAFETY DATA SHEET



Code PS-MI-14-F09 / 26 pag.3 / 25

Hazard statements

H225 : Highly flammable liquid and vapour. H301 : Toxic if swallowed. H311 : Toxic in contact with skin. H331 : Toxic if inhaled. H370 : Causes damage to organs. Additional text : Target organ : optic nervous (nervus opticus), central nervous system.

Precautionary statements

P210 : Keep away from heat/sparks/open flames/hot surfaces. – No smoking. P280 : Wear protective gloves/protective clothing/eye protection/face protection. P303 + P361+ P353: IF ON SKIN (or hair): Remove/Take off immediately all contaminated clothing. Rinse skin with water/shower. P301+ P310 : IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. P321 : Specific treatment (see supplemental informationfirst aid instructions on this label). P322 : Specific measures (see also supplemental information on this label).

Supplemental information

P304+ P340 : IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing. P307+ P311 : IF exposed: Call a POISON CENTER or doctor/physician. P263 : Avoid contact during pregnancy/while nursing. P240 : Ground/bond container and receiving equipment. P241 : Use explosion-proof electrical/ventilating/lighting/…/ equipment. P242 : Use only non-sparking tools. P260 : Do not breathe mist/vapours/spray. P264 : Wash with soap and water thoroughly after handling. P270 : Do no eat, drink or smoke when using this product. P271 : Use only outdoors or in a well-ventilated area. P403 + P235 : Store in a well-ventilated place. Keep cool. P405 : Store locked up. P233 : Keep container tightly closed. P501 : Dispose content/container according to national/international regulations. P370 + P378 : In case of fire: Use water, dry extinguishing media, carbon dioxide, alcohol resistant foam for extinction.

Hands protective equipment : Protective gloves from natural/butyl/nitric rubber (recommended) Eyes protective equipment :anti-splash goggles Face protective equipment :Helmet with visor (if necessary) Protective clothes :Individual cotton equipment

2.3. Other hazards

Methanol does not fulfill the PBT criteria (not PBT) and not the vPvB criteria (not vPvB). No other hazards were identified.

3. Composition / informations on ingredients

3.1. Substance

Main constituent :

IUPAC name Methanol CAS No. 67-56-1 CE No. 200-659-6 Typical concentration >99.90%

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SAFETY DATA SHEET



Code PS-MI-14-F09 / 26 pag.4 / 25

Impurities :

IUPAC name Ethanol CAS No. 64-17-5 CE No. 200-578-6 Typical concentration <500 ppm

IUPAC name Water CAS No. 7732-18-5 CE No. 231-791-2 Typical concentration <=150 ppm

IUPAC name Acetone CAS No. 67-64-1 CE No. 200-662-2 Typical concentration <30ppm

4. First aid measures

4.1. Description of first aid measures

General Measures : Remove immediately contaminated clothing. First aid personnel should pay attention to their own safety. Do not induce vomiting if the victim is unconscious. Avoid mouth to mouth resuscitation. Use alternative methods, oxygen or air devices are preferred.

If inhaled : Keep patient calm; remove to fresh air, seek medical attention.

In case of skin contact : Wash with water and soap.

In case of contact with eyes : Wash affected eyes for at least 15 minutes under running water with eyelids held open.

In case of ingestion : Rinse mouth immediately and then drink plenty of water , induce vomiting; seek medical attention. Administer 50mL of pure ethanol in a drinkable

concentration. Seek medical attention.

4.2. Most important symptoms and effects , both acute and delayed

In case of ingestion

Acute immediate effects : Formic acidemia, metabolic acidosis Delayed effects : occurs only after an asymptomatic period of about 12 to 24 hours;

see also 11 Information on likely routes of exposure - oral and inhalation routes of exposure

Delayed severe effects are anticipated, even if first aid and proper treatment measures are applied, because asymptomatic period is quite long.

4.3. Indication of any immediate medical attention and special treatment needed

Note to physician : Treatment: symptomatic (decontamination, vital signs ) .

5. Fire fighting measures

5.1. Extinguishing media Suitable extinguishing media : water (fog)/dry extinguishing media/alcohol resistant foam/carbon dioxide.

Unsuitable extinguishing media : direct water jet not to be used. 5.2. Special hazards arising from the substance (5)

Substances emitted in case of fire : Carbon monoxide, carbon dioxide

5.3. Advice for fire-fighters(5)

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SAFETY DATA SHEET



Code PS-MI-14-F09 / 26 pag.5 / 25

Special protective equipment. Wear proper breathing apparatus and chemical protective equipment.

Other information : Collect contaminated water resulting from extinguishing separately,not to reach in sewage or effluent. If containers are exposed to fire should be kept cool by spraying with water. If possible, use sprayed water to lower to the ground the smoke resulted from fire.

6. Accidental release measures

6.1. Personal precautions, protective equipment and emergency procedures Recommendations regarding accidental spills and dispersions: For the staff not involved in the emergency procedures:

a) Wear proper protective equipment, according to 8.2 to prevent any skin, eyes or personal clothing contamination.

b) Ensure a sufficient level of ventilation. Avoid contact with skin, eyes and clothing. Avoid inhalation. Take off contaminated clothing immediately.

c) Evacuate the dangerous area.

For the staff involved in the emergency procedures: Advise for the proper cloth used for personal protective clothing: see 8.2. Precausions after the intervention (fire fighters): wash the contaminated suit and the breathing apparatus with water before removing the face mask and the suit.

6.2. Environmental precautions

Do not release into the environment. In case of accidental dispersion into the environment, avoid water and soil pollution and take the

environmental isolation and cleaning measures as under 6.3. In case of contamination, inform responsible authorities.

6.3. Methods and material for containment and cleaning up Advice regarding isolation of amounts spilled :

a) collection in retention tanks or sewers around the storage areas. b) bunding with absorbent materials. c) capping procedures.

Advice regarding the cleaning way of a spilled amount: a) cleaning techniques :washing with water jet, recovery and decanting in proper packaging or intermediate tank; aspiration. b) absorbent materials: sand, sawdust, general-purpose binder, Kieselgur Substance spilled can be isolated by covering with foam resistant to alcohol. c) equipment needed to isolation and cleaning: aspiration device, brooms, shovels. Use pumps resistant to flame. If they are electrical, min. T3 class is requested. Insure proper grounding of pumping equipment(5)

Wastewater are directed to a treatment plant. Traces of remaining substance can be cleaned with absorbent materials.

6.4. Reference to other sections

For individual protection see 8.2. See Exposure Scenario (ES) attached for each identified use.

7. Handling and storage

7.1 . Precautions for safe handling

Handling : Einsure protection against fire and explosion. If containers are exposed to fire, should be kept cool by spraying water.

Prevent electrostatic charge - sources of ignition should be kept well clear – fire extinguisher should be kept handy. Ground/bond container and receiving equipment .

Ensure thorough ventilation of work and stores areas. Handle in accordance with good industrial hygiene and safety practice. Protection against fire

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SAFETY DATA SHEET



Code PS-MI-14-F09 / 26 pag.6 / 25

and explosion : Insure ventilation. Vapours may form explosive mixture with air. Take precautionary measures against static discharges. Keep away from sources of ignition - No smoking.

Hygiene measures : Do not eat , drink or smoke in work area. Wash with plenty of soap and water thoroughly after handling . Do no eat, drink or smoke when using this product. Take off contaminated clothing and protection equipment in the eat areas.

7.2. Conditions for safe storage, including any incompatibilities

Advice on specific requirements to risk management / effects control : a) Adequate materials for containers: Steel, Aluminium, plastic materials, composite materials. b) Inadequate materials for containers : - c) Recommendation to mentain integrity of substance: tanks located outdoors must be protected with parasol,

breathing valve, nitrogen blanket, spraying water for cooling and lightning rod installation. d) Other recommendations:

-Keep tightly closed containers in a cool, well ventilated area. -Take precautionary measures against static discharges. -Use explosion proof electrical equipment. -The warehouse floor should be waterproof and equipped with retention tubs to avoid spreading in case of accidental spill and connected to the organic sewerage. -Access to the warehouses is permitted only for instructed personnel -Requirements regarding ventilation : ventilated storage areas should be anti ex. -Incompatibilities regarding the packing : see 10.3;10.4;10.5.

7.3. Specific end uses

See note to 1.2. Specific end uses with the corresponding number for the Exposure Scenario:

ES 1 : Manufacturing of Methanol / use as an intermediate / use as an chemical process ES 2 : Distribution of the substance ES 3 : Formulation and (re) packing of substance and mixture ES 4 : Industrial use as fuel ES 5 : Professional use as fuel ES 6 : Industrial use in cleaning agents ES 7 : Professional use in cleaning agents ES 8 : Industrial use as a laboratory reagent ES 9 : Professional use as a laboratory reagent ES 10 : Industrial use as wastewater chemical ES 11 : Professional use in oilfield drilling and productions operations ES 12 : Consumer use of cleaning agents and de-icers (liquid products) ES 13 : Consumer use of cleaning agents and de-icers (spray products) ES 14a: Consumer use of fuels indoors( Domestic/hobby use e.g. in model engines, fuel cells, fondue sets) ES 14b: Consumer use of fuels outdoors ( gasoline additive )

Most common technical function of the substance : see 1.2.

8. Exposure controls /personal protection

Detailed information : in the attached Exposure Scenario

8.1. Control parameters

8.1.1. Occupational exposure limit values:

Occupational exposure limit value

Type of

limit value

Name of

substance

Nr.EC

Nr.CAS

8 ore Short term (15 minutes)

Biological limit value

Indicative/

Observation

Source

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Code PS-MI-14-F09 / 26 pag.7 / 25

Maximum

value (Romania)

Methyl alcohol

260 mg/m3

or

200 ppm

-

5 ppm

VLBO

6mg/L

( methanol in the urine,

end of shift)

P*

Law 319/2006 HG 1218 /2006 -annex I

Limit value

(UE)

Methanol

200-659-6

67-56-1

OEL 260 mg/m3

or

200 ppm

- -

Not provided

Skin

Directive 2006/15/CE

* Can enter the body through intact skin or mucous membranes

8.1.2. Recommended monitoring procedures: Determining methods according to referring standards in force

8.1.3. DNEL values for critical health effects

a. workers : DNEL Dermal : 40 mg/ kg body weight /d : acute toxicity – acute systemic effects DNEL Inhalation : 260 mg / m3 : acute toxicity – acute systemic effects DNEL Dermal : not quantifiable : – acute local effects DNEL Inhalation : 260 mg / m3 : acute toxicity – acute local effects DNEL Dermal : 40 mg/ kg body weight / d : acute toxicity – long term systemic effects DNEL Inhalation : 260 mg / m3 : acute toxicity – long term systemic effects DNEL Dermal : not quantifiable : – long term local effects DNEL Inhalation : 260 mg / m3 : acute toxicity – long term local effects

b. general population :

DNEL Dermal : 8 mg/ kg body weight / d : acute toxicity – acute systemic effects DNEL Inhalation : 50 mg / m3 : acute toxicity – acute systemic effects

DNEL Oral : 8 mg / m3 : acute toxicity – acute systemic effects DNEL Dermal : not quantifiable : – acute local effects DNEL Inhalation : 50 mg / m3 : acute toxicity – acute local effects DNEL Dermal : 8 mg/ kg body weight/d : acute toxicity – long term systemic effects DNEL Inhalation : 50 mg / m3 : acute toxicity – long term systemic effects DNEL Oral : 8 mg / m3 : acute toxicity – long term systemic effects DNEL Dermal : not quantifiable : – long term local effects DNEL Inhalation : 50 mg / m3 : acute toxicity – long term local effects

The leading effect in humans is CNS toxicity and neurotoxicity including optical nerve toxicity.

8.1.4. PNEC(predicted no effect concentration values ) for critical environmental effects:

Water : PNEC fresh water : 154 mg/L, assessment factor 100 : PNEC marine water : 15.4 mg/L, assessment factor 10 : PNEC water – intermittent releases : 1540 mg/L, assessment factor 1000

Sediment : PNEC sediment : 570.4 mg/ kg, dry weight

Soil : PNEC soil : 23.5 mg/kg, dry weight Sewage treatment plant : PNEC sewage treatment plant : 100 mg / L, assessment factor 10

8.2. Exposure controls

8.2.1 Appropriate engineering controls

Appropriate exposure control measures for each identified use, are presented in each exposure scenario (ES) annexed to SDS.

8.2.2. Individual protection measures, such as personal protective equipment

Technical conditions and measures to control dispersion from source towards the workers : ventilation as in ES

General safety and hygiene measures : immediately remove contaminated clothing.

Individual protection equipment

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Code PS-MI-14-F09 / 26 pag.8 / 25

a) Eye/face protection : Tightly fitting safety goggles (antisplash goggles) (e.g. EN 166 in force)

b) Skin protection : It will take note of information provided by the manufacturer on permeability and breakdown times, and specific conditions at work place .

(i) Hand

Gloves : Chemical resistant protective gloves Material : Suitable materials also with prolonged, direct contact to solvents

(Recommended :Protective index 6, corresponding > 480 minutes of permeation time according to EN 374 in force): e.g. natural/nitrylic rubber or another material

Body protection : chemical-protection suit ( according to EN 14605 in force) Equipment : coat / suit Material : cotton

(ii) Other c) Respiratory protection : lower concentrations on short-term: Gas mask with filter for organic

substances (concentration of noxa exceeded in the working media, in case of accidental spills) higher concentrations on long-term: Self-contained breathing apparatus.

See also 5 : protective equipment for firefighters

8.3. Environmental exposure control

Risk management measures : it was not necessary to estimate exposure, because in PBT / vPvB evaluation was not identified any risk. Therefore, all identified uses

of the substance are assessed with no risk for environment.

9. Physical and chemical properties

9.1. Information on basical physical and chemical properties

Physical state at 20 0C and 1013 hPa : liquid colourless

Odour : pungent

pH : 4.5-6.5

Melting / freezing point : - 97.8 0C ( no atmospheric pressure data)

Boiling initial point and boiling range : 64.7 0C / 64 0C - 65.5 0C (at 1013 hPa)

Flash point : 9.7 0 C at 1013 hPa [Method EU A.9 (Flash point) Abel-Pensky closed vessel]

Evaporation velocity : no available data

Flammability : highly flammable liquid (the flammabily is deduced from flash point and boiling point ; in accordance

with column 1 of Annex XI REACH, the study does not need to be performed as based on the chemical structure of the substance pyrophoric properties are not be expected and the substance does not liberate flammable gases in contact with water)

Superior/inferior flammability or explosion limit : 36.5%v/v air–6.7 v/v air(at 200C and atmospheric pressure)

Vapour pressure : 169.27 hPa at 250C

Vapour density : 1.1

Relative density : 0.79-0.8 (relative density D20/4)

Water solubility : miscible

Partition coefficient, n-octanol / water (log value) : -0.77 at 200 C

Self-ignition temperature : 455 0 C at 1013 hPa

Decomposition temperature : no available data

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Code PS-MI-14-F09 / 26 pag.9 / 25

Viscosity (dynamic) : 0.544 – 0.59 mPa.s at 250 C

Explosive properties : non explosive properties (in accordance with CSR, the explosiveness of the substance does not need to be tested)

Oxidising properties : no oxidising properties (in accordance with CSR, the oxidising properties does not need to be tested)

9.2 Other information

Miscibility : completely miscible in water at 200 C

Stability in organic solvents and identity of relevant degradation product : is not considered critical (in accordance with CSR,

the stability in organic solvents does not need to be tested)

Dissociation constant : substance does not contain any ionic structure under environmental conditions (in accordance with CSR, the dissociation constant does not need to be

performed)

Surface tension : no surface activity ( in accordance with CSR, surface activity does not need to be tested)

Granulometry : not applicable [in accordance with CSR, the particle size distribution (granulometry) does not need to be performed]

10. Stability and reactivity

10.1. Reactivity

Methanol shows no reactivity hazard under normal pressure and temperature. Keep it in container tightly closed because methanol is water avid.

10.2. Chemical stability

Methanol is stable under usual temperature and pressure. For handling and storage conditions see 7.

10.3. Possibility of hazardous reactions

Explosive reactions with : chloroform + sodium methoxide, diethyl zinc

Violent reactions with : strong oxidizers (e.g. : chlorine, bromine, fluorine, hydrogen peroxide, sodium hypochlorite, barium perchlorate ); alkyl aluminium salts; acetyle bromide; chloroform + sodium hydroxide; KOH + chloroform ; CrO3 ; cyanuric chloride ; ( I+ ethanol+ HgO) Pb(ClO4)2 ; HClO4 ; P2O3 ; nitric acid ; Measures : avoid storage with materials that can give dangerous reactions

10.4. Condition to avoid

Heat sources of ignition, sparks, open flame, hot surfaces, static discharge.

Measures : be kept away from heat, sparks, open flames, hot surfaces; use only non sparking tools ; no smoking ; at loading/unloading ground/bond

container and receiving equipment.

10.5. Incompatible materials

Incompatibility : metals (eg. potassium, magnesium) ; oxidants (eg. barium perchlorat, bromine, sodium hypochlorite, chlorine, hydrogen peroxide); carbon tetrachloride + metals (eg. aluminium, magnesium, zinc).

Measures : avoid storage in recipients of incompatible materials

10.6. Hazardous decomposition products

See 5.2.

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Code PS-MI-14-F09 / 26 pag.10 / 25

11. Toxicological information

All data from this section are according to the Chemical Safety Report (CSR)(1)

Information on toxicokinetics : absorbtion, metabolism, distribution and elimination

Methanol is readily absorbed after inhalation, ingestion and dermal contact and distributes rapidly throughout the body. Metabolism in humans, rodents, and monkeys contributes up to 98 percent of the clearance, with more than 90 percent of the administered dose exhaled as carbon dioxide. Renal and pulmonary excretion contributes only about 2 – 3 percent. The metabolism and toxicokinetics of methanol varies by species and dose. In humans, the half-life time is approximately 2.5 – 3 hours at doses lower than 100 mg/kg bw. At higher doses, the half life can be 24 hours or more. The mammalian metabolism of methanol occurs mainly in the liver, where methanol is initially converted to formaldehyde, which is in turn converted to formate. Formate is converted to carbon dioxide and water. In humans and monkeys, the conversion to formaldehyde is mediated by alcohol dehydrogenises and basically limited to the capacity of those enzymes. In rodents, the oxidation to formaldehyde predominantly employs the catalase-peroxidase pathway which is of less capacity and rate-limiting. Upon saturation at high doses, methanol accumulates in the blood of rodents and primates. Formaldehyde is further oxidized to formic acid and, finally, formic acid to carbon dioxide (CO2). In primates, the last reaction step, conversion of formate to carbon dioxide by the formyl-tetrahydrofolate synthetase, is of comparably low capacity which may lead to a disproportionate increase of formate in the blood and in sensitive target tissues (such as CNS and the retina) In humans, when exposed via inhalation up to an air concentration of 0.065 mg/L, no increase of blood methanol is expected. Up to 0.26 mg/L (single or repeated exposure), the methanol blood level is likely to increase 2 to 4- fold above the endogenous methanol concentration in humans, but still remains significantly below 10 mg/L. Air concentrations up to 1.6 mg/L resulted in similar blood methanol levels among rats, monkeys, and humans. However, above 1.6 mg/L, a steep exponential increase occurs in rats, a smaller exponential increase occurs in monkeys, whereas humans exhibit a linear relationship between air concentrations and blood methanol levels. Baseline levels of formate in blood are about 3 to 19 mg/L (0.07 – 0.4 mM) in humans. Toxic blood formate concentrations are reported to be 220 mg/L and higher (> 5 mM formate). Inhalation of about 1.20 mg methanol/L for 2.5 hours contributed only insignificantly to the internal formate pool in monkeys (in the μM-range). This also held true for folate-deficient conditions. After repeated inhalation of 2.6 mg/L for 6 hours/day, 5 days/week, for 1 or 2 weeks, monkeys showed no discernible increase in formate concentration in blood (estimated body burden 200 to 300 mg/kg bw/d). Formate accumulation, however, has been observed in primates upon bolus administration of more than 500 mg Methanol/kg bw . The critical methanol dose that saturates the folate pathway in humans is estimated to be ≥ 200 mg/kg bw. Based on data produced in monkeys, metabolic saturation in humans is also less likely to happen during inhalation where the dose is distributed over several hours. 11.1. Information on toxicological effects

Humans (and non-human primates) are uniquely sensitive to methanol poisoning and the toxic effects in these species is characterized by formic acidemia, metabolic acidosis, ocular toxicity, nervous system depression, blindness, coma and death. Nearly all of the available information on methanol toxicity in humans relates to the consequences of acute rather than chronic exposures. A vast majority of poisonings involving methanol have occurred from drinking adulterated beverages and from methanol-containing products. Although ingestion dominates as the most frequent route of poisoning, inhalation of high concentrations of methanol vapour and percutaneous absorption of methanolic liquids are as effective as the oral route in producing acute toxic effects. The most noted health consequence of longer-term exposure to lower levels of methanol is a broad range of ocular effects. The minimum lethal dose of methanol in the absence of medical treatment is between 0.3 and 1 g/kg. The minimum dose causing permanent visual defects is unknown. The symptoms and signs of methanol poisoning, which may not appear until after an asymptomatic period of about 12 to 24 hours, include visual disturbances, nausea, abdominal and muscle pain, dizziness, weakness and disturbances of consciousness ranging from coma to chronic seizures. Visual disturbances generally develop between 12 and 48 h after methanol ingestion and range from mild photophobia and misty or blurred vision to markedly reduced visual acuity and complete blindness. In extreme cases death results. The normal blood concentration of methanol from endogenous sources is less than 0.5 mg/liter (0.02 mmol/litre), but dietary sources may increase blood methanol levels. Generally, CNS effects appear above blood methanol levels of 200 mg/L (6 mmol/L), and fatalities have occurred in untreated patients with initial methanol levels in the range of 1500-2000 mg/L (47-62 mmol/L). Visual disturbances of several types (blurring, constriction of the visible field, changes in colour perception, and temporary or permanent blindness) have been reported in workers who experienced methanol air levels of about 1.6 mg/L (corresponding to 1200 ppm) or more. A widely used occupational exposure limit for methanol is 0.26 mg/L

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Code PS-MI-14-F09 / 26 pag.11 / 25

(corresponding to 200 ppm), which is designed to protect workers from any of the effects of methanol-induced formic acid metabolic acidosis and ocular and nervous system toxicity. No other adverse effects of methanol have been reported in humans except minor skin and eye irritation at exposures well above 0.27 mg/L (corresponding to 200 ppm).

11.1.1. Information on relevant hazard classes

a) Acute toxicity

Animal data Oral: LD50 (rats) : 1187 - 2769 mg/kg bw (male/female); concentration of the aqueous solutions 15 - 35%. LD50( Rhesus monkeys): 6000 mg/kg bw (4/8 animals have survived after bicarbonate application LD50 (( Rhesus macaca monkeys): 7000-9000 mg/kg Inhalation: LC50 (rats) : 87.5 mg/L (6 hours); (male/female) LC50 (rats) : 128.2 mg/L (4 hours) ; (male/female) LC50 (rats) : approx. 79 mg/L air (134 minutes). LC50 (cats) :approx. 43.7 mg/L air (6 hours) LC50 (cats) :85.4 mg/L air (4.5 hours) Lethal concentrations (Rhesus monkeys) :1.3 mg/L air (after 41 hours), (male/female) Lethal concentrations (Rhesus monkeys) :13 mg/L air (18 hours) (male/female) Lethal concentrations (Rhesus monkeys) :52 mg/L air (1 hour). (male/female) Dermal: Methanol is classified according to Annex I to the Directive 67/548/EEC with T; R 23/24/25. Therefore, animal testing regarding acute dermal toxicity is not necessary. LD50 (rabbits) :about 17,000 mg/kg bw Human: Oral ingestion dominates as the most frequent route of poisoning, but percutaneous absorption or inhalation of vapours are as effective as the oral route in producing methanol acute toxic syndrome. Serious ocular symptoms appear above 500 mg/L ranging from mild photophobia, misty or blurred vision to markedly reduced visual acuity and total blindness. The minimal acute methanol dose to humans that can result in death is considered to be 300 to 1000 mg/kg by ingestion. Fatalities have occurred in untreated patients with initial methanol blood levels in the range of 1500 to 2000 mg/L . In conclusion, formate is considered to be the ultimate toxicant in acute methanol intoxication in humans. Acidosis and ophthalmologic changes are typical effects in primates. They do not occur in rodents or rabbits, which are able to remove formate more efficiently. In these animals, CNS depression, narcosis and death are the leading symptoms of intoxication.

The following information is taken into account for any hazard / risk assessment:

Oral: LD50 (rats) :> 1187-2769 mg/kg bw LD50 (monkeys): 7000-9000 mg/kg bw LD50 (monkeys): 6000 mg/kg bw, but following bicarbonate supplementation

Dermal: LD50 (rabbits) :17100 mg/kg bw Inhalation: LD50 (rats) : 128200 mg/m³ air (4-hour s) LD50 (cats) : 85400 mg/m³ air (4.5-hours)

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LD50 (cats) : 43700 mg/m³ air ( 6-hours)

Justification for classification or non classification Although the lethal dose of methanol is high for most experimental animals (mostly > 2000 mg/kg bw after single oral administration), the substance is classified as acutely toxic by oral, dermal and inhalative exposure, and as capable of inducing serious irreversible effects upon single exposure by all of these routes. Classification according to Directive 67/548/EEC : T; R23/24/25; T; R39/23/24/25. According to (CLP) Regulation no. 1272/2008 the classification is : Acute toxicity category 3: toxic if swallowed; toxic in contact with skin; toxic if inhaled. Acute toxicity on one specific target organ, STOT single exposure, category 1 (route of exposure: oral, dermal, inhalation), H370.

b) Skin corrosion / irritation

Skin corrosion

No informations available.

Justification for classification or non classification The substance is not classified corrosive since no data are available. Based on available data, the classification criteria are not fulfilled.

Skin /eye irritation


Skin : not irritating (rabbit) Eyes : not irritating (rabbit)

Value used for CSA:

Skin irritation / corrosion: not irritating

Eye irritation : not irritating

Justification for classification or non classification Methanol exhibited no skin irritation in one reliable study. Available studies show that methanol is a slight to moderate eye irritant, but with reversibility of effects documented in one reliable study. High concentration of methanol vapours may be irritating to mucous membranes. Based on the vapour pressure of about 130 hPa at 20 °C, the molecular weight of 32 g/mol and the molar volume of about 24 L/mol, it can be estimated that the saturation concentration was ≥ 150 mg/L and, thus, clearly lethal. In conclusion, methanol is not irritating to the skin and the eyes.

Based on available data, the classification criteria are not fulfilled. c) Serious eye damage/ irritation

See conclusions of point b) . d) Respiratory or skin sensitisation

Skin sensitisation

The following information is taken into account for any hazard / risk assessment: A guinea pig maximization assay gave no evidence of contact sensitization after induction and challenge doses of 50%.

Value used for CSA: Not sensitizing.

Respiratory sensitisation


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Not required.

Justification for classification or non classification Methanol exhibited no skin sensitizing potential. The low number of 4/22 animals with slight erythema (score 1) gives no evidence of a notable sensitization potential of methanol. In conclusion, methanol is not sensitizing to the skin. No classification is required.

Based on available data, the classification criteria are not fulfilled. e) Germ cell mutagenicity


In vitro Gene mutation (Bacterial reverse mutation assay / Ames test) : S. typhimurium negative except TA 102+S9

(ambiguous) (OECD 471) Gene mutation (Mammalian cell gene mutation assay) : V79 negative, L5178Y+S9 positive (both

comparable to OECD 476) Chromosome aberration (in vitro micronucleaus assay) : V79 negative DNA damage (Damage and repair assay in bacteria) : E. coli positive Genome mutation (Mitotic chromosomal segregation assay) : A. nidullans positive In vivo Chromosome aberration (Chromosomal aberration): primary lung cells negative Chromosome aberration (Micronucleus assay): erythrocytes negative (similar OECD 474), primary lung cells negative Chromosome aberration (Synaptonemal complex): pachytene spermatocytes negative

Value used for CSA Genetic toxicity: negative.

Justification for classification or non classification Based on the negative results in the in vivo studies, methanol does not seem to be mutagenic. Furthermore, carcinogenicity studies indicated no evidence of a carcinogenic potential in rats and mice exposed to methanol. No need for classification.

Based on available data, the classification criteria are not fulfilled. f) Carcinogenicity

Justification for classification or non classification From the present evaluation it is concluded that methanol is not needed to be classified as a carcinogen. Based on available data, the classification criteria are not fulfilled. g) Reproductive toxicity

Effects on fertility Animals


NOAEC (maternal toxicity) (rats) :1.3 mg/L NOAEC (teratogenicity) (rats) :1.3 mg/L NOAEC (maternal toxicity) = 2.39 mg/L for monkeys NOAEC (teratogenicity) (monkeys) :2.39 mg/L for Negative for spermatozoon morphological anomalies: NOAEL (oral) = 1000 mg/kg bw/day

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Developmental toxicity / Teratogenity Animals

NOAEC(maternal toxicity) (rats) : 1.33 mg/L NOAEC(teratogenicity) (rats and mice) :1.33 mg/L LOAEL (maternal toxicity) (mice) :1700 mg/kg bw LOAEL(teratogenicity) (mice) :5000 mg/kg bw Human There are no relevant epidemiological studies or case reports which describe an increase in the incidence of malformations in children of mothers exposed to methanol during pregnancy. The limited data available on methanol exposure on reproductive and developmental effects do not show an association (NTP, 2003). In an epidemiological study, the reproductive effects of various occupations and associated exposures to complex mixtures were examined in women who gave birth to infants with and without cleft lip or cleft palate (Lorente et al., 2000). No association was found between methanol exposure and oral clefts. The small number of subjects exposed to methanol, the lack of individual exposure data, and confounding factors by other chemical exposures did not allow to draw firm conclusions as to the role of methanol on these outcomes. lower methanol blood levels.

The following information is taken into account for any hazard / risk assessment: NOAEC(maternal toxicity) = 1.33 mg/L for rats NOAEC(teratogenicity) = 1.33 mg/L for rats and mice LOAEL (maternal toxicity) = 1700 mg/kg bw for mice LOAEL(teratogenicity) = 5000 mg/kg bw for mice

Toxicity to reproduction: other studies

Not required.

Justification for classification or non classification Conclusive, but not sufficient for classification. Based on available data, the classification criteria are not fulfilled. h) STOT ( toxicity on specific target organ)–single exposure

See point i). i) STOT ( toxicity on specific target organ)–repeated exposure Animal data

Oral : LOAEL subacute = 2340 mg/kg/bw in monkeys (mortality 7/7 after 3 days exposure) Inhalation : NOAEC chronic = 0.013 mg/L air in monkeys (7 to 29 months exposure) Human data In male and female workers exposed to methanol from 0.3 to 7.8 years, the highly exposed workers (4.7 - 7.3 mg/L): -more often complained of blurred vision, headache and nasal irritation during or after work. -nobody stated to suffer from photophobia. -no retinal changes. Among three workers exposed to about 1.0 to 1.6 mg/L and one worker exposed to 0.12 to 3.6 mg/L:

- two showed retarded pupil reflex and one exhibited mild mydriasis - other common complaints were forgetfulness and skin sensitivity At an health hazard evaluation conducted by the National Institute for Occupational Safety and Health (NIOSH)

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with concentrations of airborne methyl alcohol ranged from 0.48 to 4.0 mg/L showed blurred vision, headaches, dizziness, nausea to the comparison group.


Oral : LOAEL subacute = 2340 mg/kg/bw in monkeys (mortality 7/7 after 3 d exposure) Inhalation : NOAEC chronic = 0.013 mg/L air in monkeys (7 to 29 months exposure)

Value used for CSA (route : oral)

LOAEL: 2340 mg/kg bw/day

Target organs: neurological: eyes (retina, optic nerve)

Value used for CSA (route: inhalation)

NOAEC: 13 mg/m³ air

Target organs: cardiovascular / hematological: heart; neurological: brain (multiple sections); digestive: liver

Justification for classification or non classification Chronic studies in monkeys clearly demonstrate the potential of methanol to cause neurological and myocardial effects. Although there is a clear potential of methanol to cause adverse health effects especially in primates, the experimental studies in animals do not provide clear evidence for the necessity for classification. However methanol is classified as acute toxic by oral, dermal and inhalative exposure, and as capable of inducing serious irreversible effects upon single exposure by the oral, dermal and inhalation route. Due to the much higher sensitivity of humans to CNS- and optic nerve toxicity, the rodent studies are of little relevance to the human situation. According to Regulation no. 1272/2008 (CLP) on classification, labeling and packaging of the substances and mixtures the classification is : (STOT SE) single exposure category 1 (route of exposure: oral, inhalation), H370. j) Aspiration hazard

Non applicable. k) Other effects

Specific investigations: other studies

Methanol intraperitoneally dosed in rats conducted to inhibition of dependence of formate oxidation with folic acid. After the initial dosage of 4000 mg/kg bw, 12 hours later an injection of 1000 or 2000 mg/kg bw followed. Formic acidemia, metabolic acidosis and visual toxicity occurred. These functional tests provide functional evidence of direct retinal toxicity in methanol poisoning at stages not yet pronounced in histopathological changes Formate oxidation was found to be about 50% lower in human than in rat retina A subacute oral toxicity study in monkeys indicated that repeated methanol dosing caused ocular lesions after a high initial dose of 2000 mg/kg bw followed by lower doses for up to 6 days, depending on the animal’s acidotic response in blood, while acute methanol toxicity did not yield signs of ocular toxicity.

The following information is taken into account for any hazard / risk assessment: LOAEL(ocular toxicity) intraperitoneal = 5000 mg/kg bw for rats (no NOAEL identified)

Justification for classification or non classification Based on available data it is concluded that methanol is not classified as a neurotoxic substance, according to Directive 67/548/EEC and the UE classification according to the (EC) Regulation nr. 1272/2008 (CLP) . Based on available data, the classification criteria are not fulfilled.

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Information on likely routes of exposure

Exposure routes : oral, dermal, inhalation. : oral ingestion is the most common route of poisoning. : vapours and percutaneous absorbtion are as effective in producing acute toxic symptom as oral ingestion Effects : metabolic acidosis, ocular and central nervous system toxicity.

Oral exposure route

Immediate effects/ human / : no data available Delayed effects /human / : the signs occur after an asymptomatic period of 12 to 24 hours Clinic symptoms : headache, dizziness, nausea and vomiting, visual disturbances, abdominal pain. It can progress to coma, convulsions and death due chronic respiratory failure. Visual disturbances generally develop between 12-48 hours after Ingestion: range from mild photophobia and visual disturbances to markedly reduced visual acuity, narrowing the visual field, changes in color perception and complete blindness.

at sanguine values of 200 mg/L : transient CNS effects at sanguine values> 500 mg/L : serious ocular symptoms (varying from a mild photophobia to complete blindness) at sanguine values 1500 - 2000mg/L : death (in case of untreated patients) ; convulsions and coma had unfavourable

prognostic Inhalation exposure route

Immediate effects / human / : no data available Delayed effects / human / : at low concentrations ( ~ 200ppm) a wide visual disturbances at high concentrations (~1200 ppm) visual disturbances :blurred vision, visual field narrowing , changes in colours perception , temporary or permanent blindness Subsequent effects / human / : at low concentrations (~200ppm) may appear minor skin and eye irritation

Dermal exposure route

Immediate effects / human / : no data available Subsequent effects / human / : see Inhalation exposure route Symptoms related to the physical, chemical and toxicological characteristics

See also subchapter Information on likely routes of exposure.

Symptoms at low exposure : - inhalation / human : see Information on likely routes of exposure –oral and inhalation routes of exposure

at low concentrations (~200 ppm) : for 4 hours without significant physiological effects

- dermal / human : see Information on likely routes of exposure-( Dermal routes of exposure)

Symptoms at severe exposure: - oral / human : see delayed effects at Information on likely routes of exposure- oral and inhalation routes of exposure Information on delayed and immediate effects as well as chronic effects from short and long term exposure

Delayed effects : effects of severe exposure occurs after a latent period asymptomatic of 12-16 hours

Immediate effects : no data available

Chronic effects from long term : blurred vision, headache and nasal irritation during or after work hours, forgetfulness and skin sensitization ( for highly exposed workers : 4.7-7.3 mg/L) ; blurred vision,

headaches, dizziness and nausea (for exposed workers : 0.48-4.0 mg/L); : see also Information on likely routes of exposure – inhalation route of exposure Chronic effects from short term : see Information on likely routes of exposure – oral and inhalation routes of exposure (at high concentrations) Interactive effects

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Methanol metabolism is slowed by the presence of ethyl alcohol in the body. See also subchapter. 4.1.

12. Ecologic information

12.1. Toxicity

Aquatic compartment (including sediment)

Acute toxicity Fish LC50 (96h) = 28100 mg/L Pimephales promelas LC50 (96h) = 20100 mg/L Oncorhynchus mykiss (=Salmo gairdneri) LC50 (96h) = 15400 mg/L Lepomis macrochirus Aquatic invertebrates EC50 (48h) > 10000 mg/L Daphnia magna Algae EC50 (96h) ca. 22000 mg/L Selenastrum capricornutum (new name: Pseudokirchnerella subcapitata)

Chronic Toxicity Fish NOEC (200h) = 7900 - 15800 mg/L Oryzias latipes Microorganisms EC 50: 19800 mg/L activated sludge IC50: >1000 mg/L activated sludge IC50: 880 mg/L Nitrosamonas Algae , Toxic limit concentration: 530 - 6600 mg/L Pseudomonas, Microcystis aeruginosa. The results indicate a very low acute toxicity for aquatic organisms, well above 10000 mg/L. Also for microorganisms data indicate a low toxicity. The PNEC for aquatic organisms was derived from the LC50 (96h) = 15400 mg/L Lepomis macrochirus using an assessment factor of 100. Although the available information on long-term toxicity in fish is not used to derive the PNEC, the reported no observed effect concentration of 7900 - 15800 mg/L in Oryzias latipes confirms the low toxicity of methanol also after chronic exposure.

Fish

Short-term toxicity to fish

In continuous flow-through systems values were:

LC50 (96 h)= 29400 mg/L (Pimephales promelas)

LC50 (96 h)= 20100 mg/L (Salmo gairdneri)

LC50 (96 h)= 15400 mg/L (Lepomis macrochirus)

LC50 (96 h)= 20100 mg/L (Salmo gairdneri) The following information is taken into account for acute fish toxicity for the derivation of PNEC LC50 (96 h): 15400 - 29400 mg/L

Value used for CSA LC50 (for freshwater fish): 15400 mg/L

Long-term toxicity to fish

In an early-life-stage bioassay conducted with Oryzias latipes available by Gonzales-Doncel et al. (2008) NOECs range

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between 7900 - 15800 mg/L. Although this study cannot be used for the derivation of the PNEC aqua (in-vitro study with reduced duration of exposure) the result indicates that methanol has a very low long-term toxicity to fish.

The following information is taken into account for long-term fish toxicity for the derivation of PNEC NOEC : 7900 - 15800 mg/L

Value used for CSA EC10/LC10 or NOEC for freshwater fish: 7900 mg/L

Aquatic invertebrates

Short-term toxicity to aquatic invertebrates

In a reliable standard static test with Daphnia magna no adverse effects were reported at 10000 mg/L after 48-h exposure (Kuehn, 1989). Toxicity values well above 10000 mg/L reported also for Daphnia magna in other studies support this finding: 22200 mg/L (EC50, 48h) 20803 mg/L (EC50, 24h), and 22910 mg/L (LC50, 24h). Additionally short-term toxicity data are available from tests conducted with other test organism: Mytilus edulis, LC50 (96h) = 15900 mg/L and Moina micrura, LC50 (96h) = 4820 mg/L. Although the lowest toxicity was reported for Moina micrura this is not a standard organism, which does not occur in cold-temperate regions. For this reason it is considered less relevant than Daphnia and was not used in the PNEC derivation.

The following information is taken into account for short-term toxicity to aquatic invertebrates for the derivation of PNEC EC50(48h) : >10000 mg/L

Long-term toxicity to aquatic invertebrates

No studies on chronic toxicity of aquatic invertebrates are available. However, several acute toxicity studies clearly demonstrate the low toxicity of methanol to aquatic invertebrates with EC50 values well above 10000 mg/L. Long-term studies with the structurally related substances 2-Propanol and 1-Butanol revealed no reproductive effects at concentrations up to 100 mg/l (NOEC > 100 mg/l) respectively 18 mg/L.

There is no need for the further conduction of chronic tests. Algae and aquatic plants

Effects on algae / cyanobacteria

Alga Scenedesmus quadricauda:TGK (toxicity threshold)= 8000 mg/L , during 8 days

Blue-green algae: LC50 =0300 - 43290 mg/L.

LC50 = 28400 mg/L, inhibition in growth rate during an exposure period of 10 – 14

Green algae ( Selenastrum capricornutum): LC50 = 22000 mg/L, 96h inhibition in growth rate , method OECD 201

The following information is taken into account for effects on algae / cyanobacteria for the derivation of PNEC:

EC50 : 20300 - 43290 mg/L TGK : 8000 mg/L

Value used for CSA:

EC50/LC50 for freshwater : 22000 mg/L

Sediment organisms

Methanol has a low potential for adsorption or bioaccumulation, exhibits a very high solubility in water and is readily biodegradable in both aerobic and anaerobic environments. In addition, results from the aquatic studies indicate no harmful effects. Therefore exposure of sediment organisms is unlikely and testing towards sediment dwelling organisms not necessary. The expected low toxicity towards sediment organisms is underlined by a case study where EC50 = 71700 mg/L (Tubifex tubifex ).

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The following information is taken into account for sediment toxicity for the derivation of PNEC No relevant information on acute or chronic effects on sediment organisms is available. However, since the substance exhibits a low log Pow and low log Koc exposure of sediment organisms is unlikely and testing towards sediment dwelling organisms not necessary.

Other aquatic organisms

This information is not available.

Terrestrial compartment The available experimental data methanol are not appropriate for a derivation of PNE Csoil. The substance however, exhibits low potential for adsorption, is not bioaccumulative and readily biodegradable in both aerobic and anaerobic environments. The results of aquatic tests revealed no harmful effects of methanol, and by thereby suggesting little hazardous potential towards soil organisms. Therefore, the equilibrium partitioning method has been used to assess the hazard potential of methanol for soil organisms.

Arthropode

Effects on soil macro-organisms except arthropods

Taking in account the potential for adsorption to soils, bioaccumulative potential, and the results of aquatic studies regarding the harmful effects of methanol, the equilibrium partitioning method has been used to assess the hazard potential to soil organisms. Based on the result( study similar to OECD 207) : LC50 (48h) >1 mg/cm2 was determined for Eisenia foetida (used as a marker, for the relative toxicities of several chemicals and other soil invertebrates) ,methanol was classified as relatively non toxic.

The following information is taken into account for effects on soil macro-organisms except arthropods for the derivation of PNEC LC50: > 1mg/cm3

Effects on soil arthropods For methanol there are no appropriate data on terrestrial toxicity available for a derivation of PNEC soil. See the second paragraph referring to the potential for adsorption, bioaccumulation and biodegradable, the results of aquatic tests, methods used to assess the hazard.

The following information is taken into account for effects on soil arthropods for the derivation of PNEC: No relevant data available.

Toxicity to terrestrial plants

Though there are no guideline conform studies available for plant toxicity tests, the results of various literature studies, show that methanol do not exhibit toxic or harmful effects below concentrations of 100 mg/L. Therefore , according to CSR the evidence approach for short term toxicity to plants may be applied. See paragraph 1 and 2 at Terrestrial compartment.

The following information is taken into account for toxicity on terrestrial plants for the derivation of PNEC Weight of evidence approach for short term toxicity tests to plants. Lactuca sativa: IC50 (3 d): ca. 41000 mg/L test mat. based on: germination Onoclea sensibilis: IC50 (63 h): ca. 20000 mg/L test mat. (nominal) based on: germination Triticum aestivum: EC50 (7 d): 60 M test mat. (nominal) based on: cell elongation (dark) Triticum aestivum: EC50 (7 d): 900 M test mat. (nominal) based on: Cell elongation (light) Triticum aestivum: EC50 (7 d): 70 M test mat. (nominal) based on: Cell multiplication (dark) Triticum aestivum: EC50 (7 d): 60 M test mat. (nominal) based on: Cell multiplication (light)

Toxicity to soil micro-organisms According to the CSR conclusions, there is not necessary to perform direct or indirect exposure studies for soil.

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The available experimental data of methanol are not appropriate for a derivation of PNEC soil.

Toxicity to other terrestrial organisms


Atmospheric compartment

Abiotic effects

Global warming Since adsorption bands of methanol are not within the range of 800-1200 nm a potential greenhouse effect is not expected.

Stratospheric ozone The atmospheric lifetime of methanol is not long enough to allow for transport into the troposphere. Furthermore, methanol does not contain one or more Cl, Br or F substituent. Therefore, ozone depletion potential is not expected.

Tropospheric ozone Methanol is expected to show a low reactivity so that it is unlikely to contribute significantly to the ozone peak values in the troposphere.

Acidification Due the molecular structure it is not expected that acidifying components are formed.

Microbiological activity in sewage treatment systems

Toxicity to aquatic micro-organisms TGK= 530 mg/L in a 192h test with Microcystis aeruginosa.

TGK= 6600 mg/L, Pseudomonas ,cell multiplication test for 16 hours,

EC50 =20000 mg/L , activated sludge

IC50= 880 mg/L, Nitrosamonas

IC50 >1000 mg/L, activated sludge, according to the OECD Guideline 209 ( respiration inhibition test considered the most appropriate for assessing the risk for wastewater treatment plant.).

The following information is taken into account for effects on aquatic micro-organisms for the derivation of PNEC:

EC 50 : 20000 mg/L IC50 : 880 - >1000 mg/L Toxic threshold values (TGK): 530 - 6600 mg/L

Non compartment specific effects relevant for the food chain (secondary poisoning)

Toxicity to birds

The following information is taken into account for effects on birds for the derivation of PNEC:

No reliable information on acute or chronic effects on birds is available. However, since the substance exhibits a low log Pow, secondary poisoning is unlikely to be a relevant exposure route.

Toxicity to mammals

Secondary poisoning is not relevant for methanol. Therefore, toxicity data on mammals are not considered in respect to this section. It should be noted, that is a large amount on information on the toxicity to mammals available (see section 11 ).

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12.2. Persistence and degradability

Biodegradation in water and sediment

According to screening testing : Methanol is readily biodegradable in freshwater based on the results of standard ready tests that show 71.5 – 95 percent removal after 5 and 20 days. In marine water degradation rates were found between 69 - 97 % .

The following information is taken into account for any hazard / risk / persistency assessment Biodegradation: 71.5 - 95 % (freshwater, wastewater); 69 - 97 % (marine water)

Value used for CSA Biodegradation in water : readily biodegradable

According to simulation testing : Methanol is readily biodegradable in freshwater and thus no additional information on degradation and simulation tests in soil or sediments is required

Additional data on biodegradation in soil and sediments are available and presented here for the sake of completeness. The degradation of methanol in anaerobic sediments collected from the upper 15 cm of a salt marsh in San Francisco Bay. The sediments were highly reduced and contained methane and hydrogen sulphide. The sediments were homogenized anaerobically with San Francisco Bay water and 310-340 µmol methanol/flask was added to make up the inocula. After 3 days incubation, 83-91% conversion of the methanol had occurred. The products of methanol degradation were methane, CO2 and water. It has been showed that the time needed to eliminate 50% Methanol by various inocula is =< 8 hours.

The following information is taken into account for any hazard / risk / persistency assessment Anaerobic degradation: 83-91 % conversion after 3 days to methane, CO2 and water.

Biodegradation in soil

Methanol is readily biodegradable in freshwater and thus no additional information on degradation and simulation tests in soil or sediments is required. However, additional data on biodegradation in soil and sediments are available and presented here for the sake of completeness. A study showed that degradation in soil was higher under aerobic than anaerobic conditions. Looking at CO2 evolution, biodegradation was 53.4 and 46.3 % after 5 days under aerobic and anaerobic conditions, respectively. Tests with radiolabelled material confirm the higher degradation under aerobic conditions.

The following information is taken into account for any hazard / risk / persistency assessment Aerobic degradation: 53.4 % after 5 days Anaerobic degradation: 46.3 % after 5 days

Abiotic degradation As regards the compartment air methanol is degraded in the atmosphere by photochemical, hydroxyl-radical dependent reactions, with a rate constant of 0.932 x 10^-12 cm³/molecule*sec . A half-life in the troposphere of about 17 – 18 days can be estimated. Methanol is thus slowly degraded by photochemical processes. With respect to the aquatic environment methanol, as an alcohol, lacks hydrolysable groups and is chemically stable in water.

Biotic degradation Methanol is readily degradable under both aerobic and anaerobic conditions in a wide variety of environmental media including fresh and salt water, sediments and soils, ground water, aquifer material and industrial wastewater.

Degradation rate in water: 1-7 days Degradation rate in sediment: 1-7 days Degradation rate in soil: 1-7 days Degradation rate in air: 1-7 days

12.3.Bioaccumulation potential

Methanol does not significantly bioaccumulate in fish. Experimental BCFs of < 10 in fish species, including Cyprinus carpio and Leuciscus idus, have been reported, according to data below

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Aquatic bioaccumulation

The study needs not be conducted since the substance has a low potential for bioaccumulation (log Kow < 3). However, the studies available on aquatic bioaccumulation are summarized below.

Cyprinus carpio / aqueous (freshwater) / static / Total uptake duration: 72 h : BCF: 1 (blood and tissues (gill, muscle, liver, kidney, intestine)

BCF: 1 (muscle) BCF: 3 (gills, liver, kidney)

BCF: 4.5 (intestine) Leuciscus idus melanotus / aqueous (freshwater) /Total uptake duration:72 h : BCF: < 10 Terrestrial bioaccumulation


The following information is taken into account for any hazard / risk / bioaccumulation assessment BCF < 10

Terrestrial bioaccumulation

log Pow =0.35 indicates a low bioaccumulation potential.

12.4. Mobility in soil

Distribution on environmental compartments

Adsorption / desorbtion

Adsorption on soil is not to be expected due to the high solubility of methanol as well as its low octanol-water partition coefficient. According to CSR studies on adsorption of methanol onto three different soil types at 6 deg C:

Adsorption coefficients: 0.13 and 0.61

Koc= 1 , calculated value

These coefficients indicate that methanol has a low adsorptive capacity on soils.

The following information is taken into account for any environmental exposure assessment: Koc : 0.13 - 1

Volatilization A value of 0.461 Pa m³/mol for the Henry’s Law constant indicates that volatilization is not a significant removal process from the aquatic compartment .

The following information is taken into account for any environmental exposure assessment Henry’s Law constant : 0.461 Pa m³/mol

Value used for CSA : Henry's law constant (H) at 20°C: 0.461 (in Pa m³/mol or dimensionless)

Discussion summary on environmental distribution

Adsorption on soil is not to be expected due to the high solubility of methanol as well as its low octanol-water partition coefficient. Adsorption coefficients between 0.13 and 1 measured and calculated indicate that methanol has a low adsorptive capacity on soils. A value of 0.461 Pa m³/mol for the Henry’s Law constant indicates that volatilization is not a significant removal process from the aquatic compartment

12.5. Assessment of PBT/vPvB Properties

Persistence Assessment

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Due to the results from chapter 12.2 Persistence and degradation, the substance is not persistent (not P) and not very persistent (not vP) in the environment.

Bioaccumulation Assessment

Due to the results from chapter 12.3 Bioaccumulation the substance is not bioaccumulative (not B) and not very bioaccumulative (not vB).

Toxicity Assessment

Due to the results of the aquatic toxicity studies (see 12.1 Aquatic compartment, including sediment) and the relevant mammalian toxicity studies (see 11.Toxicokinetic information on absorption, distribution, metabolism and elimination ), the substance is not toxic (not T).

Summary and overall conclusions on PBT or vPvB properties Regarding all available data on biotic and abiotic degradation, bioaccumulation and toxicity it can be stated that the substance does not fulfil the PBT criteria (not PBT) and not the vPvB criteria (not vPvB). As the substance does not fulfil the PBT (no PBT) as well as vPvB (not vPvB) criteria, the characterisation of emissions is not to be done. 12.6. Other adverse effects Are not known

13. Disposal considerations

National regulations : OUG 195/2005, Law 107/1996, HG 621/2005, HG 856/2002, HG 352 / 2005, HG 351 / 2005 , Law 211/2011, with the subsequent additions and amendments.

Community regulations :Directive 2000/60/CE, Directive 2008/98/CE, with the subsequent additions and amendments

13.1. Waste treatment methods

a) waste treatment containers and methods

Containers : to clean by washing with water. waste container are managed in compliance with legal requirements applicable in force Waste : water contaminated with methanol, are sent to sewage treatment plants, to be biological treated; see also 5.3.

b) Physical/chemical properties that may affect waste treatment option : no data available

c) Disposal

Dispose of container contents to hazardous or special waste collection point, in case that user does not own wastewater treatment plant.

d) Where appropriate, any special precautions for any recommended waste treatment option shall be identified.

Wear protective equipment according to 8.2.

14. Transport information

Terrestrial transport: road (ADR), rail (RID),inland waterways (ADN) : 14.1. UN Number : 1230

14.2. UN proper shipping name : METHANOL

14.3. Transport hazard class(es) : 3 Subsidiary risk class : 6.1 Classification code : FT1 Labels : 3+6.1 Hazard identification number : 336

14.4. Packing group : II 14.5. Environmentally hazardous : no

14.6. Special precautions for user : no data available Special precautions : 279

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Transport by Air (ICAO) 14.1. UN Number : 1230


14.3. Transport hazard class(es) : 3 Risk class subsidiary : 6.1 Classification code : FT1 Labels : 3+6.1 Hazard identification number :336

14.4. Packing group : II

Maritime transport (IMDG) 14.1. UN Number : 1230


14.3. Transport hazard class(es) : 3

14.4. Packing group : II Labels : 3+6.1

14.5. Environmentally hazardous : is not environmentally dangerous

14.6. Transport in bulk according to Annex II of MARPOL 73/78 and the IBC Code : Product name : Methyl alcohol Pollution category : Y Risk : P Ship type : 3 Tank type : 2G

EU regulations : Directive 2008/68/EC National (Romania ) regulations : HG 1326 / 2010

15. Regulatory information

15.1. Safety, health and environmental regulations/legislation specific for the substance

Relevant Community provisions : Directive 2007/30/EC , Directive 2006/15/EC , Directive 96/82/EC (Seveso substance )

National (Romania ) regulations : HG 398/2010, HG 937/2010, Law 319/2006, HG 1146/2006, HG 1218/2006 OUG 122/2010, HG 447/2009, HG 804/2007, Law 360/2003, OUG195/2005, with the subsequent additions and amendments

15.2. Chemical safety assessment

For methanol was performed a chemical safety assessment .

16. Other information

(a) Revision

Changes to the vers. 2.0: - at section 1.1 : completed with one more registration number - at section 1.2 : completed with "/ or" at manufacturer and / or distributor - at section 11 g) : the title " Developmental toxicity " is completed with " Teratogenity" - at section 13 - Legislation on disposal : amendments and additions at the repealed / in force legislation

(b) Legend of acronyms / abbreviations: ADN : Deoxyribonucleic acid BCF : Bioconcentration factor CAS : Chemical Abstract Service EC : European Commision CLP : Classification, Labelling , Packaging CSA : Chemical Safety Assessment CSR : Chemical Safety Report DNEL : derived no-effect level - is the level of exposure to a substance above which humans should not be exposed.

S.C. VIROMET S.A.

SAFETY DATA SHEET



Code PS-MI-14-F09 / 26 pag.25 / 25

DNEC : derived no-effect level - is the concentration of exposure to a substance above which humans should not be exposed. EC50 :effective concentration of the substance that determines 50% of the max. answer. ES : Exposure Scenario ECHA : European Chemical Agency (Helsinki, Finland) F : highly flammable SDS : Safety Data Sheet HG : Government Decision (Romania) IC50 : average of immobilization/inhibition concentration IUPAC : International Union of Pure and Applied Chemistry Koc : organic carbon normalised distribution coefficient LC50 : Lethal concentration 50% (median lethal concentration ) - concentration at which 50% of the population is expected to die LD50 : Lethal dose 50% (median lethal dose ) - the estimated dose at which 50% of the population is expected to die. LOAEL : Lowest Observed Adverse Effect Level NIOSH :National Institute for Safety and Health NOAEC : No observed adverse effect concentration NOAEL : No observed adverse effect level NTP : National Toxicology Programm (USA) OECD : Organization for Economic Co-operation and Development PBT : Persistent - Bioaccumulative -Toxic PNEC : Predicted no effect concentration Pow : partition coefficient, n- octanol / water SNC : Central nervous system STAS : Romanian standard STOT SE : specific target organ toxicity – single exposure UN : United Nations vPvB : very Persistent - very Bioaccumulative vs : versus Xn : harmful T : toxic TGK : Toxische Grenzkonzentration

(c)Bibliographic sources:

(1) Chemical Security Report (CSR) of S.C. VIROMET S.A. Methanol (2) The registration dossier of S.C. VIROMET S.A. according to (EU) Regulation no. 1907/2006 of the European

Parliament and the Council of 18 December 2006, concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH)

(3) Hazardous Chemicals- Desk Reference, (Richard J, Lewis, SR.), fourth edition (4) Cooper’s TOXIC EXPOSURE, Desk reference, 1997 (5) ERICard Methanol (ERIC 3-15)

(d) List of risk phrases (R) and safety phrases (S) : R11 - Highly flammable. R23/24/25 - Toxic by inhalation, in contact with skin and if swallowed. R39/23/24/25 - Toxic : danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed. R20/21/22 - Harmful by inhalation, in contact with skin and if swallowed. R68/20/21/22 - Harmful : possible risk of irreversible effects through inhalation, in contact with skin and if swallowed. S1/2 - Keep locked up and out of the reach of children. S7 - Keep container tightly closed. S16 - Keep away from sources of ignition - No smoking. S36/37 - Wear suitable protective clothing and gloves. S45 - In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible).

In ANNEX: Exposure Scenario (ES) corresponding to the identified uses ( totally 15 ES)

Closing Safety Data Sheet

fds methanol eng vers.3.0

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