METHYL FORMATE

Methyl formate is used as a fumigant and larvicide for tobacco and food crops. As a fumigant, it is sometimes formulated with carbon dioxide or mixed with ethyl formate (Clayton & Clayton, 1994; HSDB , 1996).
It is used in organic synthesis, especially in the preparation of antileukemic agents (Clayton & Clayton, 1994).
It is used as a cellulose acetate solvent, and is often mixed with other esters such as ethyl formate, methyl acetate, and ethyl acetate to be used as a general industrial solvent (Lewis, 1993; HSDB , 1996).
Miscellaneous uses include its use as a poisonous gas in military operations, a high-boiling-point refrigerant for house appliances, and a food additive (HSDB , 1996; Clayton & Clayton, 1994).

-CLINICAL EFFECTS

GENERAL CLINICAL EFFECTS

Methyl formate may be hazardous from inhalation, ingestion, and skin or eye exposure. It can be absorbed following inhalation, ingestion, or dermal exposure. Methyl formate is irritating to the eyes, skin, and mucous membranes.

Exposure to the vapor may cause eye and respiratory tract irritation, optic neuritis, visual disturbances (amblyopia and nystagmus), temporary blindness in one case, retching, narcosis, and death from pulmonary irritation. Workers exposed to solvents containing 30% methyl formate reported euphoria and depression.

One 19-month-old child who died after the liquid was applied under a bath cap for treatment of pediculosis capitis. On autopsy, methanol and methyl formate were found in the brain and other organs.

Effects reported in experimental animals include hyperemia of the kidneys, adrenals, liver, and meninges; pulmonary edema; CNS depression; seizures; coma; and death.

POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

May cause toxic effects if inhaled or absorbed through skin.
Inhalation or contact with material may irritate or burn skin and eyes.
Fire will produce irritating, corrosive and/or toxic gases.
Vapors may cause dizziness or suffocation.
Runoff from fire control or dilution water may cause pollution.

-MEDICAL TREATMENT

LIFE SUPPORT

Support respiratory and cardiovascular function.

SUMMARY

FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

Move victim to fresh air.
Call 911 or emergency medical service.
Give artificial respiration if victim is not breathing.
Administer oxygen if breathing is difficult.
Remove and isolate contaminated clothing and shoes.
In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes.
Wash skin with soap and water.
Keep victim warm and quiet.
In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin.
Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed.
Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.

FIRST AID

FIRST AID

EYE EXPOSURE - Immediately wash the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately. Contact lenses should not be worn when working with this chemical.
DERMAL EXPOSURE - Immediately wash the contaminated skin with soap and water. If this chemical penetrates the clothing, immediately remove the clothing, wash the skin with soap and water, and get medical attention promptly.
INHALATION EXPOSURE - Move the exposed person to fresh air at once. If breathing has stopped, perform artificial respiration. Keep the affected person warm and at rest. Get medical attention as soon as possible.
INGESTION EXPOSURE - If this chemical has been swallowed, get medical attention immediately.
TARGET ORGANS - Eyes, respiratory system, and central nervous system (National Institute for Occupational Safety and Health, 2007).

GENERAL -

Move victims of inhalation exposure from the toxic environment and administer 100% humidified supplemental oxygen with assisted ventilation as required. Exposed skin and eyes should be copiously flushed with water. Because of the potential for rapid onset of CNS depression or seizures with possible aspiration of gastric contents, EMESIS SHOULD NOT BE INDUCED. Cautious gastric lavage followed by administration of activated charcoal may be of benefit if the patient is seen soon after the exposure.

INHALATION EXPOSURE -

INHALATION: Move patient to fresh air. Monitor for respiratory distress. If cough or difficulty breathing develops, evaluate for respiratory tract irritation, bronchitis, or pneumonitis. Administer oxygen and assist ventilation as required. Treat bronchospasm with an inhaled beta2-adrenergic agonist. Consider systemic corticosteroids in patients with significant bronchospasm.
If bronchospasm and wheezing occur, consider treatment with inhaled sympathomimetic agents.
ACUTE LUNG INJURY: Maintain ventilation and oxygenation and evaluate with frequent arterial blood gases and/or pulse oximetry monitoring. Early use of PEEP and mechanical ventilation may be needed.
SEIZURES: Administer a benzodiazepine; DIAZEPAM (ADULT: 5 to 10 mg IV initially; repeat every 5 to 20 minutes as needed. CHILD: 0.1 to 0.5 mg/kg IV over 2 to 5 minutes; up to a maximum of 10 mg/dose. May repeat dose every 5 to 10 minutes as needed) or LORAZEPAM (ADULT: 2 to 4 mg IV initially; repeat every 5 to 10 minutes as needed, if seizures persist. CHILD: 0.05 to 0.1 mg/kg IV over 2 to 5 minutes, up to a maximum of 4 mg/dose; may repeat in 5 to 15 minutes as needed, if seizures continue).

Consider phenobarbital or propofol if seizures recur after diazepam 30 mg (adults) or 10 mg (children greater than 5 years).
Monitor for hypotension, dysrhythmias, respiratory depression, and need for endotracheal intubation. Evaluate for hypoglycemia, electrolyte disturbances, and hypoxia.

DERMAL EXPOSURE -

DECONTAMINATION: Remove contaminated clothing and jewelry and place them in plastic bags. Wash exposed areas with soap and water for 10 to 15 minutes with gentle sponging to avoid skin breakdown. A physician may need to examine the area if irritation or pain persists (Burgess et al, 1999).
Treat dermal irritation or burns with standard topical therapy. Patients developing dermal hypersensitivity reactions may require treatment with systemic or topical corticosteroids or antihistamines.

EYE EXPOSURE -

DECONTAMINATION: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, the patient should be seen in a healthcare facility.

INGESTION EXPOSURE -

Because of the potential for CNS depression or gastrointestinal tract irritation, do NOT induce emesis.
Significant esophageal or gastrointestinal tract irritation or burns may occur following ingestion. The possible benefit of early removal of some ingested material by cautious gastric lavage must be weighed against potential complications of bleeding or perforation.
GASTRIC LAVAGE: Consider after ingestion of a potentially life-threatening amount of poison if it can be performed soon after ingestion (generally within 1 hour). Protect airway by placement in the head down left lateral decubitus position or by endotracheal intubation. Control any seizures first.

CONTRAINDICATIONS: Loss of airway protective reflexes or decreased level of consciousness in unintubated patients; following ingestion of corrosives; hydrocarbons (high aspiration potential); patients at risk of hemorrhage or gastrointestinal perforation; and trivial or non-toxic ingestion.

ACTIVATED CHARCOAL: Administer charcoal as a slurry (240 mL water/30 g charcoal). Usual dose: 25 to 100 g in adults/adolescents, 25 to 50 g in children (1 to 12 years), and 1 g/kg in infants less than 1 year old.
SEIZURES: Administer a benzodiazepine; DIAZEPAM (ADULT: 5 to 10 mg IV initially; repeat every 5 to 20 minutes as needed. CHILD: 0.1 to 0.5 mg/kg IV over 2 to 5 minutes; up to a maximum of 10 mg/dose. May repeat dose every 5 to 10 minutes as needed) or LORAZEPAM (ADULT: 2 to 4 mg IV initially; repeat every 5 to 10 minutes as needed, if seizures persist. CHILD: 0.05 to 0.1 mg/kg IV over 2 to 5 minutes, up to a maximum of 4 mg/dose; may repeat in 5 to 15 minutes as needed, if seizures continue).

Consider phenobarbital or propofol if seizures recur after diazepam 30 mg (adults) or 10 mg (children greater than 5 years).
Monitor for hypotension, dysrhythmias, respiratory depression, and need for endotracheal intubation. Evaluate for hypoglycemia, electrolyte disturbances, and hypoxia.

Observe patients with ingestion carefully for the possible development of esophageal or gastrointestinal tract irritation or burns. If signs or symptoms of esophageal irritation or burns are present, consider endoscopy to determine the extent of injury.

-RANGE OF TOXICITY

MINIMUM LETHAL EXPOSURE

ACUTE

Clayton & Clayton (1994) reports the oral LDLo for humans as 0.5 g/kg methyl formate.
Fatalities in industrial exposures have occurred only at high concentrations (Lewis, 1992).

CASE REPORTS

A 19-month-old child died within 20 to 30 minutes of exposure to 1 ounce of methyl formate applied to the scalp (Clayton & Clayton, 1994).

ANIMAL DATA

Cats exposed to approximately 10,000 ppm (1.02%) methyl formate for 2 to 3 hours died from pulmonary edema (ACGIH, 1991).
Guinea pigs died after inhaling 25,000 ppm methyl formate (ACGIH, 1991).

MAXIMUM TOLERATED EXPOSURE

GENERAL/SUMMARY

Humans exposed to 1500 ppm methyl formate for 1 minute experienced no effects (Hathaway, 1991).

ANIMAL DATA

Exposure to 1500 to 2000 ppm methyl formate in guinea pigs was the highest concentration not causing serious disturbances after several hours (ACGIH, 1991).

Carcinogenicity Ratings for CAS107-31-3 :

ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: Methyl formate
ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: Methyl formate
EPA (U.S. Environmental Protection Agency, 2011): Not Listed
IARC (International Agency for Research on Cancer (IARC), 2016; International Agency for Research on Cancer, 2015; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010a; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2008; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2007; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2006; IARC, 2004): Not Listed
NIOSH (National Institute for Occupational Safety and Health, 2007): Not Listed ; Listed as: Methyl formate
MAK (DFG, 2002): Not Listed
NTP (U.S. Department of Health and Human Services, Public Health Service, National Toxicology Project ): Not Listed

TOXICITY AND RISK ASSESSMENT VALUES

EPA IRIS

EPA Risk Assessment Values for CAS107-31-3 (U.S. Environmental Protection Agency, 2011):

Not Listed

TOXICITY VALUES

References: RTECS, 1996 Clayton & Clayton, 1994 Lewis, 1992 ACGIH, 1991
- LCLo- (INHALATION)GUINEA_PIG:
- LD50- (ORAL)RABBIT:
- LDLo- (ORAL)HUMAN:

CALCULATIONS

AMBIENT CONVERSIONS

CONVERSION FACTORS

1 ppm = 2.50 mg/m(3)

Conversion factor at 68 degrees F and 760 mmHg (NIOSH , 1996) -

-STANDARDS AND LABELS

WORKPLACE STANDARDS

ACGIH TLV Values for CAS107-31-3 (American Conference of Governmental Industrial Hygienists, 2010):

Editor's Note: The listed values are recommendations or guidelines developed by ACGIH(R) to assist in the control of health hazards. They should only be used, interpreted and applied by individuals trained in industrial hygiene. Before applying these values, it is imperative to read the introduction to each section in the current TLVs(R) and BEI(R) Book and become familiar with the constraints and limitations to their use. Always consult the Documentation of the TLVs(R) and BEIs(R) before applying these recommendations and guidelines.

Adopted Value

Methyl formate

TLV:

TLV-TWA: 100 ppm
TLV-STEL: 150 ppm
TLV-Ceiling:

Notations and Endnotes:

Carcinogenicity Category: Not Listed
Codes: Not Listed
Definitions: Not Listed

TLV Basis - Critical Effect(s): URT, LRT, and eye irr
Molecular Weight: 65.05

For gases and vapors, to convert the TLV from ppm to mg/m(3):

[(TLV in ppm)(gram molecular weight of substance)]/24.45

For gases and vapors, to convert the TLV from mg/m(3) to ppm:

[(TLV in mg/m(3))(24.45)]/gram molecular weight of substance

Under Study

Methyl formate

TLV:

TLV-TWA:
TLV-STEL:
TLV-Ceiling:

Notations and Endnotes:

Carcinogenicity Category: Not Listed
Codes: Not Listed
Definitions: Not Listed

TLV Basis - Critical Effect(s):
Molecular Weight:

For gases and vapors, to convert the TLV from ppm to mg/m(3):

[(TLV in ppm)(gram molecular weight of substance)]/24.45

For gases and vapors, to convert the TLV from mg/m(3) to ppm:

[(TLV in mg/m(3))(24.45)]/gram molecular weight of substance

AIHA WEEL Values for CAS107-31-3 (AIHA, 2006):

Not Listed

NIOSH REL and IDLH Values for CAS107-31-3 (National Institute for Occupational Safety and Health, 2007):

Listed as: Methyl formate
REL:

TWA: 100 ppm (250 mg/m(3))
STEL: 150 ppm (375 mg/m(3))
Ceiling:
Carcinogen Listing: (Not Listed) Not Listed
Skin Designation: Not Listed
Note(s):

IDLH:

IDLH: 4500 ppm
Note(s): Not Listed

OSHA PEL Values for CAS107-31-3 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):

Listed as: Methyl formate
Table Z-1 for Methyl formate:

8-hour TWA:

ppm: 100

Parts of vapor or gas per million parts of contaminated air by volume at 25 degrees C and 760 torr.

mg/m3: 250

Milligrams of substances per cubic meter of air. When entry is in this column only, the value is exact; when listed with a ppm entry, it is approximate.

Ceiling Value:
Skin Designation: No
Notation(s): Not Listed

OSHA List of Highly Hazardous Chemicals, Toxics, and Reactives for CAS107-31-3 (U.S. Occupational Safety and Health Administration, 2010):

Not Listed

ENVIRONMENTAL STANDARDS

EPA CERCLA, Hazardous Substances and Reportable Quantities for CAS107-31-3 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA CERCLA, Hazardous Substances and Reportable Quantities, Radionuclides for CAS107-31-3 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA RCRA Hazardous Waste Number for CAS107-31-3 (U.S. Environmental Protection Agency, 2010b):

Not Listed
Editor's Note: The D, F, and K series waste numbers and Appendix VIII to Part 261 -- Hazardous Constituents were not included. Please refer to 40 CFR Part 261.

EPA SARA Title III, Extremely Hazardous Substance List for CAS107-31-3 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA SARA Title III, Community Right-to-Know for CAS107-31-3 (40 CFR 372.65, 2006; 40 CFR 372.28, 2006):

Not Listed

DOT List of Marine Pollutants for CAS107-31-3 (49 CFR 172.101 - App. B, 2005):

Not Listed

EPA TSCA Inventory for CAS107-31-3 (EPA, 2005):

Listed as: Formic acid, methyl ester

SHIPPING REGULATIONS

SURFACE

DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 1243 (49 CFR 172.101, 2005):

Hazardous materials descriptions and proper shipping name: Methyl formate

Symbol(s): Not Listed
Hazard class or Division: 3

3: Flammable and combustible liquid. See 49 CFR section 173.120 for definitions.

Identification Number: UN1243
Packing Group: I

I: Packing Group I - indicates the degree of danger presented by the material is great.

Label(s) required (if not excepted): 3

3: Flammable Liquid.

Special Provisions: T11, TP2

T11: Minimum test pressure (bar): 6; Minimum shell thickness (in mm-reference steel) (See sxn.178.274(d)): sxn.178.274(d)(2); Pressure-relief requirements (See sxn.178.275(g)): Normal; Bottom opening requirements (See sxn.178.275(d)): sxn.178.275(d)(3).
TP2: a. The maximum degree of filling must not exceed the degree of filling determined by the following: [Degree of filling = 95/1+alpha(tr - tf)], where tr is the maximum mean bulk temperature during transport, tf is the temperature in degrees celsius of the liquid during filling, and alpha is the mean coefficient of cubical expansion of the liquid between the mean temperature of the liquid during filling (tf) and the maximum mean bulk temperature during transportation (tr) both in degrees celsius; and b. For liquids transported under ambient conditions a may be calculated using the formula: [alpha = (d15-d50)/(35 x d50)], where d15 and d50 are the densities (in units of mass per unit volume) of the liquid at 15 degrees C (59 degrees F) and 50 degrees C (122 degrees F), respectively.

Packaging Authorizations (refer to 49 CFR 173.***):

Exceptions: 150
Non-bulk packaging: 201
Bulk packaging: 243

Quantity Limitations:

Passenger aircraft or railcar: 1 L
Cargo aircraft only: 30 L

Vessel Stowage Requirements:

Vessel stowage location: E

E: The material may be stowed "on deck" or "under deck" on a cargo vessel and on a passenger vessel carrying a number of passengers limited to not more than the larger of 25 passengers, or one passenger per each 3 m of overall vessel length, but is prohibited from carriage on passenger vessels in which the limiting number of passengers is exceeded.

Vessel stowage other: Not Listed

ICAO International Shipping Name for UN1243 (ICAO, 2002):

Proper Shipping Name: Methyl formate
UN Number: 1243

LABELS

NFPA

NFPA Hazard Ratings for CAS107-31-3 (NFPA, 2002):

Listed as: Methyl Formate
Hazard Ratings:

Health Rating (Blue): 2

(2) Moderately toxic material. Intense or continued exposure could cause temporary incapacitation or possible residual injury unless prompt medical treatment is given.

Flammability Rating (Red): 4

(4) Extremely flammable. Materials which will rapidly vaporize at normal pressure and temperature and will burn readily. Including: gases, cryogenic materials, any liquid or gaseous material having a flash point below 73 degrees F and a boiling point below 100 degrees F, and materials which can form explosive mixtures with air.

Instability Rating (Yellow): 0

(0) Materials which are normally stable, even under fire conditions, and which are not reactive with water.

Oxidizer/Water-Reactive Designation: Not Listed

-HANDLING AND STORAGE

STORAGE

CONTAINER

Methyl formate is normally shipped in bottles packed in insulating material, metal cans, pails, or drums. It may also be transported in tanks on trucks, rail cars, or barges (NFPA, 1994).
Containers should be kept closed and protected from physical damage (ITI, 1988).

ROOM/CABINET RECOMMENDATIONS

Methyl formate should be stored in a cool, dry, well-ventilated location, preferably outside or in a detached structure (NFPA, 1994).

INCOMPATIBILITIES

Store separately from alkalies, oxidizing materials, and moisture (NFPA, 1994).

-PERSONAL PROTECTION

SUMMARY

RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

Wear positive pressure self-contained breathing apparatus (SCBA).
Structural firefighters' protective clothing will only provide limited protection.

Personnel should keep upwind and avoid breathing methyl formate vapors. All bodily contact with methyl formate should be avoided by wearing full protective clothing, including goggles or safety glasses, rubber gloves, and positive pressure self-contained breathing apparatus. Broken packages should not be handled unless wearing appropriate protective clothing, and any methyl formate which comes in contact with the body should be flushed away with copious amounts of water (AAR, 1994; NFPA, 1994; (CHRIS , 1996).

RESPIRATORY PROTECTION

Refer to "Recommendations for respirator selection" in the NIOSH Pocket Guide to Chemical Hazards on TOMES Plus(R) for respirator information.

PROTECTIVE CLOTHING

CHEMICAL PROTECTIVE CLOTHING. Search results for CAS 107-31-3.

All data are compiled from published sources and are NOT recommended specifically by Truven Health Analytics. The appearance of specific manufacturers or products in this section does not represent an endorsement by Truven Health Analytics. No attempt has been made to verify the data presented. All product recommendations should be confirmed with the specific manufacturer for verification of product performance.
CLOTHING

Microporous Fabric

Workrite

CSP Garments

Degradation Rating: PASS
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (Workrite, 1997)

Neoprene

River City

Neoprene splash suits

Degradation Rating: Not Recommended
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (River City, 1995)

Neoprene+Latex

Neese Industries, Inc.

Neoprene splash suits

Degradation Rating: Excellent
Breakthrough Time (minutes): Not reported
Permeation Rate (mcg/cm2/min): Not reported
Notes: Not Listed
Citation: (Neese Industries, Inc., 2003)

Plastic Laminate

DuPont Personal Protection

Reflector

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None detected
Notes: Not Listed
Citation: (DuPont, 2002)

Polyurethane

Neese Industries, Inc.

Polyurethane splash suits

Degradation Rating: Good
Breakthrough Time (minutes): Not reported
Permeation Rate (mcg/cm2/min): Not reported
Notes: Not Listed
Citation: (Neese Industries, Inc., 2003)

Polyvinyl Chloride

Neese Industries, Inc.

PVC splash suits

Degradation Rating: Good
Breakthrough Time (minutes): Not reported
Permeation Rate (mcg/cm2/min): Not reported
Notes: Not Listed
Citation: (Neese Industries, Inc., 2003)

FOOTWEAR

Specific recommendations and test data for this product type were not found in the available manufacturers' product literature.

GLOVES

Natural Rubber

Boss Manufacturing Company

Not specified

Degradation Rating: Poor
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (Boss Manufacturing Company, 1998)

Neoprene

Boss Manufacturing Company

Not specified

Degradation Rating: Not Recommended
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (Boss Manufacturing Company, 1998)

Wells Lamont Industrial

Not specified

Degradation Rating: Excellent
Breakthrough Time (minutes): No Breakthrough Time provided
Permeation Rate (mcg/cm2/min): No Permeation Rate provided
Notes: Not Listed
Citation: (Wells Lamont Industrial, 2002)

Nitrile

Boss Manufacturing Company

Not specified

Degradation Rating: Poor
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (Boss Manufacturing Company, 1998)

Wells Lamont Industrial

Not specified

Degradation Rating: Fair
Breakthrough Time (minutes): No Breakthrough Time provided
Permeation Rate (mcg/cm2/min): No Permeation Rate provided
Notes: Not Listed
Citation: (Wells Lamont Industrial, 2002)

Polyvinyl Chloride

Wells Lamont Industrial

Not specified

Degradation Rating: Fair
Breakthrough Time (minutes): No Breakthrough Time provided
Permeation Rate (mcg/cm2/min): No Permeation Rate provided
Notes: Not Listed
Citation: (Wells Lamont Industrial, 2002)

GENERAL INFORMATION

This section provides a compilation of chemical resistance information and test data for specific protective clothing products. Chemical resistance information includes both degradation resistance ratings and permeation resistance data. This information is designed to assist in the selection of appropriate protective clothing. Only data on specific products and manufacturers are included. Generic information or recommendations are not provided since significant differences can exist in the chemical resistance for apparent similar product types.
Specific product information is organized by general product type (gloves, garments, and footwear), material type, and manufacturer. The category 'garments' may include totally encapsulating suits, splash suits, as well as other items (e.g., coveralls, jackets, and aprons). Specific manufacturers should be contacted to determine the features of available styles/models.
In addition to chemical resistance information, there are many critical variables in the selection of protective clothing which cannot be represented in this summary of the literature. Some factors to be considered in choosing protective clothing include, but are not limited to: overall clothing integrity, physical hazard resistance, durability, human factors, ease of decontamination, and cost. Overall clothing integrity refers to a specific design's ability to offer consistent protection for all clothing-covered areas of the body. Physical hazards include resisting the effects of abrasion, cuts, tears, and punctures. Human factors entail effects on wearer mobility, visibility, and hearing for garments; dexterity, tactility, and grip for gloves; ankle support and weight for footwear; and, any effect of the clothing on the function of the wearer. There are several variations in the design for gloves, garments, and footwear that affect these factors. Protective clothing must properly be sized and correctly fit the wearer to ensure its proper use and function.
As required in the U.S.A., protective clothing should be selected based on a risk assessment of the workplace. This risk assessment must account for the identification of existing as well as potential hazards and involve the recommendation of protective clothing appropriate for the identified hazards. Therefore, the recommendations in this section should not be used as the sole basis for decisions on choice of protective clothing, but rather should be used as a tool by qualified occupational health and safety professionals or other technically qualified persons in conjunction with a review of all mitigating factors. Consult the OSHA PPE Standard (29 CFR 1910.132 - 1910.138) for regulations and additional guidance regarding the selection and use of protective clothing and equipment. For general information on protective clothing selection, refer to the "PERSONAL PROTECTIVE EQUIPMENT - OSHA PUB 3077" document.
PROTECTIVE CLOTHING SELECTION

Determine the type of protective clothing item needed based on a risk assessment (e.g., gloves, garments, footwear).
For high risk situations, choose clothing that covers all parts of the body that may be exposed. In many cases, multiple clothing items will be required. Low risk situations may permit partial body protective clothing. Select protective clothing products that have reported chemical resistance data. High risk situations involving full body clothing or extended chemical contact often require permeation resistance data to determine the barrier effectiveness of materials used in the construction of clothing. Relatively low risk situations, where only splash or incidental exposure occur, may allow use of protective clothing based on degradation or penetration resistance data. Specifics on the interpretation of chemical resistance data are presented below.
Other factors must be considered in addition to chemical resistance. The selected chemical protective clothing item should offer the optimal combination of protection against identified hazards while allowing maximum function and comfort.

INTERPRETATION OF DEGRADATION RATINGS

Degradation refers to physical changes in a material as the result of chemical exposure. Degradation may become evident in visible changes, such as discoloration, swelling, delamination, deterioration, or disintegration. Degradation effects may also be measured by weight change or other changes in a material's physical properties (e.g., strength, elasticity, hardness).
Degradation resistance ratings are provided by manufacturers to rate the amount of degradation that occurs for a particular protective clothing material when contacted by a chemical. All degradation ratings are qualitative and include ratings, such as "EXCELLENT," "GOOD," "FAIR," "POOR," and "NOT RECOMMENDED." There is no standard test method for the measurement of chemical degradation resistance; therefore, manufacturer ratings may be based on different testing approaches. This makes comparison of degradation ratings between manufacturers unreliable.
The use of degradation resistance ratings alone to recommend protective clothing, particularly for high hazard situations, should be avoided. Degradation resistance testing does not directly assess the barrier quality of protective clothing, since materials can show relatively little degradation but still allow either permeation or penetration by a chemical. Degradation resistance ratings can be used to exclude protective clothing materials from consideration. Protective clothing materials with a "NOT RECOMMENDED" degradation resistance rating should never be used.
For some products, the rating "NO PENETRATION" is provided. This refers to penetration resistance test results that are based on a different procedure (American Society for Testing and Materials (ASTM) Standard Test Method F 903). Penetration resistance testing involves placing a material sample in a test cell, exposing the exterior side of the material to a chemical, and then observing the interior side of the material for visible signs of liquid penetration. Part of the test is conducted at an elevated pressure. Test results are reported as pass (no penetration) or fail (penetration detected). Unlike degradation testing, penetration testing provides an assessment of protective clothing material barrier performance. Since penetration resistance testing examines only observable amounts of liquid penetration, permeation may still occur. The use of penetration resistance data must be restricted to liquid chemicals, and should be limited to scenarios where there is no reasonable vapor exposure hazard under the conditions of exposure.

INTERPRETATION OF PERMEATION DATA

Permeation is the process of chemical movement through a material on a molecular level. Permeation resistance refers to the ability of a material to retard or prevent chemical movement through it. Permeation may occur without any visible signs of degradation.
Permeation resistance is measured using a test cell which is divided into two halves by a protective clothing specimen. Chemical is placed on the challenge side, while the collection side is periodically monitored for permeating chemical. Permeation data were obtained in accordance with the American Society for Testing and Materials (ASTM) Standard Test Method F 739 (Resistance of Materials Used in Protective Clothing to Permeation by Liquids and Gases), unless stated otherwise. In the case of chemicals that are classified as warfare agents, the data were obtained in accordance with the Military Standard 282 (MIL-STD-282) (Military Standard, Filter Units, Protective Clothing, Gas-Mask Components, and Related Products: Performance Test Methods).
Permeation rate is the amount of chemical that passes through a material for a measured surface area per unit time. In this section, permeation rate is expressed in micrograms per square centimeter per minute (mcg/cm(2)/min). The reported permeation rate is either the steady-state rate or the maximum rate observed during testing. In some cases, very large permeation rates exceed measurement techniques and are reported as ">" (greater than) or "HIGH."
Breakthrough time is the elapsed time, in minutes, from the time the chemical comes in contact with the material exterior surface, to the time that chemical is detected on the interior surface. When no breakthrough is detected, the breakthrough time is report as ">" the testing period. If permeation breakthrough is rapid, results are reported as "<" (less than) the earlier sampling time or as "IMMEDIATELY" (which usually means breakthrough in less than 4 minutes).
The breakthrough time should exceed the expected use period of the selected protective clothing. Additionally, there are several other factors that must be taken into account to provide appropriate protection.
Permeation testing is usually conducted with full strength, undiluted chemical for the duration of the test period. Actual exposures may involve diluted chemical for short or intermittent exposure periods.
Permeation testing is usually conducted at room temperature. Permeation occurs faster at elevated temperatures (short breakthrough times and higher permeation rates) and slower at reduced temperatures (long breakthrough times and lower permeation rates).
Permeation resistance of mixtures cannot usually be determined on the basis of the individual chemicals making up the mixture. Synergistic effects may occur and result in more rapid permeation than accounted for by the individual mixture chemicals.
Permeation rates may be used to calculate potential wearer exposure; however, several assumptions must be made about the extent of exposure and condition of clothing wear. Furthermore, there are few chemicals with dermal exposure limits, making it difficult to determine an acceptable skin exposure level.

COMPANY INFORMATION

Boss Manufacturing Company 221 W. First Street Kewanee, IL 61443 USA Phone: (309) 852-2131 Fax: (309) 852-0848 Toll-Free: (800) 447-4581 Website: http://www.bossgloves.com Email: custserv@bossgloves.com
DuPont Personal Protection P. O. Box 80705 Wilmington, DE 19880-0705 USA Phone: (302) 774-1000 Toll-Free: (800) 931-3456 Website: http://personalprotection.dupont.com Email: personalprotection@usa.dupont.com
Neese Industries, Inc. 10646 Airline Hwy Gonzales, LA 70737 USA Phone: (225) 647-6553 Fax: (225) 644-3517 Toll-Free: (800) 535-8042 Website: http://www.neeseind.com Email: customerservice@neeseind.com
River City 5321 East Shelby Dr. Memphis, TN 38188 USA Phone: (800) 888-0347 Fax: (901) 795-3815 Toll-Free: (800) 888-0347 Website: http://www.protectivewear.com Email: support@protectivewear.com
Wells Lamont Industrial 6640 W. Touhy Ave. Niles, IL 60714 USA Fax: (847) 647-6943 Toll-Free: (800) 247-3295 Website: http://www.wellslamontindustry.com Email: kmeger@wellslamont.com
Workrite 500 East Third Street Box 1192 Oxnard, CA 93032 USA Phone: (805) 483-0715 Fax: (805) 483-0678 Toll-Free: (800) 521-1888 Website: http://www.workrite.com Email: info@workrite.com

REFERENCES

CHEMICAL PROTECTIVE CLOTHING CITATIONS

The following sources were consulted for chemical protective clothing data:

(Ansell-Edmont, 2001)
(Bata Shoe Company, 1995)
(Best Manufacturing, 2002)
(Best Manufacturing, 2004)
(Boss Manufacturing Company, 1998)
(ChemFab Corporation, 1993)
(Comasec Safety, Inc., 2003)
(Comasec Safety, Inc., 2003a)
(DuPont, 2002)
(DuPont, 2002)
(DuPont, 2003)
(Guardian Manufacturing Group, 2001)
(ILC Dover, Inc., 1998)
(Kappler Inc., 2001)
(Kimberly-Clark, 2002)
(LaCrosse-Rainfair, 1997)
(MAPA Professional, 2003)
(MAPA Professional, 2004)
(Mar-Mac Manufacturing, Inc, 1995)
(Marigold Industrial, 2003)
(Memphis Glove Company, 2001)
(Montgomery Safety Products, 1995)
(Nat-Wear, 2001)
(Neese Industries, Inc., 2003)
(North, 2002)
(North, 2002)
(Playtex, 1995)
(River City, 1995)
(Safety 4, 2002)
(Servus, 1995)
(Standard Safety Equipment, 1995)
(Tingley, 2002)
(Trelleborg-Viking, Inc., 2001)
(Trelleborg-Viking, Inc., 2002)
(Wells Lamont Industrial, 2002)
(Workrite, 1997)

-PHYSICAL HAZARDS

FIRE HAZARD

SUMMARY

POTENTIAL FIRE OR EXPLOSION HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)
- HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames.
- Vapors may form explosive mixtures with air.
- Vapors may travel to source of ignition and flash back.
- Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks).
- Vapor explosion hazard indoors, outdoors or in sewers.
- Those substances designated with a "P" may polymerize explosively when heated or involved in a fire.
- Runoff to sewer may create fire or explosion hazard.
- Containers may explode when heated.
- Many liquids are lighter than water.
Methyl formate is a very dangerous fire hazard in the presence of heat or flame (Lewis, 1996).
It is a flammable liquid with vapors which are heavier than air. The vapors may travel to an ignition source and flash back (NFPA, 1994).

FLAMMABILITY CLASSIFICATION

NFPA Flammability Rating for CAS107-31-3 (NFPA, 2002):

Listed as: Methyl Formate
Flammability Rating: 4

(4) Extremely flammable. Materials which will rapidly vaporize at normal pressure and temperature and will burn readily. Including: gases, cryogenic materials, any liquid or gaseous material having a flash point below 73 degrees F and a boiling point below 100 degrees F, and materials which can form explosive mixtures with air.

FIRE CONTROL/EXTINGUISHING AGENTS

FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

CAUTION: All these products have a very low flash point: Use of water spray when fighting fire may be inefficient.

SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

Dry chemical, CO2, water spray or alcohol-resistant foam.
Do not use dry chemical extinguishers to control fires involving nitromethane or nitroethane.

LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

Water spray, fog or alcohol-resistant foam.
Do not use straight streams.
Move containers from fire area if you can do it without risk.

TANK OR CAR/TRAILER LOAD FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

Fight fire from maximum distance or use unmanned hose holders or monitor nozzles.
Cool containers with flooding quantities of water until well after fire is out.
Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank.
ALWAYS stay away from tanks engulfed in fire.
For massive fire, use unmanned hose holders or monitor nozzles; if this is impossible, withdraw from area and let fire burn.

NFPA Extinguishing Methods for CAS107-31-3 (NFPA, 2002):

Listed as: Methyl Formate
Extinguishing Method(s): 1, 5

1: "Water may be ineffective" applies to a situation where materials with a flash point below 100 degrees F (37.8 degrees C) are burning. Water will only be effective if used by experienced fire fighters under favorable conditions. Even though water may not put the fire out, it can be used to protect equipment and structures.
5: Flammable liquid fires can be extinguished using carbon dioxide, dry chemical, foam, and vaporizing liquid extinguishers, as long as the fires are small to moderate in size and the flammable liquid reservoir is shallow. Use of foam to form a blanket over a flammable liquid is not effective when the liquid is water-soluble. Certain alcohol resistant foams are effective extinguishing agents for polar, non-polar, and water-soluble liquid fires. These foams are preferred for fighting flammable liquid fires except those that involve water reactive flammable liquids.

Extinguish methyl formate fires with dry chemical, carbon dioxide, or alcohol foam. Fires should only be extinguished if the flow of methyl formate can be stopped or safely confined (AAR, 1994).

Water may be ineffective in fighting fires involving methyl formate, and should not be used on the material itself. Water spray should be used to cool containers exposed to fire, and should be applied from as far away as possible (AAR, 1994; NFPA, 1994).

COMBUSTION TOXICITY

Acrid smoke and irritating fumes are produced when methyl formate is heated to decomposition (Lewis, 1992).

EXPLOSION HAZARD

Methyl formate vapors may explode when exposed to heat or flame, especially if ignited in an enclosed area (Lewis, 1992; CHRIS , 1996).

An explosive reaction may occur if methyl formate is exposed to methanol plus sodium methoxide (Lewis, 1992).

Methyl formate containers may explode in a fire (CHRIS , 1996).

DUST/VAPOR HAZARD

Acrid smoke and irritating fumes are produced when methyl formate is heated to decomposition (Lewis, 1992).

REACTIVITY HAZARD

Methyl formate will react vigorously with oxidizing materials (Lewis, 1992).

An explosive reaction may occur if methyl formate is exposed to methanol plus sodium methoxide (Lewis, 1992).

Methyl formate reacts slowly with water, yielding corrosive formic acid and methyl alcohol, another flammable liquid (AAR, 1994).

EVACUATION PROCEDURES

SUMMARY

Editor's Note: This material is not listed in the Table of Initial Isolation and Protective Action Distances.

LARGE SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

Consider initial downwind evacuation for at least 300 meters (1000 feet).

FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions.

PUBLIC SAFETY MEASURES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)

CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number:

MEXICO:

SETIQ:

01-800-00-214-00 in the Mexican Republic;
For calls originating in Mexico City and the Metropolitan Area: 5559-1588;
For calls originating elsewhere, call: 011-52-555-559-1588.

CENACOM:

01-800-00-413-00 in the Mexican Republic;
For calls originating in Mexico City and the Metropolitan Area: 5550-1496, 5550-1552, 5550-1485, or 5550-4885;
For calls originating elsewhere, call: 011-52-555-550-1496, or 011-52-555-550-1552; 011-52-555-550-1485, or 011-52-555-550-4885.

ARGENTINA:

CIQUIME:

0-800-222-2933 in the Republic of Argentina;
For calls originating elsewhere, call: +54-11-4613-1100.

BRAZIL:

PRÓ-QUÍMICA:

0-800-118270 (Toll-free in Brazil);
For calls originating elsewhere, call: +55-11-232-1144 (Collect calls are accepted).

COLUMBIA:

CISPROQUIM:

01-800-091-6012 in Colombia;
For calls originating in Bogotá, Colombia, call: 288-6012;
For calls originating elsewhere, call: 011-57-1-288-6012.

CANADA:

CANUTEC:

613-996-6666 (Collect calls are accepted);
*666 cellular (in Canada only).

UNITED STATES:

CHEMTREC®:

1-800-424-9300 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
703-527-3887 for calls originating elsewhere (Collect calls are accepted).

CHEM-TEL, INC.:

1-800-255-3924 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
813-248-0585 for calls originating elsewhere (Collect calls are accepted).

INFOTRAC:

1-800-535-5053 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
352-323-3500 for calls originating elsewhere (Collect calls are accepted).

3E COMPANY:

1-800-451-8346 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
760-602-8703 for calls originating elsewhere (Collect calls are accepted).

NATIONAL RESPONSE CENTER (NRC):

1-800-424-8802 - (24 hours) (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
202-267-2675 for calls in the District of Columbia.

MILITARY SHIPMENTS:

703-697-0218 - Explosives/ammunition incidents (Collect calls are accepted);
1-800-851-8061 - All other dangerous goods incidents.

NATIONWIDE POISON CONTROL CENTER (United States only):

1-800-222-1222 (Toll-free in the U.S.).

For additional details see the section entitled "WHO TO CALL FOR ASSISTANCE" under the ERG Instructions.
As an immediate precautionary measure, isolate spill or leak area for at least 50 meters (150 feet) in all directions.
Keep unauthorized personnel away.
Stay upwind.
Keep out of low areas.
Ventilate closed spaces before entering.

Consider evacuation of one-third mile radius if fire involving methyl formate becomes uncontrollable or containers are exposed to direct flame (AAR, 1994).

AIHA ERPG Values for CAS107-31-3 (AIHA, 2006):

Not Listed

DOE TEEL Values for CAS107-31-3 (U.S. Department of Energy, Office of Emergency Management, 2010):

Listed as Methyl formate (Formic acid, methyl ester)
TEEL-0 (units = ppm): 100
TEEL-1 (units = ppm): 150
TEEL-2 (units = ppm): 750
TEEL-3 (units = ppm): 4,500
Definitions:

TEEL-0: The threshold concentration below which most people will experience no adverse health effects.
TEEL-1: The airborne concentration (expressed as ppm [parts per million] or mg/m(3) [milligrams per cubic meter]) of a substance above which it is predicted that the general population, including susceptible individuals, could experience notable discomfort, irritation, or certain asymptomatic, nonsensory effects. However, these effects are not disabling and are transient and reversible upon cessation of exposure.
TEEL-2: The airborne concentration (expressed as ppm or mg/m(3)) of a substance above which it is predicted that the general population, including susceptible individuals, could experience irreversible or other serious, long-lasting, adverse health effects or an impaired ability to escape.
TEEL-3: The airborne concentration (expressed as ppm or mg/m(3)) of a substance above which it is predicted that the general population, including susceptible individuals, could experience life-threatening adverse health effects or death.

AEGL Values for CAS107-31-3 (National Research Council, 2010; National Research Council, 2009; National Research Council, 2008; National Research Council, 2007; NRC, 2001; NRC, 2002; NRC, 2003; NRC, 2004; NRC, 2004; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; United States Environmental Protection Agency Office of Pollution Prevention and Toxics, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; 62 FR 58840, 1997; 65 FR 14186, 2000; 65 FR 39264, 2000; 65 FR 77866, 2000; 66 FR 21940, 2001; 67 FR 7164, 2002; 68 FR 42710, 2003; 69 FR 54144, 2004):

Not Listed

NIOSH IDLH Values for CAS107-31-3 (National Institute for Occupational Safety and Health, 2007):

IDLH: 4500 ppm
Note(s): Not Listed

CONTAINMENT/WASTE TREATMENT OPTIONS

SUMMARY

SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)
- ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area).
- All equipment used when handling the product must be grounded.
- Do not touch or walk through spilled material.
- Stop leak if you can do it without risk.
- Prevent entry into waterways, sewers, basements or confined areas.
- A vapor suppressing foam may be used to reduce vapors.
- Absorb or cover with dry earth, sand or other non-combustible material and transfer to containers.
- Use clean non-sparking tools to collect absorbed material.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)
- Wear positive pressure self-contained breathing apparatus (SCBA).
- Structural firefighters' protective clothing will only provide limited protection.
For spills of methyl formate which are not on fire, all sources of ignition should be kept away. Material should be kept out of water sources and sewers, and dikes should be constructed to contain the flow of material. Personnel should attempt to stop the leak if it can be done without undue hazard. Water spray may be effective in dispersing vapors and diluting spills. Runoff should be contained for proper disposal (AAR, 1994; NFPA, 1994).

LARGE LEAK/SPILL

LARGE SPILL PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 129 (ERG, 2004)
- Dike far ahead of liquid spill for later disposal.
- Water spray may reduce vapor; but may not prevent ignition in closed spaces.

WASTE TREATMENT OPTIONS

RECYCLING/RECLAMATION

Large quantities from cleanup operations may be reclaimed (HSDB , 1996).
Waste management activities associated with material disposition are unique to individual situations. Proper waste characterization and decisions regarding waste management should be coordinated with the appropriate local, state, or federal authorities to ensure compliance with all applicable rules and regulations.

PHYSICAL TREATMENT

Small quantities may be absorbed on paper towels and evaporated in a fume hood. The paper towels may then be burned away from other combustibles (HSDB , 1996).
Large quantities may be disposed of by spraying into a suitable incinerator. More effective incineration will take place by mixing with a more flammable solvent (HSDB , 1996; ITI, 1988).

-ENVIRONMENTAL HAZARD MANAGEMENT

POLLUTION HAZARD

There are many sources of methyl formate. It is a component of cigarette smoke and a combustion product of petroleum fuels and organic matter such as wood. It is a photolytic oxidation product of kraft air pollutants, a by-product of the photochemical reaction involving methane and hydroxyl radicals, and it is a waste product of urea-formaldehyde foam manufacturing (Clayton & Clayton, 1994).

It is created by various chemical processes including the production of methanol and formamide. It may also be released to the environment through its use as a fumigant and larvicide (HSDB, 2004).

Methyl formate occurs naturally in tomatoes, apples, and coffee (HSDB, 2004).

ENVIRONMENTAL FATE AND KINETICS

Methyl formate will exist almost entirely in the vapor phase in the atmosphere, based on its vapor pressure of 585.7 mmHg at 25 degrees C. It will react relatively slowly with photochemically produced hydroxyl radicals with a degradation half-life estimated at 74 days (Verschueren, 2001; HSDB, 2004).
Since methyl formate is very soluble in water, wet deposition is likely to be an important removal process (HSDB, 2004).
Direct photolysis of methyl formate did not occur when it was irradiated with ultraviolet light at wavelength greater than 300 nm (HSDB, 2004).

WATER

SURFACE WATER
- For methyl formate released to water, hydrolysis and volatilization are likely to be important fate processes, while aquatic bioconcentration, direct photolysis, and adsorption to sediment are not expected to be as important (HSDB, 2004).
- Although volatilization may be important, it will probably occur slowly due to the Henry's Law Constant of 2.23 x 10(-4) atm-m(3)/mole at 25 degrees C (HSDB, 2004).
- Experimental hydrolysis half-lives for methyl formate in water at 25 degrees C are predicted to be 21.9 days, 2.19 days, 9.1 hours, and 0.91 hours at respective pHs of 6, 7, 8, and 9 (Verschueren, 2001; HSDB, 2004).
- The volatilization half-lives from a model river 1 meter deep and a model pond are estimated to be 5.3 hours and 60 hours, respectively (Verschueren, 2001; HSDB, 2004).

SOIL

TERRESTRIAL
- Relatively rapid hydrolysis of methyl formate in moist soil will be an important fate process, and the rate of hydrolysis will increase in alkaline soils (HSDB, 2004).
- Methyl formate will be expected to leach readily from soils due to its organic carbon partition coefficient (Koc) of 5, but this will be a less important fate process due to concurrent hydrolysis which occurs at a faster rate (HSDB, 2004).
- Methyl formate will evaporate quickly from dry surfaces due to its relatively high vapor pressure of 585.7 mmHg at 25 degrees C (HSDB, 2004).

ABIOTIC DEGRADATION

Methyl formate exists almost entirely in the vapor phase in air, reacting relatively slowly with photochemically produced hydroxyl radicals. Methyl formate is very soluble in water, hence, wet deposition is a likely and important removal process. Hydrolysis and volatilization are important fate processes in water; bioconcentration, direct photolysis, and adsorption to sediment re not expected to be as important. In soil, methyl formate is expected to evaporate or leach, with relatively rapid hydrolysis becoming an important fate process in moist soil. Methyl formate is considered unlikely to bioconcentrate significantly in aquatic organisms (HSDB, 2004).

BIODEGRADATION

There are insufficient data to be able to predict the role of biodegradation of methyl formate in water or soil, but anaerobic biodegradation should be possible (HSDB, 2004).

BIOACCUMULATION

BIOCONCENTRATION FACTOR

The bioconcentration factor for methyl formate is estimated to be 0.6, which suggests it will not bioconcentrate significantly in aquatic organisms (HSDB, 2004).

ENVIRONMENTAL TOXICITY

The effects of low concentrations of methyl formate on aquatic organisms are unknown (CHRIS , 1996).

-PHYSICAL/CHEMICAL PROPERTIES

MOLECULAR WEIGHT

60.06 (Lewis, 1992)

DESCRIPTION/PHYSICAL STATE

Methyl formate is a clear, colorless liquid with an agreeable odor (AAR, 1994).

No information found at the time of this review.

VAPOR PRESSURE

585.7 mmHg (at 25 degrees C) (HSDB , 1996)

476 mmHg (at 20 degrees C) (ACGIH, 1991)

400 mmHg (at 16 degrees C) (Clayton & Clayton, 1994)

SPECIFIC GRAVITY

OTHER TEMPERATURE AND/OR PRESSURE

0.9742 (at 20/4 degrees C) (Clayton & Clayton, 1994)
0.975 (at 20/4 degrees C) (Lewis, 1992)
0.98149 (at 15/4 degrees C) (Lewis, 1992)
0.987 (at 15/15 degrees C) (Budavari, 1989)

FREEZING/MELTING POINT

MELTING POINT

-99 degrees C; -146 degrees F (NFPA, 1994)

BOILING POINT

32 degrees C; 89 degrees F (NFPA, 1994)

FLASH POINT

-19 degrees C; -2 degrees F (NFPA, 1994)

-27 degrees F (AAR, 1994)

AUTOIGNITION TEMPERATURE

456 degrees C; 853 degrees F (NFPA, 1994)

449 degrees C; 840 degrees F (NFPA, 1994)

869 degrees F (Lewis, 1992)

EXPLOSIVE LIMITS

LOWER

4.5% (NFPA, 1994)
5.9% (Lewis, 1992)

UPPER

23% (NFPA, 1994)
20% (Lewis, 1992)

SOLUBILITY

IN WATER

Methyl formate is moderately soluble in water (Lewis, 1992).
It is soluble in about 3.3 parts water or 230,000 mg/L at 25 degrees C (Budavari, 1989; HSDB , 1996).
Its solubility by weight in water is 30% (NIOSH , 1996).

IN ORGANIC SOLVENTS

Methyl formate is soluble in methanol and ether and miscible in alcohol (Lewis, 1992; Lewis, 1993).

HENRY'S CONSTANT

2.23 X 10(-4) atm-m(3)/mol (at 25 degrees C) (experimentally measured) (HSDB , 1996)

SPECTRAL CONSTANTS

693 (Sadtler Research Laboratories Prism Collection) (HSDB , 1996)

7-4 (Organic Electronic Spectral Data) (HSDB , 1996)

MASS

36 (Atlas of Mass Spectral Data) (HSDB , 1996)
9 (National Bureau of Standards EPA-NIH Mass Spectra Data Base) (HSDB , 1996)

OTHER/PHYSICAL

INDEX OF REFRACTION

1.3433 (at 20 degrees C/D) (HSDB , 1996)

-REFERENCES

GENERAL BIBLIOGRAPHY

40 CFR 372.28: Environmental Protection Agency - Toxic Chemical Release Reporting, Community Right-To-Know, Lower thresholds for chemicals of special concern. National Archives and Records Administration (NARA) and the Government Printing Office (GPO). Washington, DC. Final rules current as of Apr 3, 2006.

40 CFR 372.65: Environmental Protection Agency - Toxic Chemical Release Reporting, Community Right-To-Know, Chemicals and Chemical Categories to which this part applies. National Archives and Records Association (NARA) and the Government Printing Office (GPO), Washington, DC. Final rules current as of Apr 3, 2006.

49 CFR 172.101 - App. B: Department of Transportation - Table of Hazardous Materials, Appendix B: List of Marine Pollutants. National Archives and Records Administration (NARA) and the Government Printing Office (GPO), Washington, DC. Final rules current as of Aug 29, 2005.

49 CFR 172.101: Department of Transportation - Table of Hazardous Materials. National Archives and Records Administration (NARA) and the Government Printing Office (GPO), Washington, DC. Final rules current as of Aug 11, 2005.

62 FR 58840: Notice of the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances - Proposed AEGL Values, Environmental Protection Agency, NAC/AEGL Committee. National Archives and Records Administration (NARA) and the Government Publishing Office (GPO), Washington, DC, 1997.

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METHYL FORMATE

Classification | Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents