METHYL MERCAPTAN

Methyl mercaptan is used as an intermediate in the production of pesticides, fungicides, jet fuel and plastics, in the synthesis of methionine, as a catalyst, and as a gas odorant for natural gas, propane, and butane (ACGIH, 1991; (Budavari, 1996; CGA, 1990; Clayton & Clayton, 1994) Hathaway et al, 1996; (Lewis, 1997; Lewis, 1998).

FORMS

Methyl mercaptan is a colorless, flammable gas that liquefies at 6 degrees C; it is shipped as a liquefied gas (98% pure) under its vapor pressure (AAR, 1998; ACGIH, 1991; (Ashford, 1994; Budavari, 1996; CGA, 1990; Clayton & Clayton, 1994) Hathaway et al, 1996; (ILO, 1998; Lewis, 1996; Lewis, 1997; NFPA, 1997) Raffle et al, 1994; (Verschueren, 1983).

SOURCES

Methyl mercaptan is produced from methanol and hydrogen sulfide, from sodium methyl sulfate and potassium hydrosulfide, and from methyl chloride and sodium hydrosulfide. It is also found as an emission from paper and pulp mills. Methyl mercaptan occurs naturally in a wide variety of vegetables (e.g., onions and garlic), in "sour" gas in West Texas oil fields, in coal tar and petroleum distillates, and it is a major contributor to normal human mouth odor (ACGIH, 1991; (Ashford, 1994; Clayton & Clayton, 1994; Lewis, 1997).

-CLINICAL EFFECTS

GENERAL CLINICAL EFFECTS

USES: Methyl mercaptan, also called methanethiol, is a sulfhydryl compound, used as an intermediate in the production of pesticides, fungicides, jet fuel and plastics, in the synthesis of methionine, as a catalyst, and as a gas odorant for natural gas, propane, and butane.

TOXICOLOGY: Methyl mercaptan is a colorless, flammable gas that liquefies at 6 degrees C. It is shipped as a cryogenic liquefied gas (98% pure). Methyl mercaptan causes CNS depression and depresses the respiratory center in a fashion similar to hydrogen sulfide. It appears to have a mechanism of toxicity similar to that of hydrogen sulfide in that it reversibly impairs rat mitochondrial respiration by inhibiting cytochrome C oxidase. One human study has suggested that exposure to methyl mercaptan and inorganic mercaptans may impair heme synthesis by interfering with the activities of enzymes involved in the biosynthetic heme pathway.

EPIDEMIOLOGY: Exposure is rare.

WITH POISONING/EXPOSURE

Lower-level exposure produces eye, skin, and respiratory tract irritation, and signs of CNS depression such as headache, weakness, dizziness, and loss of coordination and judgement. Contact with the liquid or compressed gas may cause frostbite injury. Other symptoms of acute exposure include fever, cough, dyspnea, a feeling of tightness and burning in the chest, nausea, vomiting, diarrhea, tachycardia, hypertension, restlessness, renal dysfunction, proteinuria, and hematuria.
Inhalation of the gas may cause CNS depression, respiratory irritation, respiratory paralysis, pulmonary edema, tremors, and seizures. Pulmonary embolism and pneumonia have rarely been reported in humans. Methemoglobinemia and severe hemolytic anemia with hematuria and proteinuria have been reported in a patient with glucose-6-phosphate dehydrogenase (G-6-PD) deficiency.

POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (ERG, 2004)

TOXIC; Extremely Hazardous.
May be fatal if inhaled or absorbed through skin.
Initial odor may be irritating or foul and may deaden your sense of smell.
Contact with gas or liquefied gas may cause burns, severe injury and/or frostbite.
Fire will produce irritating, corrosive and/or toxic gases.
Runoff from fire control may cause pollution.

ACUTE CLINICAL EFFECTS

SUMMARY

TOXICOLOGY: Methyl mercaptan is a colorless, flammable gas that liquefies at 6 degrees C. It is shipped as a cryogenic liquefied gas (98% pure). Methyl mercaptan causes CNS depression and depresses the respiratory center in a fashion similar to hydrogen sulfide. It appears to have a mechanism of toxicity similar to that of hydrogen sulfide in that it reversibly impairs rat mitochondrial respiration by inhibiting cytochrome C oxidase. One human study has suggested that exposure to methyl mercaptan and inorganic mercaptans may impair heme synthesis by interfering with the activities of enzymes involved in the biosynthetic heme pathway.
EPIDEMIOLOGY: Exposure is rare.
TOXICITY: Lower-level exposure produces eye, skin, and respiratory tract irritation, and signs of CNS depression such as headache, weakness, dizziness, and loss of coordination and judgement. Contact with the liquid or compressed gas may cause frostbite injury. Other symptoms of acute exposure include fever, cough, dyspnea, a feeling of tightness and burning in the chest, nausea, vomiting, diarrhea, tachycardia, hypertension, restlessness, renal dysfunction, proteinuria, and hematuria. Inhalation of the gas may cause CNS depression, respiratory irritation, respiratory paralysis, pulmonary edema, tremors, and seizures. Pulmonary embolism and pneumonia have rarely been reported in humans. Methemoglobinemia and severe hemolytic anemia with hematuria and proteinuria have been reported in a patient with glucose-6-phosphate dehydrogenase (G-6-PD) deficiency.

CARDIOVASCULAR

HYPERTENSION: Elevated blood pressure occurred in a man fatally exposed to methyl mercaptan (Shults et al, 1970).
TACHYCARDIA: Tachycardia was noted in man exposed to an unknown concentration leaking from cylinders (Shults et al, 1970).

DERMAL

Dermatitis has developed in workers exposed to chronic, low level concentrations (Kvartovkina & Meerson, 1974).
Frostbite injury can result from dermal exposure to liquid methyl mercaptan (Chemsoft(R) , 1996; OHM/TADS , 1996).

GASTROINTESTINAL

Nausea and vomiting may occur (Clayton & Clayton, 1994; Pickler, 1918).

GENITOURINARY

Hematuria and proteinuria were seen in one case of methyl mercaptan poisoning with severe hemolytic anemia and methemoglobinemia (Shults et al, 1970).

HEENT

IRRITATION: Methyl mercaptan is an eye and mucous membrane irritant (Clayton & Clayton, 1994).

HEMATOLOGIC

METHEMOGLOBINEMIA: Methemoglobinemia and severe hemolytic anemia, both of brief duration and associated with a deficiency in red blood cell glucose-6-phosphate dehydrogenase (G-6-PD), occurred in a man exposed to an unknown concentration of methyl mercaptan for about an hour (Shults et al, 1970).

MUSCULOSKELETAL

Muscular rigidity of the extremities occurred in one man exposed to an unknown concentration of methyl mercaptan (Shults et al, 1970).

NEUROLOGIC

COMA: Irreversible coma developed in a man exposed to an unknown concentration for 1 hour. The man expired 28 days after exposure (Shults et al, 1970).
Staggering, headache, and dizziness can occur (Clayton & Clayton, 1994; Pickler, 1918).
HEADACHE: Headache (statistically significant), dizziness, and decreased ability to concentrate were reported more frequently in workers exposed to methyl mercaptan, hydrogen sulfide, dimethyl sulfide and dimethyl disulfide in the pulp industry, as compared to controls (Kangas et al, 1984).
SEIZURES: Seizures developed in a man 4 days after a one-hour exposure to an unknown concentration of methyl mercaptan (Shults et al, 1970).
RESTLESSNESS: Restlessness was reported more frequently (not statistically significant) in workers exposed to methyl mercaptan, hydrogen sulfide, dimethyl sulfide and dimethyl disulfide in the pulp industry than in controls (Kangas et al, 1984).

RESPIRATORY

PULMONARY EMBOLISM: A man who developed coma, hemolytic anemia, and methemoglobinemia died 28 days later of a massive embolus which occluded both main pulmonary arteries (Shults et al, 1970).
PNEUMONIA: Bronchopneumonia was reported in a worker exposed to unknown concentrations (Spacilova, 1971).

CHRONIC CLINICAL EFFECTS

Repeated exposure to airborne concentrations up to 57 ppm for 3 months caused liver damage in rats (Tansy et al, 1981).

-FIRST AID

FIRST AID AND PREHOSPITAL TREATMENT

Prehospital gastrointestinal decontamination is generally not recommended because of the potential for CNS depression or persistent seizures and subsequent aspiration.

-MEDICAL TREATMENT

LIFE SUPPORT

Support respiratory and cardiovascular function.

SUMMARY

FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (ERG, 2004)

Move victim to fresh air.
Call 911 or emergency medical service.
Give artificial respiration if victim is not breathing.
Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device.
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.
In case of contact with liquefied gas, thaw frosted parts with lukewarm water.
In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin.
Keep victim warm and quiet.
Keep victim under observation.
Effects of contact or inhalation may be delayed.
Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.

FIRST AID

FIRST AID

The following first aid measures are suggested (National Institute for Occupational Safety and Health, 2007):

EYE EXPOSURE: Liquid State - 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.

Compressed (cryogenic) Gas: If eye tissue is frozen, seek medical attention immediately; if tissue is not frozen, immediately and thoroughly flush the eyes with large amounts of water for at least 15 minutes, occasionally lifting the lower and upper eyelids. If irritation, pain, swelling, lacrimation, or photophobia persist, get medical attention as soon as possible.

DERMAL EXPOSURE: Liquid State - Immediately flush the contaminated skin with water. If this chemical penetrates the clothing, immediately remove the clothing and flush the skin with water. Get medical attention promptly.

Compressed (cryogenic) Gas - If frostbite has occurred, seek medical attention immediately; do NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT attempt to remove frozen clothing from frostbitten areas. If frostbite has NOT occurred, immediately and thoroughly wash contaminated skin with soap and water.

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.
TARGET ORGANS: Eyes, skin, respiratory system, central nervous system and blood.

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.
Respiratory tract irritation, if severe, can progress to pulmonary edema which may be delayed in onset up to 24 to 72 hours after exposure in some cases.
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.

METHEMOGLOBINEMIA: Determine the methemoglobin concentration and evaluate the patient for clinical effects of methemoglobinemia (ie, dyspnea, headache, fatigue, CNS depression, tachycardia, metabolic acidosis). Treat patients with symptomatic methemoglobinemia with methylene blue (this usually occurs at methemoglobin concentrations above 20% to 30%, but may occur at lower methemoglobin concentrations in patients with anemia, or underlying pulmonary or cardiovascular disorders). Administer oxygen while preparing for methylene blue therapy.
METHYLENE BLUE: INITIAL DOSE/ADULT OR CHILD: 1 mg/kg IV over 5 to 30 minutes; a repeat dose of up to 1 mg/kg may be given 1 hour after the first dose if methemoglobin levels remain greater than 30% or if signs and symptoms persist. NOTE: Methylene blue is available as follows: 50 mg/10 mL (5 mg/mL or 0.5% solution) single-dose ampules and 10 mg/1 mL (1% solution) vials. Additional doses may sometimes be required. Improvement is usually noted shortly after administration if diagnosis is correct. Consider other diagnoses or treatment options if no improvement has been observed after several doses. If intravenous access cannot be established, methylene blue may also be given by intraosseous infusion. Methylene blue should not be given by subcutaneous or intrathecal injection. NEONATES: DOSE: 0.3 to 1 mg/kg.
Concomitant use of methylene blue with serotonergic drugs, including serotonin reuptake inhibitors (SRIs), selective serotonin reuptake inhibitors (SSRIs), serotonin and norepinephrine reuptake inhibitors (SNRIs), tricyclic antidepressants (TCAs), norepinephrine-dopamine reuptake inhibitors (NDRIs), triptans, and ergot alkaloids may increase the risk of potentially fatal serotonin syndrome.

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.
If frostbite has occurred, seek medical attention immediately. DO NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT remove frozen clothing from frostbitten areas.
PREHOSPITAL

Rewarming of a localized area should only be considered if the risk of refreezing is unlikely. Avoid rubbing the frozen area which may cause further damage to the area (Grieve et al, 2011; Hallam et al, 2010).

REWARMING

Do not institute rewarming unless complete rewarming can be assured; refreezing thawed tissue increases tissue damage. Place affected area in a water bath with a temperature of 40 to 42 degrees Celsius for 15 to 30 minutes until thawing is complete. The bath should be large enough to permit complete immersion of the injured part, avoiding contact with the sides of the bath. A whirlpool bath would be ideal. Some authors suggest a mild antibacterial (ie, chlorhexidine, hexachlorophene or povidone-iodine) be added to the bath water. Tissues should be thoroughly rewarmed and pliable; the skin will appear a red-purple color (Grieve et al, 2011; Hallam et al, 2010; Murphy et al, 2000).
Correct systemic hypothermia which can cause cold diuresis due to suppression of antidiuretic hormone; consider IV fluids (Grieve et al, 2011).
Rewarming may be associated with increasing acute pain, requiring narcotic analgesics.
For severe frostbite, clinical trials have shown that pentoxifylline, a phosphodiesterase inhibitor, can enhance tissue viability by increasing blood flow and reducing platelet activity (Hallam et al, 2010).

WOUND CARE

Digits should be separated by sterile absorbent cotton; no constrictive dressings should be used. Protective dressings should be changed twice per day.
Perform twice daily hydrotherapy for 30 to 45 minutes in warm water at 40 degrees Celsius. This helps debride devitalized tissue and maintain range of motion. Keep the area warm and dry between treatments (Hallam et al, 2010; Murphy et al, 2000).
The injured extremities should be elevated and should not be allowed to bear weight.
In patients at risk for infection of necrotic tissue, prophylactic antibiotics and tetanus toxoid have been recommended by some authors (Hallam et al, 2010; Murphy et al, 2000).
Non-tense clear blisters should be left intact due to the risk of infection; tense or hemorrhagic blisters may be carefully aspirated in a setting where aseptic technique is provided (Hallam et al, 2010).
Further surgical debridement should be delayed until mummification demarcation has occurred (60 to 90 days). Spontaneous amputation may occur.
Analgesics may be required during the rewarming phase; however, patients with severe pain should be evaluated for vasospasm.
IMAGING: Arteriography and noninvasive vascular techniques (e.g., plain radiography, laser Doppler studies, digital plethysmography, infrared thermography, isotope scanning), have been useful in evaluating the extent of vasospasm after thawing and assessing whether debridement is needed (Hallam et al, 2010). In cases of severe frostbite, Technetium 99 (triple phase scanning) and MRI angiography have been shown to be the most useful to assess injury and determine the extent or need for surgical debridement (Hallam et al, 2010).
TOPICAL THERAPY: Topical aloe vera may decrease tissue destruction and should be applied every 6 hours (Murphy et al, 2000).
IBUPROFEN THERAPY: Ibuprofen, a thromboxane inhibitor, may help limit inflammatory damage and reduce tissue loss (Grieve et al, 2011; Murphy et al, 2000). DOSE: 400 mg orally every 12 hours is recommended (Hallam et al, 2010).
THROMBOLYTIC THERAPY: Thrombolysis (intra-arterial or intravenous thrombolytic agents) may be beneficial in those patients at risk to lose a digit or a limb, if done within the first 24 hours of exposure. The use of tissue plasminogen activator (t-PA) to clear microvascular thromboses can restore arterial blood flow, but should be accompanied by close monitoring including angiography or technetium scanning to evaluate the injury and to evaluate the effects of t-PA administration. Potential risk of the procedure includes significant tissue edema that can lead to a rise in interstitial pressures resulting in compartment syndrome (Grieve et al, 2011).
CONTROVERSIAL: Adjunct pharmacological agents (ie, heparin, vasodilators, prostacyclins, prostaglandin synthetase inhibitors, dextran) are controversial and not routinely recommended. The role of hyperbaric oxygen therapy, sympathectomy remains unclear (Grieve et al, 2011).
CHRONIC PAIN: Vasomotor dysfunction can produce chronic pain. Amitriptyline has been used in some patients; some patients may need a referral for pain management. Inability to tolerate the cold (in the affected area) has been observed following a single episode of frostbite (Hallam et al, 2010).
MORBIDITIES: Frostbite can produce localized osteoporosis and possible bone loss following a severe case. These events may take a year or more to develop. Children may be at greater risk to develop more severe events (ie, early arthritis) (Hallam et al, 2010).

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.
If eye tissue is frozen, seek ophthalmologic consultation immediately.

ORAL EXPOSURE

Prehospital gastrointestinal decontamination is generally not recommended because of the potential for CNS depression or persistent seizures and subsequent aspiration.
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.
Respiratory tract irritation, if severe, can progress to pulmonary edema which may be delayed in onset up to 24 to 72 hours after exposure in some cases.
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.
METHEMOGLOBINEMIA: Determine the methemoglobin concentration and evaluate the patient for clinical effects of methemoglobinemia (ie, dyspnea, headache, fatigue, CNS depression, tachycardia, metabolic acidosis). Treat patients with symptomatic methemoglobinemia with methylene blue (this usually occurs at methemoglobin concentrations above 20% to 30%, but may occur at lower methemoglobin concentrations in patients with anemia, or underlying pulmonary or cardiovascular disorders). Administer oxygen while preparing for methylene blue therapy.
METHYLENE BLUE: INITIAL DOSE/ADULT OR CHILD: 1 mg/kg IV over 5 to 30 minutes; a repeat dose of up to 1 mg/kg may be given 1 hour after the first dose if methemoglobin levels remain greater than 30% or if signs and symptoms persist. NOTE: Methylene blue is available as follows: 50 mg/10 mL (5 mg/mL or 0.5% solution) single-dose ampules and 10 mg/1 mL (1% solution) vials. Additional doses may sometimes be required. Improvement is usually noted shortly after administration if diagnosis is correct. Consider other diagnoses or treatment options if no improvement has been observed after several doses. If intravenous access cannot be established, methylene blue may also be given by intraosseous infusion. Methylene blue should not be given by subcutaneous or intrathecal injection. NEONATES: DOSE: 0.3 to 1 mg/kg.
Concomitant use of methylene blue with serotonergic drugs, including serotonin reuptake inhibitors (SRIs), selective serotonin reuptake inhibitors (SSRIs), serotonin and norepinephrine reuptake inhibitors (SNRIs), tricyclic antidepressants (TCAs), norepinephrine-dopamine reuptake inhibitors (NDRIs), triptans, and ergot alkaloids may increase the risk of potentially fatal serotonin syndrome.

-RANGE OF TOXICITY

MINIMUM LETHAL EXPOSURE

Human toxicity data are insufficient to be definitive, but methyl mercaptan should be treated as dangerously toxic (ACGIH, 1996; Clayton & Clayton, 1994; Hathaway et al, 1996; Lewis, 1998).

MAXIMUM TOLERATED EXPOSURE

Methyl mercaptan is a central nervous system (CNS) depressant and is extremely irritating to the eyes and the respiratory system. Signs and symptoms of exposure to methyl mercaptan include eye and mucous membrane irritation, headache, dizziness, staggering gait, nausea, and vomiting. Lower concentrations cause pulmonary edema; higher concentrations can cause hepatic and renal damage, coma, and death by respiratory paralysis (similar to hydrogen sulfide) (ACGIH, 1996; Clayton & Clayton, 1994; Hathaway et al, 1996) Raffle et al, 1994).

Odor and symptoms of irritation do not provide adequate warning of exposure to high concentrations of methyl mercaptan due to olfactory fatigue (Clayton & Clayton, 1994).
Exposure to 4 ppm resulted in nausea, headache and, in one of 28 cases, slight liver damage (Pickler, 1918).

Carcinogenicity Ratings for CAS74-93-1 :

ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: Methyl mercaptan
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 mercaptan
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 CAS74-93-1 (U.S. Environmental Protection Agency, 2011):

Not Listed

TOXICITY VALUES

LC50- (INHALATION)MOUSE:
- 6530 mcg/m(3) for 2H (RTECS, 2006)
LC50- (INHALATION)RAT:
- 675 ppm -- changes in respiration, gastrointestinal hypermotility, diarrhea, increased urine volume (RTECS, 2006)
- 1664 ppm/4H (HSDB, 2000)

CALCULATIONS

AMBIENT CONVERSIONS

CONVERSION FACTORS

1 mg/m(3) = 4.88 ppm (Verschueren, 1983)

1.96 mg/m(3) = 1 ppm (Clayton & Clayton, 1994)
1 ppm = 2.05 mg/m(3) (Verschueren, 1983)

-STANDARDS AND LABELS

WORKPLACE STANDARDS

ACGIH TLV Values for CAS74-93-1 (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 mercaptan

TLV:

TLV-TWA: 0.5 ppm
TLV-STEL:
TLV-Ceiling:

Notations and Endnotes:

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

TLV Basis - Critical Effect(s): Liver dam
Molecular Weight: 48.11

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 CAS74-93-1 (AIHA, 2006):

Not Listed

NIOSH REL and IDLH Values for CAS74-93-1 (National Institute for Occupational Safety and Health, 2007):

Listed as: Methyl mercaptan
REL:

TWA:
STEL:
Ceiling: 0.5 ppm (1 mg/m(3)) [15-minute]
Carcinogen Listing: (Not Listed) Not Listed
Skin Designation: Not Listed
Note(s):

IDLH:

IDLH: 150 ppm
Note(s): Not Listed

OSHA PEL Values for CAS74-93-1 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):

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

8-hour TWA:

ppm: 10

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

mg/m3: 20

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: (C) - An employee's exposure to this substance shall at no time exceed the exposure limit given.
Skin Designation: No
Notation(s): Not Listed

OSHA List of Highly Hazardous Chemicals, Toxics, and Reactives for CAS74-93-1 (U.S. Occupational Safety and Health Administration, 2010):

Threshold Quantity, in pounds:5000

ENVIRONMENTAL STANDARDS

EPA CERCLA, Hazardous Substances and Reportable Quantities for CAS74-93-1 (U.S. Environmental Protection Agency, 2010):

Listed as: Methyl mercaptan
Final Reportable Quantity, in pounds (kilograms):

100 (45.4)

Additional Information:
Listed as: Thiomethanol
Final Reportable Quantity, in pounds (kilograms):

100 (45.4)

Additional Information:
Listed as: Methanethiol
Final Reportable Quantity, in pounds (kilograms):

100 (45.4)

Additional Information:

EPA CERCLA, Hazardous Substances and Reportable Quantities, Radionuclides for CAS74-93-1 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA RCRA Hazardous Waste Number for CAS74-93-1 (U.S. Environmental Protection Agency, 2010b):

Listed as: Methanethiol
P or U series number: U153
Footnote:
Listed as: Thiomethanol
P or U series number: U153
Footnote:
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 CAS74-93-1 (U.S. Environmental Protection Agency, 2010):

Listed as: Methyl Mercaptan
Reportable Quantity, in pounds: 100

Only the statutory or final RQ is shown. For more information, see 40 CFR table 302.4.

Threshold Planning Quantity, in pounds:

500
Amount necessary to be covered by this standard. See 40 CFR 355.30.

Note(s): f

f: Chemicals on the original list that do not meet toxicity criteria but because of their acute lethality, high production volume and known risk are considered chemicals of concern ("Other chemicals"). (November 17, 1986, and February 15, 1990.)

EPA SARA Title III, Community Right-to-Know for CAS74-93-1 (40 CFR 372.65, 2006; 40 CFR 372.28, 2006):

Listed as: Methyl mercaptan
Effective Date for Reporting Under 40 CFR 372.30: 1/1/94
Lower Thresholds for Chemicals of Special Concern under 40 CFR 372.28:

DOT List of Marine Pollutants for CAS74-93-1 (49 CFR 172.101 - App. B, 2005):

Listed as Methanethiol
Severe Marine Pollutant: No
Listed as Methyl mercaptan
Severe Marine Pollutant: No

EPA TSCA Inventory for CAS74-93-1 (EPA, 2005):

Listed as: Methanethiol

SHIPPING REGULATIONS

SURFACE

DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 1064 (49 CFR 172.101, 2005):

Hazardous materials descriptions and proper shipping name: Methyl mercaptan

Symbol(s): Not Listed
Hazard class or Division: 2.3

2.3: Poisonous gas. See 49 CFR section 173.115 for definitions.

Identification Number: UN1064
Packing Group: Not Listed
Label(s) required (if not excepted): 2.3, 2.1

2.3: Poison Gas.
2.1: Flammable Gas.

Special Provisions: 3, B7, B9, B14, T50

3: This material is poisonous by inhalation (see sxn. 171.8 of this subchapter) in Hazard Zone C (see sxn. 173.116(a) of this subchapter), and must be described as an inhalation hazard under the provisions of this subchapter.
B7: Safety relief devices are not authorized on multi-unit tank car tanks. Openings for safety relief devices on multi-unit tank car tanks shall be plugged or blank flanged.
B9: Bottom outlets are not authorized.
B14: Each bulk packaging, except a tank car or a multi-unit-tank car tank, must be insulated with an insulating material so that the overall thermal conductance at 15.5 °C (60 °F) is no more than 1.5333 kilojoules per hour per square meter per degree Celsius (0.075 Btu per hour per square foot per degree Fahrenheit) temperature differential. Insulating materials must not promote corrosion to steel when wet.
T50: Applicable liquefied compressed gases are authorized to be transported in portable tanks in accordance with the requirements of sxn. 173.313 of this subchapter.

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

Exceptions: None
Non-bulk packaging: 304
Bulk packaging: 314, 315

Quantity Limitations:

Passenger aircraft or railcar: Forbidden
Cargo aircraft only: Forbidden

Vessel Stowage Requirements:

Vessel stowage location: D

D: The material must be stowed "on deck only" 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 the material is prohibited on passenger vessels in which the limiting number of passengers is exceeded.

Vessel stowage other: 40

40: Stow "clear of living quarters".

ICAO International Shipping Name for UN1064 (ICAO, 2002):

Proper Shipping Name: Methyl mercaptan
UN Number: 1064

LABELS

NFPA

NFPA Hazard Ratings for CAS74-93-1 (NFPA, 2002):

Listed as: Methyl Mercaptan
Hazard Ratings:

Health Rating (Blue): 4

(4) Highly toxic material. Very limited exposure could cause death or major injury even though prompt medical treatment is given. Includes known or suspect human carcinogens, mutagens, or teratogens.

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): 1

(1) Materials which are normally stable, but which can become unstable at elevated temperatures and pressures, or which may react with water with some release of energy, but not violently.

Oxidizer/Water-Reactive Designation: Not Listed

-HANDLING AND STORAGE

SUMMARY

INDUSTRIAL CHEMICALS

Methyl mercaptan is poisonous by inhalation, irritating to the eyes, skin, and respiratory system, and is a cryogenic hazard. Wear appropriate protective clothing whenever using or handling methyl mercaptan; remove clothing immediately if it becomes wet or contaminated with methyl mercaptan to avoid fire hazard (Lewis, 1996; NFPA, 1997; Sittig, 1991).
It is a very dangerous fire hazard. Smoking, open flames, and other sources of ignition should be prohibited in areas where methyl mercaptan is used or stored. Only non-sparking tools should be used around this compound, especially when its containers are being opened or closed (Lewis, 1996; Sittig, 1991).

HANDLING

Wear appropriate protective clothing whenever using or handling methyl mercaptan. Only non-sparking tools should be used around this compound, especially when its containers are being opened or closed (Sittig, 1991).

STORAGE

CONTAINER

Store methyl mercaptan in tightly closed containers. Methyl mercaptan is typically shipped in stainless steel cylinders. It is often shipped in bulk by rail or truck; typical containers for bulk shipments of methyl mercaptan are single-unit tank cars, multi-unit tank cars, and cargo tanks. Ground and bond metal containers when used in the transfer of 5 gallons or more of this compound; equip drums with pressure vacuum bungs, self-closing valves, and flame arrestors (CGA, 1990; NFPA, 1997; Sittig, 1991).

ROOM/CABINET RECOMMENDATIONS

Store in a cool, dry, well-ventilated area away from heat and sparks (NFPA, 1997; Sittig, 1991).

INCOMPATIBILITIES

Methyl mercaptan is incompatible with water, steam, strong acids (eg, hydrochloric, sulfuric, and nitric), oxidizers, and mercury (II) oxide (NFPA, 1997; Pohanish & Greene, 1997; Sittig, 1991).

-PERSONAL PROTECTION

SUMMARY

RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (ERG, 2004)

Wear positive pressure self-contained breathing apparatus (SCBA).
Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection.
Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.

Methyl mercaptan is poisonous by inhalation, irritating to the eyes, skin, and respiratory system. Avoid breathing methyl mercaptan vapors; keep upwind. Wear a positive pressure self-contained breathing apparatus (AAR, 1998; (Lewis, 1996) NFPA, 1994; (Sittig, 1991).

Methyl mercaptan is a cryogenic hazard; wear appropriate protective clothing to prevent skin freezing. Do not handle broken or leaking containers of methyl mercaptan unless wearing appropriate protective clothing and equipment. Wash away any methyl mercaptan that contacts the skin with copious amounts of water or soap and water (AAR, 1998; (CGA, 1990).

Methyl mercaptan is a very dangerous fire hazard; clothing should be immediately removed when contaminated with methyl mercaptan (AAR, 1998; (Lewis, 1996; Sittig, 1991).

EYE/FACE PROTECTION

Eye protection should be worn when working with methyl mercaptan (Sittig, 1991).

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 74-93-1.

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

Plastic Laminate

DuPont Personal Protection

Responder

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

Responder Plus

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

Tychem 10,000

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): 0.029
Notes: gas
Citation: (DuPont, 2002)

Tychem 7500

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): 0.05
Notes: gas
Citation: (DuPont, 2002)

Tychem 9400

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.001
Notes: gas
Citation: (DuPont, 2002)

Tychem BR

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.001
Notes: Not Listed
Citation: (DuPont, 2002)

Tychem F

Degradation Rating: Not Listed
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): 0.05
Notes: Not Listed
Citation: (DuPont, 2003)

Tychem LV

Degradation Rating: Not Listed
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.001
Notes: Not Listed
Citation: (DuPont, 2003)

Tychem QC

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: gas
Citation: (DuPont, 2002)

Tychem SL

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: gas
Citation: (DuPont, 2002)

Tychem ThermoPro

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): 0.05
Notes: Not Listed
Citation: (DuPont, 2003)

Tychem TK

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.001
Notes: Not Listed
Citation: (DuPont, 2002)
Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.001
Notes: gas
Citation: (DuPont, 2002)

FOOTWEAR

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

GLOVES

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

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

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

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 117 (ERG, 2004)
- These materials are extremely flammable.
- May form explosive mixtures with air.
- May be ignited by heat, sparks or flames.
- Vapors from liquefied gas are initially heavier than air and spread along ground.
- Vapors may travel to source of ignition and flash back.
- Runoff may create fire or explosion hazard.
- Cylinders exposed to fire may vent and release toxic and flammable gas through pressure relief devices.
- Containers may explode when heated.
- Ruptured cylinders may rocket.
Under exposure to heat or flame, methyl mercaptan vapor is explosive, and the compound presents an extremely dangerous fire hazard. Containers of methyl mercaptan may rupture or rocket when exposed to intense heat or fire for prolonged periods of time (AAR, 1998; (Lewis, 1996; Sittig, 1991).

FLAMMABILITY CLASSIFICATION

NFPA Flammability Rating for CAS74-93-1 (NFPA, 2002):

Listed as: Methyl Mercaptan
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 117 (ERG, 2004)

DO NOT EXTINGUISH A LEAKING GAS FIRE UNLESS LEAK CAN BE STOPPED.

SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (ERG, 2004)

Dry chemical, CO2, water spray or regular foam.

LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (ERG, 2004)

Water spray, fog or regular foam.
Move containers from fire area if you can do it without risk.
Damaged cylinders should be handled only by specialists.

TANK FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (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.
Do not direct water at source of leak or safety devices; icing may occur.
Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank.
ALWAYS stay away from tanks engulfed in fire.

NFPA Extinguishing Methods for CAS74-93-1 (NFPA, 2002):

Listed as: Methyl Mercaptan
Extinguishing Method(s): 5, 6

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.
6: Flammable gas fires are only safe to extinguish once the gas flow has been turned off. Attempting to fight a gas fire without turning off the gas can cause formation of an explosive gas cloud.

Use water in flooding quantities as fog and from as far away as possible to extinguish fires involving methyl mercaptan only if the flow can be stopped. Use water to cool affected containers, and stay away from the ends of tanks. If the tank becomes discolored due to the fire or if a rising sound is heard coming from venting safety devices, withdraw immediately. Alcohol foam, carbon dioxide, or dry chemical can be used to fight the fire. If leaks cannot be stopped immediately, allow small fires to burn (AAR, 1998; (NFPA, 1997; Lewis, 1996; Sittig, 1991).

Alcohol-resistant fire fighting foam is recommended for use on all water-soluble liquids or polar solvent-type liquids, except those that are only "very slightly" soluble. Certain judgement factors are introduced, however, since ordinary fire fighting foam may be used on some liquids that are only "slightly" soluble, particularly if the foam is applied at higher-than-normal application rates. Conversely, some flammable liquids, such as the higher molecular weight alcohols and amines, will destroy alcohol-resistant foams, even when applied at very high rates. Foams should not be used on water reactive materials. Some recently developed alcohol-resistant foams have been listed for use on both polar and nonpolar liquids. These 'multipurpose" foams are suitable for use on nearly all flammable liquid fires because they greatly minimize the problems of foam selection. Fire fighting foam suppliers should be consulted for recommendations regarding types of foam and application rates (NFPA, 1997).

COMBUSTION TOXICITY

Combustion of methyl mercaptan emits highly toxic fumes of sulfur oxides (Lewis, 1996; NFPA, 1997; Sittig, 1991).

EXPLOSION HAZARD

Under exposure to heat or flame, methyl mercaptan vapors are explosive. Containers of this compound may rupture or rocket when exposed to fire or intense heat for prolonged periods of time (AAR, 1998; (Lewis, 1996).

DUST/VAPOR HAZARD

Methyl mercaptan vapors can displace oxygen in the air and act as a simple asphyxiant (AAR, 1998; (CGA, 1990).

Methyl mercaptan vapors are explosive when exposed to heat or flame. The vapors are heavier than air; they can travel along the ground to a source of ignition and flash back (AAR, 1998; (ILO, 1998; Lewis, 1996; NFPA, 1997; Sittig, 1991).

Methyl mercaptan decomposes when heated and produces toxic oxides of sulfur. Toxic and flammable vapors are produced by its reaction with water, steam, or acids (ILO, 1998; Lewis, 1996; Sittig, 1991).

REACTIVITY HAZARD

Methyl mercaptan may accumulate static electrical charges which may cause ignition of its vapors (Pohanish & Greene, 1997).

It easily forms explosive air-gas mixtures due to its low flash point (-18 degrees C; 0 degrees F) (AAR, 1998; (Pohanish & Greene, 1997).

It reacts violently with strong oxidizers (eg, perchlorates, peroxides, permanganates, chlorates, and nitrates) causing fire and explosions (ILO, 1998; Lewis, 1996; NFPA, 1997; Pohanish & Greene, 1997; Sittig, 1991).

It has a violent reaction with mercury (II) oxide (Lewis, 1996; NFPA, 1997; Urben, 1996).

Methyl mercaptan decomposes when heated and produces toxic oxides of sulfur. It reacts with water, steam, or acids (eg, hydrochloric, sulfuric, and nitric) to produce toxic and flammable vapors (ILO, 1998; Lewis, 1996; Sittig, 1991).

Methyl mercaptan attacks some plastics, coatings, and rubber (Pohanish & Greene, 1997).

EVACUATION PROCEDURES

SUMMARY

Initial Isolation and Protective Action Distances (ERG, 2004)

Data presented from the Emergency Response Guidebook Table of Initial Isolation and Protective Action Distances are for use when a spill has occurred and there is no fire. If there is a fire, or if a fire is involved, evacuation information presented under FIRE - PUBLIC SAFETY EVACUATION DISTANCES should be used.
Generally, a small spill is one that involves a single, small package such as a drum containing up to approximately 200 liters, a small cylinder, or a small leak from a large package. A large spill is one that involves a spill from a large package, or multiple spills from many small packages.
Suggested distances to protect from vapors of toxic-by-inhalation and/or water-reactive materials during the first 30 minutes following the spill.

DOT ID No. 1064 - Methyl mercaptan

SMALL SPILLS

First isolate in all directions: 30 meters (100 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 0.1 kilometers (0.1 miles); or
during the NIGHT for: 0.2 kilometers (0.2 miles).

LARGE SPILLS

First isolate in all directions: 150 meters (500 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 1.3 kilometers (0.8 miles); or
during the NIGHT for: 4.5 kilometers (2.8 miles).

SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (ERG, 2004)

Increase, in the downwind direction, as necessary, the isolation distance of at least 100 meters (330 feet) in all directions.

FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (ERG, 2004)

If tank, rail car or tank truck is involved in a fire, ISOLATE for 1600 meters (1 mile) in all directions; also, consider initial evacuation for 1600 meters (1 mile) in all directions.

PUBLIC SAFETY MEASURES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (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 100 meters (330 feet) in all directions.
Keep unauthorized personnel away.
Stay upwind.
Many gases are heavier than air and will spread along the ground and collect in low or confined areas (sewers, basements, tanks).
Keep out of low areas.
Ventilate closed spaces before entering.

The evacuation of a one-half mile radius should be considered if the fire becomes uncontrollabe or a container is directly exposed to flames (AAR, 1998).

If methyl mercaptan is leaking but not on fire, consider evacuation from the downwind areas based on the amount of spilled methyl mercaptan, the location of the spill, and the weather (AAR, 1998).

AIHA ERPG Values for CAS74-93-1 (AIHA, 2006):

Listed as Methyl Mercaptan
ERPG-1 (units = ppm): 0.005
ERPG-2 (units = ppm): 25
ERPG-3 (units = ppm): 100
Under Ballot, Review, or Consideration: No
Definitions:

ERPG-1: The ERPG-1 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing more than mild, transient adverse health effects or perceiving a clearly defined objectionable odor.
ERPG-2: The ERPG-2 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing or developing irreversible or other serious health effects or symptoms that could impair an individual's ability to take protective action.
ERPG-3: The ERPG-3 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing or developing life-threatening health effects.

DOE TEEL Values for CAS74-93-1 (U.S. Department of Energy, Office of Emergency Management, 2010):

Listed as Methyl mercaptan
TEEL-0 (units = ppm): 0.5
TEEL-1 (units = ppm): 6
TEEL-2 (units = ppm): 47
TEEL-3 (units = ppm): 68
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 CAS74-93-1 (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):

Listed as: Methyl mercaptan
Proposed Value:

AEGL-1

10 min exposure:

ppm: insufficient data
mg/m3:

30 min exposure:

ppm: insufficient data
mg/m3:

1 hr exposure:

ppm: insufficient data
mg/m3:

4 hr exposure:

ppm: insufficient data
mg/m3:

8 hr exposure:

ppm: insufficient data
mg/m3:

Definitions:

AEGL-1 is the airborne concentration of a substance above which it is predicted that the general population, including susceptible individuals, could experience notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effects are not disabling, are transient, and are reversible upon cessation of exposure.

Listed as: Methyl mercaptan
Proposed Value:

AEGL-2

10 min exposure:

ppm: 59 ppm
mg/m3:

30 min exposure:

ppm: 59 ppm
mg/m3:

1 hr exposure:

ppm: 47 ppm
mg/m3:

4 hr exposure:

ppm: 30 ppm
mg/m3:

8 hr exposure:

ppm: 19 ppm
mg/m3:

Definitions:

AEGL-2 is the airborne concentration 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.

Listed as: Methyl mercaptan
Proposed Value:

AEGL-3

10 min exposure:

ppm: 120 ppm
mg/m3:

30 min exposure:

ppm: 86 ppm
mg/m3:

1 hr exposure:

ppm: 68 ppm
mg/m3:

4 hr exposure:

ppm: 43 ppm
mg/m3:

8 hr exposure:

ppm: 22 ppm
mg/m3:

Definitions:

AEGL-3 is the airborne concentration of a substance above which it is predicted that the general population, including susceptible individuals, could experience life-threatening health effects or death.

NIOSH IDLH Values for CAS74-93-1 (National Institute for Occupational Safety and Health, 2007):

IDLH: 150 ppm
Note(s): Not Listed

CONTAINMENT/WASTE TREATMENT OPTIONS

SUMMARY

SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (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.
- Fully encapsulating, vapor protective clothing should be worn for spills and leaks with no fire.
- Do not touch or walk through spilled material.
- Stop leak if you can do it without risk.
- Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material.
- Do not direct water at spill or source of leak.
- If possible, turn leaking containers so that gas escapes rather than liquid.
- Prevent entry into waterways, sewers, basements or confined areas.
- Isolate area until gas has dispersed.
- Consider igniting spill or leak to eliminate toxic gas concerns.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 117 (ERG, 2004)
- Wear positive pressure self-contained breathing apparatus (SCBA).
- Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection.
- Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
If methyl mercaptan is not on fire and not involved in a fire, keep sparks, flames and other sources of ignition away from the area. Stay upwind and stay out of low areas. Attempt to stop the leak if this can be done without undue personnel hazard. Use water spray to disperse vapors, protect personnel, and dilute the spill to form a nonflammable mixture. Keep methyl mercaptan out of water sources and sewers; control the runoff and isolate the spilled methyl mercaptan for proper disposal (AAR, 1998; (NFPA, 1997; Sittig, 1991).
A holding area should be created to contain liquid methyl mercaptan when spilled onto land. Surface flow should be diked using soil, sand bags, foamed concrete, or foamed polyurethane. Bulk liquid can be absorbed with fly ash or cement powder (AAR, 1998).
Natural barriers or oil spill control booms should be used to limit spill travel when methyl mercaptan is spilled into water. If the spill dissolves to a concentration of about 10 ppm or greater, apply activated carbon at ten times the spilled amount. Immobilized masses of methyl mercaptan can be removed by mechanical dredges or lifts (AAR, 1998).
If methyl mercaptan is spilled in air, apply water spray or mist to knock down the vapors (AAR, 1998).

SMALL LEAK/SPILL

If methyl mercaptan is spilled, isolate the area and deny entry to unnecessary people to the area. Ventilate the area; do not enter the area without first ventilating it or wearing respiratory protection. Stop the leak quickly if this can be done without risk. Eliminate all sources of ignition. Use a weak solution of calcium hypochlorite (up to 15%) to cover small spills; after transferring the solution into a large beaker and letting set for 12 hours, add 6M hydrogen chloride or 6M ammonium hydroxide until solution is neutralized (CGA, 1990; ITI, 1995; Sittig, 1991).

WASTE TREATMENT OPTIONS

PHYSICAL TREATMENT

Dissolve small amounts of waste methyl mercaptan in a combustible solvent (eg, alcohols, benzene, etc.) and burn it in a furnace with an afterburner and scrubber to neutralize the sulfur dioxide (ITI, 1995; Sittig, 1991).
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.

-ENVIRONMENTAL HAZARD MANAGEMENT

POLLUTION HAZARD

Methyl mercaptan enters the environment as a result of its use, handling, and shipment in industry (eg, it is found as an emission from paper and pulp mills). Methyl mercaptan occurs naturally in a wide variety of vegetables (eg, onions and garlic), in "sour" gas in West Texas oil fields, and in coal tar and petroleum distillates, (ACGIH, 1991; (Ashford, 1994; Clayton & Clayton, 1994; Lewis, 1997).

An air pollution study in a town near a sulfate paper mill in Finland examined the effects of low level exposure to malodorous sulfur compounds on eye irritation, the respiratory system, and the central nervous system (CNS). The mill was a significant source for environmental total reduced sulfur (TRS) compounds, including methyl mercaptan. The study concluded that residents living near a sulfate paper mill experience an increased prevalence of cough, headache, and respiratory infection, despite the low level of TRS emissions. This indicates that adverse health affects caused by malodorous TRSs can occur at lower concentrations than previously thought (Partti-Pellinen et al, 1996).

ENVIRONMENTAL FATE AND KINETICS

OTHER

OTHER
- Methyl mercaptan released from kraft plant air was photochemically degraded to methane, methanol, formic acid, sulfur di- and trioxide, ethyl mercaptan, dimethyl disulfide, & methyl sulfonic acid (p 17). In atmospheric air, the thiol of methyl mercaptan reacts with ozone to produce sulfur dioxide and methane sulfonic acid (76:95).

ENVIRONMENTAL TOXICITY

Methyl mercaptan is harmful to aquatic life; fish are highly sensitive to it. Methyl mercaptan was lethal at 1 ppm to white bass, yellow perch, large- and smallmouth bass, bluegills, and rockbass (Clayton & Clayton, 1994).

The no-effect level in fish is estimated at 0.5 ppm, the MLC for cutthroat trout and king and silver salmon is approximately 0.9 ppm (Haydu et al, 1952).

Ecotoxicity (Clayton & Clayton, 1994; Verschueren, 1983):

TLm - Salmonides: 0.55-0.9 mg/L
LC50 - Daphnia: 7.86 ppm

-PHYSICAL/CHEMICAL PROPERTIES

MOLECULAR WEIGHT

48.11

DESCRIPTION/PHYSICAL STATE

Methyl mercaptan is a colorless, flammable gas that liquefies at 6 degrees C and has a strong, very disagreeable, "rotten cabbage" odor. The odor is similar to hydrogen sulfide, but it can be detected at much lower concentrations (ACGIH, 1991; (Ashford, 1994; Budavari, 1996; CGA, 1990; Clayton & Clayton, 1994) Hathaway et al, 1996; (ILO, 1998; Lewis, 1996; Lewis, 1997) HSDB, 2000).

No information found at the time of this review.

VAPOR PRESSURE

1520 mmHg (at 26.1 degrees C; 79 degrees F) (Clayton & Clayton, 1994; ILO, 1998)

1692 mmHg (ACGIH, 1991)

1 atm (at 6.8 degrees C) (Verschueren, 1983)

2 atm (at 26.1 degrees C) (Verschueren, 1983)

5 atm (at 55.9 degrees C) (Verschueren, 1983)

SPECIFIC GRAVITY

NORMAL TEMPERATURE AND PRESSURE

(25 degrees C; 77 degrees F and 760 mmHg)
0.9600 (at 25/4 degrees C) (Budavari, 1996)

OTHER TEMPERATURE AND/OR PRESSURE

0.8665 (at 20/4 degrees C) (Budavari, 1996; Lewis, 1996)
0.868 (at 20/4 degrees C) (Verschueren, 1983)

DENSITY

STANDARD TEMPERATURE AND PRESSURE

(0 degrees C; 32 degrees F and 760 mmHg)
0.90 kg/L (Ashford, 1994)

FREEZING/MELTING POINT

FREEZING POINT

-121 degrees C (Lewis, 1997)

MELTING POINT

-120 degrees C; -184 degrees F (NFPA, 1994)
-122 degrees C (Ashford, 1994)
-123 degrees C (ACGIH, 1991; (Budavari, 1996; Clayton & Clayton, 1994; ILO, 1998; Lide, 1996; Verschueren, 1983)

BOILING POINT

5.95 degrees C (at 760 mmHg) (Budavari, 1996; Clayton & Clayton, 1994; ILO, 1998; Lewis, 1996; Lewis, 1997)

6 degrees C; 43 degrees F (Ashford, 1994) NFPA, 1994)

6.2 degrees C (ACGIH, 1991)

279 degrees K (at 1 atm) (Lide, 1996)

FLASH POINT

-17 degrees C; 0 degrees F (Lewis, 1997)

<-17.78 degrees C (open cup) (ACGIH, 1991)

-18 degrees C; -0.4 degrees F (ILO, 1998; Lewis, 1996)

AUTOIGNITION TEMPERATURE

No information found at the time of this review.

EXPLOSIVE LIMITS

LOWER

3.9% (ACGIH, 1991; (ILO, 1998; Lewis, 1996; Lewis, 1997) NFPA, 1994; Raffle et al, 1994)

UPPER

21.8% (ACGIH, 1991; (ILO, 1998; Lewis, 1996; Lewis, 1997) NFPA, 1994; Raffle et al, 1994)

SOLUBILITY

IN WATER

Methyl mercaptan is slightly soluble to soluble in water (AAR, 1998; ACGIH, 1991; (Ashford, 1994; ILO, 1998; Lewis, 1996; Lewis, 1997) NFPA, 1994).

23.3 g/L (at 20 degree C) (ACGIH, 1991; (Budavari, 1996).

It decomposes in water (Clayton & Clayton, 1994).

IN ORGANIC SOLVENTS

It is soluble in oxygenated solvents, and soluble to very soluble in alcohol, ether, and petroleum naphtha (ACGIH, 1991; (Ashford, 1994; Clayton & Clayton, 1994; Lewis, 1997).

HENRY'S CONSTANT

4.0x10(-3) atm-m(3)/mol (Ehrenfeld et al, 1986)

0.123 (nondimesional) (HSDB , 1999)

SPECTRAL CONSTANTS

17224 (HSDB , 1999)

3-1 (HSDB , 1999)

MASS

17 (HSDB , 1999)

OTHER/PHYSICAL

ODOR THRESHOLD

1.1 ppb (Verschueren, 1983)
2 ppb (Clayton & Clayton, 1994)

SURFACE TENSION

31 dynes/cm; 0.031 N/m (at 5 degrees C) (HSDB , 1999)

CRITICAL PRESSURE

71.4 atm (Budavari, 1996)
7.23 MPa (Lide, 1996)

CRITICAL TEMPERATURE

196.8 degrees C (ACGIH, 1991; (Budavari, 1996)
470 degrees K (Lide, 1996)

DISSOCIATION CONSTANT

pKa = 10.33 (at 25 degrees C) (HSDB , 1999)

HEAT OF COMBUSTION

-11,054 Btu/lb; -6141 cal/g; -257.0x10(5) J/kg (HSDB , 1999)

INDEX OF REFRACTION

1.4331 (at 20 degrees C) (HSDB , 1999)

NUCLEAR MAGNETIC RESONANCE

8209 (HSDB , 1999)

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METHYL MERCAPTAN

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Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents