DIMETHYL SULFATE

Dimethyl sulfate is used with boron compounds to stabilize liquid sulfur trioxide (HSDB , 2000).
It is used in dyes, perfumes, pesticides, fabric softeners, agrichemicals, and pharmaceuticals (HSDB , 2000; Sittig, 1991a).
It is used as a solvent for separation of mineral oils (Sittig, 1991a).
Dimethyl sulfate was used as an irritant and vesicant chemical warfare agent in World War I (HSDB , 2000). It was known as D-Stoff in Germany and tested as a potential war gas (Haswell, 1960).
Dimethyl sulfate has been used as a reagent in genetic research laboratories for "DNA footprinting," a method of determining specific sites of DNA-protein and DNA-DNA interactions (Dolle & Stratling, 1989; Kim et al, 1995).
It is used in the preparation of anhydrous cadmium sulfate and methyl iodide (HSDB , 2000).
It is used in the production of cationic emulsion polymers (HSDB , 2000).
It is used in analysis of auto fluids (HSDB , 2000).
It is a methylating agent used in the manufacture of polyurethane-based adhesives and organic chemicals including esters, ethers, anisole, nerolin, phenols, and amines (ACGIH, 1991a; HSDB , 2000; ITI, 1995; Sittig, 1991a). It is also used to convert thiols to corresponding methyl derivatives (HSDB , 2000).
It is used as a sulfating and sulfonating agent (HSDB , 2000).

FORMS

It is an oily, colorless liquid with a faint onion-like odor (Budavari, 2000; Haswell, 1960).
Dimethyl sulfate may contain sulfuric acid as an impurity (HSDB , 2000).

SOURCES

It is prepared by reaction of gaseous dimethyl ether and liquid sulfur trioxide (Budavari, 2000; HSDB , 2000).
It is produced by esterification of methanol and oleum (Ashford, 1994; HSDB , 2000).
It is derived from addition of fuming sulfuric acid to methanol with distillation in vacuo (HSDB , 2000; Lewis, 1997a).

-CLINICAL EFFECTS

GENERAL CLINICAL EFFECTS

Dimethyl sulfate (DMS) is extremely irritating to the eyes, skin, and mucous membranes. Toxicity is most common following inhalation of vapors or dermal exposure. Symptoms may be delayed for several hours after inhalation or dermal exposure. several hours.

Presenting symptoms following vapor exposure may include eye pain, photophobia, lacrimation, blurred vision, corneal edema, and angioneurotic edema, followed by pharyngolaryngeal inflammation, dysphonia, aphonia, dysphagia, productive cough, dyspnea, and cyanosis. Delayed pulmonary edema may occur. Other effects may include fever, delirium, seizures, coma, ECG changes, liver and kidney damage, hematuria, and albuminuria.

Contact with the liquid can cause irritation with severe ocular and dermal chemical burns. Dermal exposures may have a 1 to 2 hour delay before onset of symptoms which may include severe local burn with redness, swelling, pain, and bleb formation.

Oral exposure may result in nausea; vomiting; burns of the mouth, pharynx, and stomach; seizures; areflexia; cyanosis; pulmonary edema; and circulatory failure.

POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)

TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death.
Contact with molten substance may cause severe burns to skin and eyes.
Reaction with water or moist air will release toxic, corrosive or flammable gases.
Reaction with water may generate much heat that will increase the concentration of fumes in the air.
Fire will produce irritating, corrosive and/or toxic gases.
Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

-FIRST AID

FIRST AID AND PREHOSPITAL TREATMENT

SUMMARY

Rapid decontamination is paramount. Monitor respiration and airway status. Provide humidified oxygen to all patients with respiratory symptoms.

DILUTION

If no respiratory compromise is present, administer milk or water as soon as possible after ingestion. The exact ideal amount is unknown; no more than 8 ounces (240 mL) in adults and 4 ounces (120 mL) in children is recommended to minimize the risk of vomiting (Caravati, 2004).
USE OF DILUENTS IS CONTROVERSIAL: While experimental models have suggested that immediate dilution may lessen caustic injury (Homan et al, 1993; Homan et al, 1994; Homan et al, 1995), this has not been adequately studied in humans.
DILUENT TYPE: Use any readily available nontoxic, cool liquid. Both milk and water have been shown to be effective in experimental studies of caustic ingestion (Maull et al, 1985; Rumack & Burrington, 1977; Homan et al, 1995; Homan et al, 1994; Homan et al, 1993).
ADVERSE EFFECTS: Potential adverse effects include vomiting and airway compromise (Caravati, 2004).
CONTRAINDICATIONS: Do NOT attempt dilution in patients with respiratory distress, altered mental status, severe abdominal pain, nausea or vomiting, or patients who are unable to swallow or protect their airway. Diluents should not be force fed to any patient who refuses to swallow (Rao & Hoffman, 2002).

EMESIS/ NOT RECOMMENDED

Inducing emesis is CONTRAINDICATED due to the vesicant, corrosive nature of dimethyl sulfate.

ACTIVATED CHARCOAL

There are no reports of activated charcoal use in patients poisoned with DMS, but theoretically it would adsorb the chemical. Activated charcoal may interfere with endoscopic visualization of burns.
PREHOSPITAL ACTIVATED CHARCOAL ADMINISTRATION

Consider prehospital administration of activated charcoal as an aqueous slurry in patients with a potentially toxic ingestion who are awake and able to protect their airway. Activated charcoal is most effective when administered within one hour of ingestion. Administration in the prehospital setting has the potential to significantly decrease the time from toxin ingestion to activated charcoal administration, although it has not been shown to affect outcome (Alaspaa et al, 2005; Thakore & Murphy, 2002; Spiller & Rogers, 2002).

In patients who are at risk for the abrupt onset of seizures or mental status depression, activated charcoal should not be administered in the prehospital setting, due to the risk of aspiration in the event of spontaneous emesis.
The addition of flavoring agents (cola drinks, chocolate milk, cherry syrup) to activated charcoal improves the palatability for children and may facilitate successful administration (Guenther Skokan et al, 2001; Dagnone et al, 2002).

CHARCOAL DOSE

Use a minimum of 240 milliliters of water per 30 grams charcoal (FDA, 1985). Optimum dose not established; usual dose is 25 to 100 grams in adults and adolescents; 25 to 50 grams in children aged 1 to 12 years (or 0.5 to 1 gram/kilogram body weight) ; and 0.5 to 1 gram/kilogram in infants up to 1 year old (Chyka et al, 2005).

Routine use of a cathartic with activated charcoal is NOT recommended as there is no evidence that cathartics reduce drug absorption and cathartics are known to cause adverse effects such as nausea, vomiting, abdominal cramps, electrolyte imbalances and occasionally hypotension (None Listed, 2004).

ADVERSE EFFECTS/CONTRAINDICATIONS

Complications: emesis, aspiration (Chyka et al, 2005). Aspiration may be complicated by acute respiratory failure, ARDS, bronchiolitis obliterans or chronic lung disease (Golej et al, 2001; Graff et al, 2002; Pollack et al, 1981; Harris & Filandrinos, 1993; Elliot et al, 1989; Rau et al, 1988; Golej et al, 2001; Graff et al, 2002). Refer to the ACTIVATED CHARCOAL/TREATMENT management for further information.
Contraindications: unprotected airway (increases risk/severity of aspiration) , nonfunctioning gastrointestinal tract, uncontrolled vomiting, and ingestion of most hydrocarbons (Chyka et al, 2005).

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.
Laryngeal edema may necessitate airway management.

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.

DERMAL EXPOSURE

Rapid decontamination is necessary, but may not prevent systemic toxicity.
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).

-MEDICAL TREATMENT

LIFE SUPPORT

Support respiratory and cardiovascular function.

SUMMARY

FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (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.
For minor skin contact, avoid spreading material on unaffected skin.
Keep victim warm and quiet.
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. Primary eye protection (spectacles or goggles), as defined by the Occupational Safety and Health Administration (OSHA), should be used when working with this chemical. Face shields should only be worn over primary eye protection.

Contact lens use is not recommended when working with this chemical. If contact lenses are worn, then appropriate eye and face protection devices must be used. OSHA emphasizes that dusty and/or chemical environments may represent an additional hazard to contact lens wearers.

DERMAL EXPOSURE - 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.
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.
ORAL EXPOSURE - If this chemical has been swallowed, get medical attention immediately.
TARGET ORGANS - Eyes, skin, respiratory system, liver, kidneys, and CNS [in animals: nasal and lung cancer](National Institute for Occupational Safety and Health, 2007).

GENERAL

Rapid decontamination is paramount. Monitor respiration and airway status. Provide humidified oxygen to all patients with respiratory symptoms.

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.

DERMAL EXPOSURE

Rapid decontamination is necessary, but may not prevent systemic toxicity.
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.
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.
Some chemicals can produce systemic poisoning by absorption through intact skin. Carefully observe patients with dermal exposure for the development of any systemic signs or symptoms and administer symptomatic treatment as necessary.

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.

ORAL EXPOSURE

Because of the potential for gastrointestinal tract irritation and seizures, DO NOT induce emesis.
There are no reports of activated charcoal use in patients poisoned with dimethyl sulfate, but theoretically it would adsorb the chemical. Activated charcoal may interfere with endoscopic visualization of burns.
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.
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.
Laryngeal edema may necessitate airway management.
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.

-RANGE OF TOXICITY

MINIMUM LETHAL EXPOSURE

ADULT

It has been estimated that inhalation exposure in humans to 100 parts per million for 10 minutes may be fatal (Hathaway et al, 1996).

ANIMAL DATA

Rats died after a 4-hour inhalation exposure to 30 parts per million (ACGIH, 1991).
Cats continuously exposed to air concentraton of 195 ppm, died in 1.5 weeks (ACGIH, 1991).
Monkeys died after 3 days at 26 ppm (ACGIH, 1991).

MAXIMUM TOLERATED EXPOSURE

ADULT

Even small amounts of dimethyl sulfate accidentally splashed on the skin have resulted in serious toxicity, without fatality (Littler & McConnell, 1955).
Eye irritation occurs at concentrations greater than approximately 5 mg/m(3) or 1 ppm (HSDB , 2000).
IARC classifies dimethyl sulfate as a group 2A: Probably carcinogenic to humans (IARC , 2000). The ACGIH places dimethyl sulfate in Group A3: Confirmed animal carcinogen (ACGIH, 2000).

ANIMAL STUDIES

Rats were seriously poisoned at 13 ppm for 20 minutes (ACGIH, 1991).

Carcinogenicity Ratings for CAS77-78-1 :

ACGIH (American Conference of Governmental Industrial Hygienists, 2010): A3 ; Listed as: Dimethyl sulfate

A3 :Confirmed Animal Carcinogen with Unknown Relevance to Humans: The agent is carcinogenic in experimental animals at a relatively high dose, by route(s) of administration, at site(s), of histologic type(s), or by mechanism(s) that may not be relevant to worker exposure. Available epidemiologic studies do not confirm an increased risk of cancer in exposed humans. Available evidence does not suggest that the agent is likely to cause cancer in humans except under uncommon or unlikely routes or levels of exposure.

EPA (U.S. Environmental Protection Agency, 2011): B2 ; Listed as: Dimethyl sulfate

B2 : Probable human carcinogen - based on sufficient evidence of carcinogenicity in animals.

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): 2A ; Listed as: Dimethyl sulfate

2A : The agent (mixture) is probably carcinogenic to humans. The exposure circumstance entails exposures that are probably carcinogenic to humans. This category is used when there is limited evidence of carcinogenicity in humans and sufficient evidence of carcinogenicity in experimental animals. In some cases, an agent (mixture) may be classified in this category when there is inadequate evidence of carcinogenicity in humans and sufficient evidence of carcinogenicity in experimental animals and strong evidence that the carcinogenesis is mediated by a mechanism that also operates in humans. Exceptionally, an agent, mixture or exposure circumstance may be classified in this category solely on the basis of limited evidence of carcinogenicity in humans.

NIOSH (National Institute for Occupational Safety and Health, 2007): Ca ; Listed as: Dimethyl sulfate

Ca : NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A in the NIOSH Pocket Guide to Chemical Hazards).

MAK (DFG, 2002): Category 2 ; Listed as: Dimethyl sulfate

Category 2 : Substances that are considered to be carcinogenic for man because sufficient data from long-term animal studies or limited evidence from animal studies substantiated by evidence from epidemiological studies indicate that they can make a significant contribution to cancer risk. Limited data from animal studies can be supported by evidence that the substance causes cancer by a mode of action that is relevant to man and by results of in vitro tests and short-term animal studies.

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 CAS77-78-1 (U.S. Environmental Protection Agency, 2011):

Oral:

Slope Factor:
RfD:

Inhalation:

Unit Risk:
RfC:

Drinking Water:

Unit Risk:

TOXICITY VALUES

References: Budavari, 2000 HSDB, 2000 OHM/TADS, 2000 RTECS, 2000
- LC50- (INHALATION)GUINEA_PIG:
- LC50- (INHALATION)MOUSE:
- LC50- (INHALATION)RAT:
- LCLo- (INHALATION)HUMAN:
- LCLo- (INHALATION)RAT:
- LD50- (ORAL)MOUSE:
- LD50- (INHALATION)RAT:
- LD50- (ORAL)RAT:
- LD50- (SUBCUTANEOUS)RAT:
- LDLo- (INTRAVENOUS)RABBIT:
- LDLo- (ORAL)RABBIT:
- LDLo- (SUBCUTANEOUS)RABBIT:
- TCLo- (INHALATION)RAT:
- TDLo- (INTRAVENOUS)RAT:
- TDLo- (SUBCUTANEOUS)RAT:

CALCULATIONS

AMBIENT CONVERSIONS

CONVERSION FACTORS

1 ppm = 5.16 mg/m(3) (at 68 degrees F and 760 mmHg) (NIOSH , 2000)

-STANDARDS AND LABELS

WORKPLACE STANDARDS

ACGIH TLV Values for CAS77-78-1 (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

Dimethyl sulfate

TLV:

TLV-TWA: 0.1 ppm
TLV-STEL:
TLV-Ceiling:

Notations and Endnotes:

Carcinogenicity Category: A3
Codes: Skin
Definitions:

A3: Confirmed Animal Carcinogen with Unknown Relevance to Humans: The agent is carcinogenic in experimental animals at a relatively high dose, by route(s) of administration, at site(s), of histologic type(s), or by mechanism(s) that may not be relevant to worker exposure. Available epidemiologic studies do not confirm an increased risk of cancer in exposed humans. Available evidence does not suggest that the agent is likely to cause cancer in humans except under uncommon or unlikely routes or levels of exposure.
Skin: This refers to the potential significant contribution to the overall exposure by the cutaneous route, including mucous membranes and the eyes, either by contact with vapors or, of likely greater significance, by direct skin contact with the substance. It should be noted that although some materials are capable of causing irritation, dermatitis, and sensitization in workers, these properties are not considered relevant when assigning a skin notation. Rather, data from acute dermal studies and repeated dose dermal studies in animals or humans, along with the ability of the chemical to be absorbed, are integrated in the decision-making toward assignment of the skin designation. Use of the skin designation provides an alert that air sampling would not be sufficient by itself in quantifying exposure from the substance and that measures to prevent significant cutaneous absorption may be warranted. Please see "Definitions and Notations" (in TLV booklet) for full definition.

TLV Basis - Critical Effect(s): Eye and skin irr
Molecular Weight: 126.1

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 CAS77-78-1 (AIHA, 2006):

Not Listed

NIOSH REL and IDLH Values for CAS77-78-1 (National Institute for Occupational Safety and Health, 2007):

Listed as: Dimethyl sulfate
REL:

TWA: 0.1 ppm (0.5 mg/m(3))
STEL:
Ceiling:
Carcinogen Listing: (Ca) NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A in the NIOSH Pocket Guide to Chemical Hazards).
Skin Designation: [skin]

Indicates the potential for dermal absorption; skin exposure should be prevented as necessary through the use of good work practices and gloves, coveralls, goggles, and other appropriate equipment.

Note(s): See Appendix A

IDLH:

IDLH: 7 ppm
Note(s): Ca

Ca: NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A).

OSHA PEL Values for CAS77-78-1 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):

Listed as: Dimethyl sulfate
Table Z-1 for Dimethyl sulfate:

8-hour TWA:

ppm: 1

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

mg/m3: 5

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: Yes
Notation(s): Not Listed

OSHA List of Highly Hazardous Chemicals, Toxics, and Reactives for CAS77-78-1 (U.S. Occupational Safety and Health Administration, 2010):

Not Listed

ENVIRONMENTAL STANDARDS

EPA CERCLA, Hazardous Substances and Reportable Quantities for CAS77-78-1 (U.S. Environmental Protection Agency, 2010):

Listed as: Sulfuric acid, dimethyl ester
Final Reportable Quantity, in pounds (kilograms):

100 (45.4)

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

100 (45.4)

Additional Information:

EPA CERCLA, Hazardous Substances and Reportable Quantities, Radionuclides for CAS77-78-1 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA RCRA Hazardous Waste Number for CAS77-78-1 (U.S. Environmental Protection Agency, 2010b):

Listed as: Dimethyl sulfate
P or U series number: U103
Footnote:
Listed as: Sulfuric acid, dimethyl ester
P or U series number: U103
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 CAS77-78-1 (U.S. Environmental Protection Agency, 2010):

Listed as: Dimethyl Sulfate
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): Not Listed

EPA SARA Title III, Community Right-to-Know for CAS77-78-1 (40 CFR 372.65, 2006; 40 CFR 372.28, 2006):

Listed as: Dimethyl sulfate
Effective Date for Reporting Under 40 CFR 372.30: 1/1/87
Lower Thresholds for Chemicals of Special Concern under 40 CFR 372.28:

DOT List of Marine Pollutants for CAS77-78-1 (49 CFR 172.101 - App. B, 2005):

Not Listed

EPA TSCA Inventory for CAS77-78-1 (EPA, 2005):

Listed as: Sulfuric acid, dimethyl ester

SHIPPING REGULATIONS

SURFACE

DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 1595 (49 CFR 172.101, 2005):

Hazardous materials descriptions and proper shipping name: Dimethyl sulfate

Symbol(s): Not Listed
Hazard class or Division: 6.1

6.1: Poisonous materials. See 49 CFR section 173.132 for definitions.

Identification Number: UN1595
Packing Group: I

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

Label(s) required (if not excepted): 6.1, 8

6.1: Poison Inhalation Hazard (inhalation hazard, Zone A or B) or Poison (other than inhalation hazard, Zone A or B; the packing group for a material is indicated in column 5 of the table.).
8: Corrosive.

Special Provisions: 2, B9, B14, B32, B74, B77, T20, TP2, TP13, TP38, TP45

2: This material is poisonous by inhalation (see sxn. 171.8 of this subchapter) in Hazard Zone B (see sxn. 173.116(a) or sxn. 173.133(a) of this subchapter), and must be described as an inhalation hazard under the provisions of this subchapter.
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.
B32: MC 312, MC 330, MC 331, DOT 412 cargo tanks and DOT 51 portable tanks must be made of stainless steel, except that steel other than stainless steel may be used in accordance with the provisions of sxn. 173.24b(b) of this subchapter. Thickness of stainless steel for tank shell and heads for cargo tanks and portable tanks must be the greater of 6.35 mm (0.250 inch) or the thickness required for a tank with a design pressure at least equal to 1.3 times the vapor pressure of the lading at 46 °C (115 °F). In addition, MC 312 and DOT 412 cargo tank motor vehicles must: a. Be ASME Code (U) stamped for 100% radiography of all pressure-retaining welds; b. Have accident damage protection which conforms with sxn. 178.345-8 of this subchapter; c. Have a MAWP or design pressure of at least 87 psig; and d. Have a bolted manway cover.
B74: Tank cars must have a test pressure of 20.68 Bar (300 psig) or greater and conform to Class 105S, 106, 110, 112J, 114J or 120S.
B77: Other packaging are authorized when approved by the Associate Administrator.
T20: Minimum test pressure (bar): 10; Minimum shell thickness (in mm-reference steel) (See sxn.178.274(d)): 8 mm; Pressure-relief requirements (See sxn.178.275(g)): sxn. 178.275(g)(3); Bottom opening requirements (See sxn.178.275(d)): Prohibited.
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.
TP13: Self-contained breathing apparatus must be provided when this hazardous material is transported by sea.
TP38: Each portable 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 may not promote corrosion to steel when wet.
TP45: Each portable tank must be made of stainless steel, except that steel other than stainless steel may be used in accordance with the provisions of 173.24b(b) of this subchapter. Thickness of stainless steel for portable tank shells and heads must be the greater of 6.35 mm (0.250 inch) or the thickness required for a portable tank with a design pressure at least equal to 1.3 times the vapor pressure of the hazardous material at 46 °C (115 °F).

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

Exceptions: None
Non-bulk packaging: 227
Bulk packaging: 244

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 UN1595 (ICAO, 2002):

Proper Shipping Name: Dimethyl sulphate
UN Number: 1595

LABELS

NFPA

NFPA Hazard Ratings for CAS77-78-1 (NFPA, 2002):

Listed as: Dimethyl Sulfate
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): 2

(2) Combustible. Materials that must be moderately heated before ignition can occur. Including liquids having a flash point above 100 degrees F, and solids that readily give off flammable vapors.

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

A regulated and clearly marked area should be established where dimethyl sulfate is handled and stored (Sittig, 1991).

HANDLING

It should be handled away from sources of ignition (such as smoking areas and areas with open flames) due to the potential fire or explosion hazard (Sittig, 1991).

Broken packages should not be handled without wearing appropriate personal protective equipment (AAR, 2000).

All equipment used should be grounded (HSDB , 2000).

Untrained workers should be strictly forbidden to attempt to clean up any massive spills (such as a container breakage). "Many accidents with dimethyl supfate have been the result of hasty and uninformed clean-up attempts" (ILO, 1998).

STORAGE

CONTAINER

In smaller volumes, it should be stored in glass bottles sealed in cans. Larger volumes should be stored in metal barrels, metal drums, tanks cars, or tank trucks (OHM/TADS , 2000).
- Dimethyl sulfate should be stored away from moisture as it can corrode metal (such as steel) when wet (CHRIS , 2000; OHM/TADS , 2000).
It should be stored and shipped in a container with pressure-vacuum type venting (CHRIS , 2000).

ROOM/CABINET RECOMMENDATIONS

Dimethyl sulfate is stable at room temperature (HSDB , 2000).
Protect against physical damage, store in a cool and well-ventilated location, away from area where fire hazard may be acute (HSDB , 2000).
"Outside or detached storage is preferred" (ITI, 1995).
Dimethyl sulfate should be stored away from moisture as it can corrode metal (such as steel) containers when wet (CHRIS , 2000; OHM/TADS , 2000).
It should be stored away from sources of ignition (such as smoking area and area with open flames) due to the potential fire or explosion hazard (Sittig, 1991).

INCOMPATIBILITIES

Dimethyl sulfate should be stored away from water, strong oxidizers, and ammonia solutions (Sittig, 1991).
- Dimethyl sulfate can corrode metal (such as steel) when wet (CHRIS , 2000).
- It reacts violently with strong oxidizers (such as chlorine, bromine, and fluorine), ammonia, and ammonium hydroxide (HSDB , 2000; NIOSH , 2000; Pohanish & Greene, 1997).
It attacks some plastics, rubber, and coatings (Pohanish & Greene, 1997).
It should be stored away from explosives, organic peroxides, oxidizable substances, flammable solids, toxicants, and radioactive substances (ITI, 1995).

-PERSONAL PROTECTION

SUMMARY

RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (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.

"Established procedures for the handling of human carcinogens should be followed" (ILO, 1998).

Proper protective gear should be worn (HSDB , 2000).

Persons in contact with dimethyl sulfate liquid or vapor at concentrations greater than 1 ppm should seek immediate medical treatment as either can be absorbed through the skin or respiratory tract and cause local and systemic toxicity. Symptoms may be delayed (to 10 hours or more). Major residual damage is likely to remain in spite of treatment (Budavari, 2000; CHRIS , 2000) Hathaway, 1996; (OHM/TADS , 2000).
Dimethyl sulfate in its liquid form causes severe irritation to eyes, respiratory system, and skin, and it can cause second or third degree burns. Flush skin areas with plenty of water for at least 15 minutes. Speed of removal is extremely important. This compound can be poisonous if exposed and absorbed. Remove and isolate contaminated clothing (AAR, 2000; CHRIS , 2000; OHM/TADS , 2000).

EYE/FACE PROTECTION

Goggles and face shields should be worn when working with dimethyl sulfate in its liquid form as this can prevent slashing into eyes (Grant, 1993; HSDB , 2000).

Dimethyl sulfate in its liquid form is very injurious (can cause a combination of immediate acid-type burn and delayed sever denaturation and necrosis from the methylation capability) if exposed. Hold eyelids open and flush with plenty of water for at least 15 minutes if this compound gets into the eyes (CHRIS , 2000; Grant, 1993).
Dimethyl sulfate in its liquid form is a severe skin irritant, and it can cause second or third degrees burns on the exposed face area upon short contact. Flush face with plenty of water (CHRIS , 2000).
Vapors of dimethyl sulfate cause severe irritation to eyes and throat and they cannot be tolerated even at low concentration (CHRIS , 2000). Injury of the eyes by vapors is a more common industrial occurence than injury by splashing of the liquid form (Grant, 1993).

RESPIRATORY PROTECTION

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

Positive-pressure airline hose masks or self-contained breathing apparatus should be worn; canister-type gas masks are not safe (HSDB , 2000).

Dimethyl sulfate causes severe irritation to respiratory system (CHRIS , 2000).

PROTECTIVE CLOTHING

CHEMICAL PROTECTIVE CLOTHING. Search results for CAS 77-78-1.

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

CPF 2

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

CPF 3

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

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): <0.001
Notes: liquid
Citation: (DuPont, 2002)

Tychem 7500

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

Tychem 9400

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

Tychem SL

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

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: liquid
Citation: (DuPont, 2002)

FOOTWEAR

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

GLOVES

Butyl

Best Manufacturing

Butyl 878

Degradation Rating: Excellent (after 60 minutes of testing)
Breakthrough Time (minutes): >240
Permeation Rate (mcg/cm2/min): None Detected
Notes: Tested with Limited Exposure Method (ASTM F 1383)
Citation: (Best Manufacturing, 2004)
Degradation Rating: Excellent (after 60 minutes of testing)
Breakthrough Time (minutes): 30
Permeation Rate (mcg/cm2/min): 0.9
Notes: Not Listed
Citation: (Best Manufacturing, 2004)

Natural Rubber

Best Manufacturing

Original Nitty Gritty

Degradation Rating: Excellent (after 60 minutes of testing)
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None Detected
Notes: Not Listed
Citation: (Best Manufacturing, 2004)
Degradation Rating: Excellent (after 60 minutes of testing)
Breakthrough Time (minutes): >240
Permeation Rate (mcg/cm2/min): None Detected
Notes: Tested under limited exposure method (ASTM F 1383)
Citation: (Best Manufacturing, 2004)

Neoprene

Best Manufacturing

Chloroflex 723

Degradation Rating: Excellent (after 60 minutes)
Breakthrough Time (minutes): >240
Permeation Rate (mcg/cm2/min): None detected
Notes: tested through limited exposure method (ATSM F 1383)
Citation: (Best Manufacturing, 2002)
Degradation Rating: Excellent (after 60 minutes)
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None detected
Notes: Not Listed
Citation: (Best Manufacturing, 2002)

Neoprene 6780 Series

Degradation Rating: Not Tested
Breakthrough Time (minutes): 15
Permeation Rate (mcg/cm2/min): 47
Notes: Not Listed
Citation: (Best Manufacturing, 2002)
Degradation Rating: Not Tested
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: tested through limited exposure method (ATSM F 1383)
Citation: (Best Manufacturing, 2002)

Ultraflex Neoprene 32

Degradation Rating: Excellent (after 60 minutes)
Breakthrough Time (minutes): 30
Permeation Rate (mcg/cm2/min): 78
Notes: tested through limited exposure method (ATSM F 1383)
Citation: (Best Manufacturing, 2002)
Degradation Rating: Excellent (after 60 minutes)
Breakthrough Time (minutes): 15
Permeation Rate (mcg/cm2/min): 94
Notes: Not Listed
Citation: (Best Manufacturing, 2002)

Neoprene+NatR

Best Manufacturing

Chem Master CHM

Degradation Rating: Excellent (after 60 minutes)
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None detected
Notes: Not Listed
Citation: (Best Manufacturing, 2002)
Degradation Rating: Excellent (after 60 minutes)
Breakthrough Time (minutes): >240
Permeation Rate (mcg/cm2/min): None detected
Notes: tested through limited exposure method (ATSM F 1383)
Citation: (Best Manufacturing, 2002)

Nitrile

Best Manufacturing

N-DEX 8005

Degradation Rating: Poor (after 60 minutes)
Breakthrough Time (minutes): 40
Permeation Rate (mcg/cm2/min): 74
Notes: tested through limited exposure method (ATSM F 1383)
Citation: (Best Manufacturing, 2002)
Degradation Rating: Poor (after 60 minutes)
Breakthrough Time (minutes): 30
Permeation Rate (mcg/cm2/min): 99
Notes: Not Listed
Citation: (Best Manufacturing, 2002)

Nitri-Solve 727

Degradation Rating: Good (after 60 minutes)
Breakthrough Time (minutes): 120
Permeation Rate (mcg/cm2/min): 97
Notes: tested through limited exposure method (ATSM F 1383)
Citation: (Best Manufacturing, 2002)
Degradation Rating: Good (after 60 minutes)
Breakthrough Time (minutes): 15
Permeation Rate (mcg/cm2/min): 158
Notes: Not Listed
Citation: (Best Manufacturing, 2002)

Ultimate N-Dex 9905

Degradation Rating: Poor (after 60 minutes of testing)
Breakthrough Time (minutes): 30
Permeation Rate (mcg/cm2/min): 99
Notes: Not Listed
Citation: (Best Manufacturing, 2004)
Degradation Rating: Poor (after 60 minutes of testing)
Breakthrough Time (minutes): 40
Permeation Rate (mcg/cm2/min): 74
Notes: Tested with Limited Exposure Method (ASTM F 1383)
Citation: (Best Manufacturing, 2004)

Ultraflex Nitrile 22R

Degradation Rating: Good (after 60 minutes of testing)
Breakthrough Time (minutes): 30
Permeation Rate (mcg/cm2/min): 87
Notes: Not Listed
Citation: (Best Manufacturing, 2004)
Degradation Rating: Good (after 60 minutes of testing)
Breakthrough Time (minutes): None Detected
Permeation Rate (mcg/cm2/min): 71
Notes: Tested through limited exposure method (ATSM F 1383)
Citation: (Best Manufacturing, 2004)

Nitrile+PVC

Best Manufacturing

Hustler 725R

Degradation Rating: Excellent (after 60 minutes)
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None detected
Notes: Not Listed
Citation: (Best Manufacturing, 2002)
Degradation Rating: Excellent (after 60 minutes)
Breakthrough Time (minutes): >240
Permeation Rate (mcg/cm2/min): None detected
Notes: tested through limited exposure method (ATSM F 1383)
Citation: (Best Manufacturing, 2002)

Plastic Laminate

North -- Safety 4H

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >240
Permeation Rate (mcg/cm2/min): Not reported
Notes: tested at 35 degrees C; 95 degrees F
Citation: (Safety 4, 2002)
Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >240
Permeation Rate (mcg/cm2/min): Not reported
Notes: tested at 21 degrees C; 70 degrees F
Citation: (Safety 4, 2002)

Viton over Butyl

Best Manufacturing

Viton #890

Degradation Rating: Good (after 60 minutes of testing)
Breakthrough Time (minutes): 300
Permeation Rate (mcg/cm2/min): 83
Notes: Not Listed
Citation: (Best Manufacturing, 2004)
Degradation Rating: Good (after 60 minutes of testing)
Breakthrough Time (minutes): >240
Permeation Rate (mcg/cm2/min): None Detected
Notes: Tested with limited exposure method (ASTM F 1383)
Citation: (Best Manufacturing, 2004)

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

Best Manufacturing 579 Edison Street Menlo, GA 30731 USA Phone: (706) 862-2302 Fax: (706) 862-6000 Toll-Free: (800) 241-0323 Website: http://www.bestglove.com Email: USA@bestglove.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
North -- Safety 4H 2000 Plainfield Pike Cranston, RI 02921 USA Phone: (800) 430-4110 Fax: (800) 572-6346 Toll-Free: (800) 430-4110 Website: http://www.safety4.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)

ENGINEERING CONTROLS

"All industrial operations involving the use of dimethyl sulfate should be carried out in fully enclosed systems" (ILO, 1998).

-PHYSICAL HAZARDS

FIRE HAZARD

SUMMARY

POTENTIAL FIRE OR EXPLOSION HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
- Combustible material: may burn but does not ignite readily.
- Substance will react with water (some violently) releasing flammable, toxic or corrosive gases and runoff.
- When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards.
- Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks).
- Vapors may travel to source of ignition and flash back.
- Contact with metals may evolve flammable hydrogen gas.
- Containers may explode when heated or if contaminated with water.
When heated to decomposition, dimethyl sulfate releases highly toxic fumes of sulfur oxides (Lewis, 2000; OHM/TADS , 2000).
If fire becomes uncontrollable or container is exposed to a direct flame, consider evacuation of one-third mile radius (AAR, 2000).

FLAMMABILITY CLASSIFICATION

NFPA Flammability Rating for CAS77-78-1 (NFPA, 2002):

Listed as: Dimethyl Sulfate
Flammability Rating: 2

(2) Combustible. Materials that must be moderately heated before ignition can occur. Including liquids having a flash point above 100 degrees F, and solids that readily give off flammable vapors.

INITIATING OR CONTRIBUTING PROPERTIES

Dimethyl sulfate can ignite in contact with the unheated chlorite. This is presumably due to the formation of very unstable methyl chlorite (Urben, 2000).
It is of moderate flammability when exposed to heat or flame (HSDB , 2000; OHM/TADS , 2000). However, it "evolves flammable and toxic gas when exposed to high temperatures and flames" (ITI, 1995).

FIRE CONTROL/EXTINGUISHING AGENTS

FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)

Note: Most foams will react with the material and release corrosive/toxic gases.

SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)

CO2, dry chemical, dry sand, alcohol-resistant foam.

LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)

Water spray, fog or alcohol-resistant foam.
FOR CHLOROSILANES, DO NOT USE WATER; use AFFF alcohol-resistant medium expansion foam.
Move containers from fire area if you can do it without risk.
Use water spray or for; do not use straight streams.

TANK OR CAR/TRAILER LOAD FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)

Fight fire from maximum distance or use unmanned hose holders or monitor nozzles.
Do not get water inside containers.
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.

NFPA Extinguishing Methods for CAS77-78-1 (NFPA, 2002):

Listed as: Dimethyl Sulfate
Extinguishing Method(s): 3

3: "Water may be used to blanket fire" applies when the liquid has a specific gravity of 1.1 or greater, or is not water-soluble. In this case, water can be gently applied in a fine spray or fog to the liquid surface.

Choose an extinguishing agent suitable for fires in surrounding material as alcohol-resistant foam, carbon dioxide, dry chemical, and carbon tetrachloride base can all be used on dimethyl sulfate itself (AAR, 2000; OHM/TADS , 2000).

Care should be taken if using water directly on dimethyl sulfate. In case of runoff, the hydrolysis to sulfuric acid and methanol evolves heat which can increase concentration of fumes in the air and pollute the environment (AAR, 2000; HSDB , 2000).

Water may be used in flooding quantities as fog and to knock-down vapors (AAR, 2000).

Move containers from fire area if it can be done without risk, and cool exposed containers with water (care should be taken as not to get water inside containers) (HSDB , 2000; Sittig, 1991).

COMBUSTION TOXICITY

When heated to decomposition, dimethyl sulfate releases highly toxic fumes of sulfur oxides (Lewis, 2000; OHM/TADS , 2000).

EXPLOSION HAZARD

"Pure dimethyl sulfate and concentrated aqueous ammonia react extremely violently with one another" (NFPA, 1997).

Dimethyl sulfate is used in production of methyl azide in a reaction with sodium azide. If the pH of this reaction is allowed to fall below 5, highly explosive hydrazoic acid can form (NFPA, 1997).

"In absence of diluent, quaternation of some tertiary organic bases may proceed explosively" (Urben, 2000).

Containers of dimethyl sulfate may explode if exposed to heat or contaminated with water (HSDB , 2000).

DUST/VAPOR HAZARD

When heated to decomposition, dimethyl sulfate releases highly toxic fumes of sulfur oxides (Lewis, 2000; OHM/TADS , 2000).

Vapors of dimethyl sulfate cause severe irritation to eyes and throat and they cannot be tolerated even at low concentrations (CHRIS , 2000).

REACTIVITY HAZARD

When heated to decomposition, dimethyl sulfate releases highly toxic fumes of oxides of carbon and sulfur (Lewis, 2000; OHM/TADS , 2000).

It reacts with strong oxidizers (such as chlorine, bromine, and fluorine) and ammonia solutions (NIOSH , 2000; Sittig, 1991).

"Pure dimethyl sulfate and concentrated aqueous ammonia react extremely violently with one another" (NFPA, 1997).

Dimethyl sulfate is used in production of methyl azide in a reaction with sodium azide. If the pH of this reaction is allowed to fall below 5, highly explosive hydrazoic acid can form (NFPA, 1997).

In absence of diluent, quaternation of some tertiary organic bases may proceed explosively (Urben, 2000).

Dimethyl sulfate is hydrolyzed to sulfuric acid and methanol with evolution of heat (this can increase concentration of fumes in the air). It is noncorrosive when anhydrous, but can corrode metal (such as steel) when wet (CHRIS , 2000; HSDB , 2000; OHM/TADS , 2000).

It is incompatible with strong acids, strong alkalies (Pohanish & Greene, 1997).

Dimethyl sulfate can ignite in contact with the unheated chlorite. This is presumably due to the formation of very unstable methyl chlorite (Urben, 2000).

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. 1595 - Dimethyl sulfate

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: 0.1 kilometers (0.1 miles).

LARGE SPILLS

First isolate in all directions: 60 meters (200 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 0.5 kilometers (0.3 miles); or
during the NIGHT for: 0.8 kilometers (0.5 miles).

DOT ID No. 1595 - Dimethyl sulphate

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: 0.1 kilometers (0.1 miles).

LARGE SPILLS

First isolate in all directions: 60 meters (200 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 0.5 kilometers (0.3 miles); or
during the NIGHT for: 0.8 kilometers (0.5 miles).

SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)

Increase, in the downwind direction, as necessary, the isolation distance of at least 50 meters (150 feet) for liquids and 25 meters (75 feet) for solids in all directions.

FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (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 156 (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 in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.
Keep unauthorized personnel away.
Stay upwind.
Keep out of low areas.
Ventilate enclosed areas.

If fire becomes uncontrollable or container is exposed to direct flame, consider evacuation of one-third mile radius (AAR, 2000).

AIHA ERPG Values for CAS77-78-1 (AIHA, 2006):

Listed as Dimethyl Sulfate
ERPG-1 (units = ):
ERPG-2 (units = ):
ERPG-3 (units = ):
Under Ballot, Review, or Consideration: Yes
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 CAS77-78-1 (U.S. Department of Energy, Office of Emergency Management, 2010):

Listed as Dimethyl sulfate
TEEL-0 (units = ppm): 0.024
TEEL-1 (units = ppm): 0.024
TEEL-2 (units = ppm): 0.12
TEEL-3 (units = ppm): 1.6
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 CAS77-78-1 (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):

Not Listed

NIOSH IDLH Values for CAS77-78-1 (National Institute for Occupational Safety and Health, 2007):

IDLH: 7 ppm
Note(s): Ca

(Ca) NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A).

CONTAINMENT/WASTE TREATMENT OPTIONS

SUMMARY

SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (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 damaged containers or spilled material unless wearing appropriate protective clothing.
- Stop leak if you can do it without risk.
- A vapor suppressing foam may be used to reduce vapors.
- FOR CHLOROSILANES, use AFFF alcohol-resistant medium expansion foam to reduce vapors.
- DO NOT GET WATER on spilled substance or inside containers.
- Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material.
- Prevent entry into waterways, sewers, basements or confined areas.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (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.
LAND SPILLS
- Ventilate the area of spill or leak and stay upwind (AAR, 1998; Sittig, 1991).
- Absorb with vermiculite, dry sand, or soil or neutralize with crushed limestone, soda ash, or lime, then deposit in sealed containers for proper disposal (AAR, 1998; Sittig, 1991).
WATER SPILLS
- Pump or vacuum undissolved portion from the bottom and use carbon or peat on dissolved portion (OHM/TADS , 2000).
Persons in charge of vessels or facilities are required to notify the National Response Center immediately when there is a release in an amount equal to or greater than 100 lb or 45.4 kg (HSDB , 2000).

SMALL LEAK/SPILL

SMALL SPILL PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
- Cover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain.
- Use clean non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal.

LARGE LEAK/SPILL

Untrained workers should be strictly forbidden to attempt to clean up any massive spills (such as a container breakage). "Many accidents with dimethyl supfate have been the result of hasty and uninformed clean-up attempts" (ILO, 1998). Workers who enter the area should wear positive-pressure airline hose masks or self-contained breathing apparatus; canister-type gas masks are not safe. After building is evacuated, water or 5% sodium hydroxide (caustic soda) should be used to decompose dimethyl sulfate (HSDB , 2000).

WASTE TREATMENT OPTIONS

CHEMICAL TREATMENT

Alkaline hydrolysis may be used to dispose dimethyl sulfate (Sittig, 1991). It can be neutralized by sodium bicarbonate, lime, 2-5 % solution of soda ash, or caustic soda (CHRIS , 2000; HSDB , 2000; OHM/TADS , 2000).
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

"Incineration (1800 degrees F, 1.5 seconds minimum) of dilute, neutralized dimethyl sulfate waste is recommended. The incinerator must be equipped with efficient scrubbing devices for oxides of sulfur" (Sittig, 1991).
For disposal, first, pour dimethyl sulfate onto vermiculite, sodium bicarbonate, or a sand-soda ash (90:10) mixture; secondly, mix and shovel into paper boxes; lastly, place in a closed incinerator with afterburner (OHM/TADS , 2000).
Dimethyl sulfate can also be dissolved in a flammable solvent and sprayed into the fire box of an incinerator equipped with afterburner and alkali scrubber (OHM/TADS , 2000).

-ENVIRONMENTAL HAZARD MANAGEMENT

POLLUTION HAZARD

Dimethyl sulfate has been identified as an air pollutant in Los Angeles It was present in both particles and the gas phase. Dimethyl sulfate, along with monomethyl hydrogen sulfate, constituted the majority of airborne sulfate species during a smog episode (Eatough et al, 1986).

Dimethyl sulfate has been found in coal fly ash at levels as high as 830 ppm (Tan et al, 1983).

Dimethyl sulfate enters the environment during its production and use as an industrial methylating agent as well as in emissions from power plants burning coal (HSDB , 2000).

ENVIRONMENTAL FATE AND KINETICS

Dimethyl sulfate is an air pollutant and is present in both the particulate and gas phases (Eatough et al, 1986).
If released into the atmosphere, dimethyl sulfate will be subject to gravitational settling and rain-out (HSDB , 1992).
"Vapor-phase dimethyl sulfate will be degraded in the atmosphere by reaction with water and photochemically-produced hydroxyl radicals" (HSDB , 2000).
Dimethyl sulfate is likely to become incorporated into fog and cloudwater and then hydrolyzed (HSDB , 2000).

WATER

SURFACE WATER
- It will rapidly hydrolyze in groundwater to sulfuric acid and methanol (HSDB , 2000).

SOIL

TERRESTRIAL
- If dimethyl sulfate is released on land,because of the hydroylsis, it would not be expected to leach into soil because of its low adsorptivity (HSDB , 2000).
- It will rapidly hydrolyze in damp soil (HSDB , 2000).

OTHER

OTHER
- It has an estimated half-life of >32 days in the atmosphere with 5x10(5) hydroxyl radicals per cubic centimeter (HSDB , 2000).
- It has a half-life in air of between 36.5 hours to 365 hours, based on the estimated photooxidation half-life in air (Howard et al, 1991).
- It has a half-life in water (both surface water and ground water) of between 1.2 hours (based on measured overall hydrolysis rate constant at pH 7 and 25 degrees C) to 12 hours (based on maximum time observed for complete hydrolysis in neutral, slightly basic, and acidic aqueous solutions) (Howard et al, 1991).
- It has a half-life in soil of between 1.2 hours (based on measured overall hydrolysis rate constant for pH 7 at 25 degrees C) to 12 hours (based on maximum time observed for complete hydrolysis in neutral, slightly basic, and acidic aqueous solutions) (Howard et al, 1991).

BIODEGRADATION

Based on scientific judgment, it has an unacclimated aqueous aerobic biodegradation half-life of between 168 hours (7 days) and 672 hours (4 weeks) (Howard et al, 1991).

Based on scientific judgment, it has an unacclimated aqueous anaerobic biodegradation half-life of between 672 hours (28 days) and 2688 hours (16 weeks) (Howard et al, 1991).

BIOACCUMULATION

FISH

Dimethyl sulfate is not expected to bioconcentrate in fish (HSDB , 2000).

ENVIRONMENTAL TOXICITY

Freshwater toxicity:

TL50 - BLUEGILL: 7.5 ppm for 96H (OHM/TADS , 2000)

Saltwater toxicity:

TL50 - ATLANTIC SILVERSIDE: 15 ppm for 96H (OHM/TADS , 2000)

-PHYSICAL/CHEMICAL PROPERTIES

MOLECULAR WEIGHT

126.13

DESCRIPTION/PHYSICAL STATE

Dimethyl sulfate is a colorless, oily liquid with a faint, onion-like odor (Budavari, 2000; Haswell, 1960).

VAPOR PRESSURE

0.1 mmHg (NIOSH , 2000)

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

<1 mmHg (at 20 degrees C) (NFPA, 1997)

0.677 mmHg (at 25 degrees C) (HSDB , 2000)

15 mmHg (at 76 degrees C) (OHM/TADS , 2000)

SPECIFIC GRAVITY

OTHER TEMPERATURE AND/OR PRESSURE

1.3322 (at 20/4 degrees C) (Budavari, 2000; HSDB , 2000)
1.332 (at 20 degrees C) (ACGIH, 1991)

TEMPERATURE AND/OR PRESSURE NOT LISTED

1.3332 (ITI, 1995)
1.3516 (Lewis, 1997)
1.33 (NFPA, 1997; OHM/TADS , 2000)

DENSITY

OTHER TEMPERATURE AND/OR PRESSURE

1.33 g/cm(3) (at 15 degrees C) (CHRIS , 2000)
1.332 g/cm(3) (at 15 degrees C) (Lewis, 2000)
1.332 kg/L (at 20 degrees C) (ACGIH, 1991)
1.33 kg/L (at 20 degrees C) (Ashford, 1994a)

FREEZING/MELTING POINT

FREEZING POINT

-26.8 degrees C (Lewis, 1997a)
-27 degrees C (Lewis, 2000a)
-31.8 degrees C; -25.2 degrees F; 241.4 K (CHRIS, 2000; ITI, 1995)

MELTING POINT

-27 degrees C (ACGIH, 1991a; Ashford, 1994; Budavari, 2000; HSDB , 2000)
-31.7 degrees C (Weast, 1989)
-31.8 degrees C (Lewis, 2000a; OHM/TADS, 2000)
-32 degrees C; -25 degrees F (NFPA, 1997)

BOILING POINT

76 degrees C (at 15 mmHg) (HSDB , 2000)

370 degrees F (decomposition) (NFPA, 1997; NIOSH , 2000)

188 degrees C (decomposition) (Budavari, 2000; HSDB , 2000; NFPA, 1997)

188.8 degrees C; 371.8 degrees F; 462.0 K (CHRIS , 2000; ITI, 1995)

FLASH POINT

83.3 degrees C; 182 degrees F (closed cup) (CHRIS , 2000; HSDB , 2000; Lewis, 1997)

84.4 degrees C (closed cup) (ITI, 1995)

115.6 degrees C (open cup) (ITI, 1995)

240 degrees F (open cup) (CHRIS , 2000)

AUTOIGNITION TEMPERATURE

187.8 degrees C; 370 degrees F (ACGIH, 1991; CHRIS , 2000; NFPA, 1997)

188 degrees C (NFPA, 1997)

SOLUBILITY

IN WATER

2.8 g/100 mL (at 18 degrees C) (Budavari, 2000)
28000 ppm (at 25 degrees C) (OHM/TADS , 2000)
3% (at 64 degrees F) (NIOSH , 2000)
It sinks and mixes slowly with water in a non-hazardous reaction (CHRIS , 2000).
Hydrolysis is rapid at or above 18 degrees C (Budavari, 2000).

IN ORGANIC SOLVENTS

It is soluble in acetone, alcohol, aromatic hydrocarbons, dioxane, benzene, and ether (Budavari, 2000; HSDB , 2000).
It is sparingly soluble in aliphatic hydrocarbons and carbon disulfide (Budavari, 2000)

OCTANOL/WATER PARTITION COEFFICIENT

log Kow = 0.032 (estimated) (HSDB , 2000)

HENRY'S CONSTANT

3.37x10(-6) atm-m(3)/mol (Ehrenfeld et al, 1986)

SPECTRAL CONSTANTS

15253 (Sadtler Research Laboratories IR Grating Collection) (HSDB , 2000)

MASS

219 (National Bureau of Standards EPA-NIH Mass Spectra Data Base, NSRDS-NBS-63) (HSDB , 2000)

OTHER/PHYSICAL

ODOR THRESHOLD

Currently not available (CHRIS , 2000)

INDEX OF REFRACTION

1.3874 (at 20 degrees C/d) (Budavari, 2000; ITI, 1995)

LIQUID WATER INTERFACIAL TENSION

20 dynes/cm; 0.02 N/m (at 20 degrees C) (CHRIS , 2000; HSDB , 2000)

-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.

65 FR 14186: 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, 2000.

65 FR 39264: 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, 2000.

65 FR 77866: 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, 2000.

66 FR 21940: 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, 2001.

67 FR 7164: 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, 2002.

68 FR 42710: 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, 2003.

69 FR 54144: 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, 2004.

AAR: Emergency Handling of Hazardous Materials in Surface Transportation, Bureau of Explosives, Association of American Railroads, Washington, DC, 1998.

AAR: Emergency Handling of Hazardous Materials in Surface Transportation, Bureau of Explosives, Association of American Railroads, Washington, DC, 2000.

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DIMETHYL SULFATE

Classification | Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents