Dimethyl Sulfate

H301: Toxic if swallowed [Danger Acute toxicity, oral]

H314: Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H317: May cause an allergic skin reaction [Warning Sensitization, Skin]

H330: Fatal if inhaled [Danger Acute toxicity, inhalation]

H341: Suspected of causing genetic defects [Warning Germ cell mutagenicity]

H350: May cause cancer [Danger Carcinogenicity]

P203, P260, P261, P264, P270, P271, P272, P280, P284, P301+P316, P301+P330+P331, P302+P352, P302+P361+P354, P304+P340, P305+P354+P338, P316, P318, P320, P321, P330, P333+P317, P362+P364, P363, P403+P233, P405, and P501 (click each P-code to see the statement)

This chemical does not meet GHS hazard criteria for < 0.1% (1 of 1004) of reports.

H301 (> 99.9%): Toxic if swallowed [Danger Acute toxicity, oral]

H310 (43.9%): Fatal in contact with skin [Danger Acute toxicity, dermal]

H314 (> 99.9%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H317 (> 99.9%): May cause an allergic skin reaction [Warning Sensitization, Skin]

H318 (21.2%): Causes serious eye damage [Danger Serious eye damage/eye irritation]

H319 (43.9%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]

H330 (> 99.9%): Fatal if inhaled [Danger Acute toxicity, inhalation]

H335 (52.7%): May cause respiratory irritation [Warning Specific target organ toxicity, single exposure; Respiratory tract irritation]

H341 (99.8%): Suspected of causing genetic defects [Warning Germ cell mutagenicity]

H350 (99.8%): May cause cancer [Danger Carcinogenicity]

P203, P260, P261, P262, P264, P264+P265, P270, P271, P272, P280, P284, P301+P316, P301+P330+P331, P302+P352, P302+P361+P354, P304+P340, P305+P351+P338, P305+P354+P338, P316, P317, P318, P319, P320, P321, P330, P333+P317, P337+P317, P361+P364, P362+P364, P363, P403+P233, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 1004 reports by companies from 23 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Reported as not meeting GHS hazard criteria per 1 of 1004 reports by companies.

There are 22 notifications provided by 1003 of 1004 reports by companies with hazard statement code(s).

Information may vary between notifications depending on impurities, additives, and other factors. The percentage value in parenthesis indicates the notified classification ratio from companies that provide hazard codes. Only hazard codes with percentage values above 10% are shown. For more detailed information, please visit ECHA C&L website.

H301 (100%): Toxic if swallowed [Danger Acute toxicity, oral]

H314 (100%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H317 (100%): May cause an allergic skin reaction [Warning Sensitization, Skin]

H330 (100%): Fatal if inhaled [Danger Acute toxicity, inhalation]

H341 (100%): Suspected of causing genetic defects [Warning Germ cell mutagenicity]

H350 (100%): May cause cancer [Danger Carcinogenicity]

Aggregated GHS information provided per 39 reports by companies from 2 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

H334 (97.4%): May cause allergy or asthma symptoms or breathing difficulties if inhaled [Danger Sensitization, respiratory]

P203, P233, P260, P261, P264, P270, P271, P272, P280, P284, P301+P316, P301+P330+P331, P302+P352, P302+P361+P354, P304+P340, P305+P354+P338, P316, P318, P320, P321, P330, P333+P317, P342+P316, P362+P364, P363, P403, P403+P233, P405, and P501 (click each P-code to see the statement)

H227: Combustible liquid [Warning Flammable liquids]

H402: Harmful to aquatic life [Hazardous to the aquatic environment, acute hazard]

P210, P273, P280, P370+P378, P403, and P501 (click each P-code to see the statement)

H318: Causes serious eye damage [Danger Serious eye damage/eye irritation]

H335: May cause respiratory irritation [Warning Specific target organ toxicity, single exposure; Respiratory tract irritation]

H361: Suspected of damaging fertility or the unborn child [Warning Reproductive toxicity]

H370: Causes damage to organs [Danger Specific target organ toxicity, single exposure]

H373: May causes damage to organs through prolonged or repeated exposure [Warning Specific target organ toxicity, repeated exposure]

Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer immediately for medical attention.

Remove contaminated clothes. Rinse skin with plenty of water or shower. Refer immediately for medical attention.

Rinse with plenty of water (remove contact lenses if easily possible). Refer immediately for medical attention.

Rinse mouth. Give one or two glasses of water to drink. Do NOT induce vomiting. Refer immediately for medical attention.

Warning: Symptoms may be delayed up to 12 hours.

Signs and Symptoms of Dimethyl Sulfate Exposure: Dimethyl sulfate is irritating to the eyes, skin, mucous membranes, and respiratory tract. Severe dermal burns may be seen. Headache and giddiness are early signs of acute exposure which may be followed by changes in vision, lacrimation (tearing), photophobia, cough, difficulty in breathing, nausea, and vomiting. In severe cases, seizures, paralysis, delirium, and coma may occur.

Emergency Life-Support Procedures: Acute exposure to dimethyl sulfate may require decontamination and life support for the victims. Emergency personnel should wear protective clothing appropriate to the type and degree of contamination. Air-purifying or supplied-air respiratory equipment should also be worn, as necessary. Rescue vehicles should carry supplies such as plastic sheeting and disposable plastic bags to assist in preventing spread of contamination.

Inhalation Exposure:

1. Move victims to fresh air. Emergency personnel should avoid self-exposure to dimethyl sulfate.

2. Evaluate vital signs including pulse and respiratory rate, and note any trauma. If no pulse is detected, provide CPR. If not breathing, provide artificial respiration. If breathing is labored, administer oxygen or other respiratory support.

3. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures.

4. Transport to a health care facility.

Dermal/Eye Exposure:

1. Remove victims from exposure. Emergency personnel should avoid self-exposure to dimethyl sulfate.

3. Remove contaminated clothing as soon as possible.

4. If eye exposure has occurred, eyes must be flushed with copious amounts of lukewarm water for at least 15 minutes.

5. Wash exposed skin areas thoroughly with soap and water.

6. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures.

7. Transport to a health care facility.

Ingestion Exposure:

1. Evaluate vital signs including pulse and respiratory rate, and note any trauma. If no pulse is detected, provide CPR. If not breathing, provide artificial respiration. If breathing is labored, administer oxygen or other respiratory support.

2. DO NOT induce vomiting or attempt to neutralize!

4. Give the victims water or milk: children up to 1 year old, 125 mL (4 oz or 1/2 cup); children 1 to 12 years old, 200 mL (6 oz or 3/4 cup); adults, 250 mL (8 oz or 1 cup). Water or milk should be given only if victims are conscious and alert.

5. Activated charcoal may be administered if victims are conscious and alert. Use 15 to 30 g (1/2 to 1 oz) for children, 50 to 100 g (1-3/4 to 3-1/2 oz) for adults, with 125 to 250 mL (1/2 to 1 cup) of water.

6. Promote excretion by administering a saline cathartic or sorbitol to conscious and alert victims. Children require 15 to 30 g (1/2 to 1 oz) of cathartic; 50 to 100 g (1-3/4 to 3- 1/2 oz) is recommended for adults.

7. Transport to a health care facility. (EPA, 1998)

General First Aid:

· Call 911 or emergency medical service.

· Ensure that medical personnel are aware of the material(s) involved, take precautions to protect themselves and avoid contamination.

· Move victim to fresh air if it can be done safely.

· Administer oxygen if breathing is difficult.

· If victim is not breathing:

-- DO NOT perform mouth-to-mouth resuscitation; the victim may have ingested or inhaled the substance.

-- If equipped and pulse detected, wash face and mouth, then give artificial respiration using a proper respiratory medical device (bag-valve mask, pocket mask equipped with a one-way valve or other device).

-- If no pulse detected or no respiratory medical device available, provide continuous compressions. Conduct a pulse check every two minutes or monitor for any signs of spontaneous respirations.

· Remove and isolate contaminated clothing and shoes.

· For minor skin contact, avoid spreading material on unaffected skin.

· In case of contact with substance, remove immediately by flushing skin or eyes with running water for at least 20 minutes.

· For severe burns, immediate medical attention is required.

· Effects of exposure (inhalation, ingestion, or skin contact) to substance may be delayed.

Wear positive pressure breathing apparatus and special protective clothing. Dike fire control water for later disposal. Do not scatter material.

To extinguish small fires use water, foam, carbon dioxide, and dry chemicals. For large fires use water spray, fog, or foam. Move container from fire area if you can do it without risk. Cool containers exposed to flames with water. Fight fire from a maximum distance. (EPA, 1998)

Use powder, foam, carbon dioxide, water spray.

Water, foam, carbon dioxide, dry chemical ... .

If material on fire or involved in fire: Use dry chemical, dry sand, or carbon dioxide. Do not use water on material itself. If large quantities of combustibles are involved, use water in flooding quantities as spray and fog. Use water spray to knock down vapors. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible.

Use dry chemical., foam, carbon dioxide, or water spray. Use water spray to keep fire-exposed containers cool. Approach fire from upwind to avoid hazardous vapors and toxic decomposition products.

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.

· Keep unauthorized personnel away.

· Stay upwind, uphill and/or upstream.

· Ventilate closed spaces before entering, but only if properly trained and equipped.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from 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 alcohol-resistant 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.

Small Spill

· 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.

Excerpt from ERG Guide 156 [Substances - Toxic and/or Corrosive (Combustible / Water-Sensitive)]:

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.

SPILL: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 1595 datasheet.

FIRE: If tank, rail tank car or highway tank 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. (ERG, 2024)

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.

· For highlighted materials: see Table 1 - Initial Isolation and Protective Action Distances.

· For non-highlighted materials: increase the immediate precautionary measure distance, in the downwind direction, as necessary.

· If tank, rail tank car or highway tank 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.

Small spill:

- ISOLATE in all directions: 30 m (100 ft)

Large spill:

- ISOLATE in all directions: 60 m (200 ft)

- PROTECT people from downwind during DAY time: 0.1 km (0.1 mi)

- PROTECT people from downwind during NIGHT time: 0.1 km (0.1 mi)

- PROTECT people from downwind during DAY time: 0.2 km (0.1 mi)

- PROTECT people from downwind during NIGHT time: 0.7 km (0.4 mi)

Evacuate danger area! Consult an expert! Personal protection: complete protective clothing including self-contained breathing apparatus. Ventilation. Do NOT let this chemical enter the environment. Collect leaking liquid in sealable containers. Absorb remaining liquid in dry sand or inert absorbent. Then store and dispose of according to local regulations.

Spillage should only be dealt with by trained personnel wearing full protective clothing, a full-face mask, and positive-pressure breathing apparatus. Soda ash or 3% ammonia solution may be applied to liquid spills. Sprays of 3% ammonia solution may be used to "knock down" the vapor over spillages. After complete neutralization, spillages may be washed away... If dimethyl sulfate has entered a watercourse ... or contaminated soil or vegetation, advise the police and public authorities.

Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or similar material and deposit in sealed containers. Keep this chemical out of a confined space ... because of the possibility of an explosion ... It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Contact your Department of Environmental Protection or your regional office of the federal EPA for specific recommendations. If employees are required to clean up spills, they must be properly trained and equipped. OSHA 1910.120(q) may be applicable.

PRECAUTIONS FOR "CARCINOGENS": A high-efficiency particulate arrestor (HEPA) or charcoal filter can be used to minimize amt of carcinogen in exhausted air, ventilated safety cabinets, lab hoods, glove boxes, or animal rooms. ... Filter housing that is designed so that used filters can be transferred into plastic bags without contaminating maintenance staff is avail commercially. Filters should be placed in plastic bags immediately after removal. ... The plastic bag should be sealed immediately .... The sealed bag should be labelled properly. Waste liquids ... should be placed or collected in proper containers for disposal. The lid should be secured & the bottles properly labelled. Once filled, bottles should be placed in plastic bags, so that outer surface ... is not contaminated. ... The plastic bag should also be sealed & labelled. ... Broken glassware ... should be decontaminated by solvent extraction, by chemical destruction, or in specially designed incinerators. /Chemical Carcinogens/

1. Ventilate areas of spill or leak. 2. For small quantities, absorb on paper towels. Evaporate in a safe place (such as fume hood). Allow sufficient time for evaporating vapors to completely clear the hood ductwork. Burn the paper in a suitable location away from combustible materials. Large quantities can be collected and atomized in a suitable combustion chamber equipped with an appropriate effluent gas cleaning device.

For more Cleanup Methods (Complete) data for DIMETHYL SULFATE (8 total), please visit the HSDB record page.

For the treatment and disposal of waste, the recommended methods are alkaline hydrolysis, incineration, and landfill. Do not use open burning (e.g., as a boiler fuel) or evaporation for waste disposal. For incineration, dimethyl sulfate should be dissolved in a combustible solvent and sprayed into a furnace with an afterburner and an alkali scrubber. Dimethyl sulfate may be decomposed by adding a dilute alkaline solution; the mixture should be stirred and then allowed to settle. The resulting solution is then neutralized by acid or alkali as appropriate and drained into a sewer. When rapid decomposition is needed the waste may be warmed. It may also be adsorbed on vermiculite, packed in drums, buried and covered immediately.

Excerpt from ERG Guide 156 [Substances - Toxic and/or Corrosive (Combustible / Water-Sensitive)]:

ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from 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 alcohol-resistant 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.

SMALL SPILL: 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. (ERG, 2024)

Separated from food and feedstuffs and incompatible materials. See Chemical Dangers. Cool. Dry. Well closed. Ventilation along the floor. Store in an area without drain or sewer access.

PRECAUTIONS FOR "CARCINOGENS": Storage site should be as close as practicable to lab in which carcinogens are to be used, so that only small quantities required for ... expt need to be carried. Carcinogens should be kept in only one section of cupboard, an explosion-proof refrigerator, or freezer (depending on chemicophysical properties ...) that bears appropriate label. An inventory ... should be kept, showing quantity of carcinogen & date it was acquired ... . Facilities for dispensing ... should be contiguous to storage area. /Chemical Carcinogens/

Store in a cool, dry, well-ventilated location. Separate from bases, oxidizing materials, water and metal.

· Wear positive pressure self-contained breathing apparatus (SCBA).

· Wear chemical protective clothing that is specifically recommended by the manufacturer when there is NO RISK OF FIRE.

· Structural firefighters' protective clothing provides thermal protection but only limited chemical protection.

TIH (Toxic Inhalation Hazard) - Term used to describe gases and volatile liquids that are toxic when inhaled. Some are TIH materials themselves, e.g., chlorine, and some release TIH gases when spilled in water, e.g., chlorosilanes. [ERG 2016].

AEGL 1: Notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effects are not disabling and are transient and reversible upon cessation of exposure (Unit: ppm)

AEGL 2: Irreversible or other serious, long-lasting adverse health effects or an impaired ability to escape (Unit: ppm)

AEGL 3: Life-threatening health effects or death (Unit: ppm)

AEGLs Status: Interim

0.024 [ppm]

0.12 [ppm]

1.6 [ppm]

0.1 ppm (0.5 mg/m³)

Ca TWA 0.1 ppm (0.5 mg/m3) [skin] See Appendix A

1.0 [ppm]

1 ppm (5 mg/m³)

TWA 1 ppm (5 mg/m3) [skin] See Appendix G

7 ppm ; A potential occupational carcinogen. (NIOSH, 2024)

7.0 [ppm]

Excerpts from Documentation for IDLHs: The chosen IDLH is based on the statement by Patty [1963] that a 20­minute exposure to 13 ppm caused severe symptoms in monkeys and a 20­minute exposure to 75 ppm resulted in the LC50 for guinea pigs [Ghiringhelli et al. 1957; Ghiringhelli and Sironi 1958].

NIOSH considers dimethyl sulfate to be a potential occupational carcinogen.

Ca [7 ppm]

See: 77781

0.1 [ppm]

8 hr Time Weighted Avg (TWA): 0.1 ppm, skin

Excursion Limit Recommendation: Excursions in worker exposure levels may exceed 3 times the TLV-TWA for no more than a total of 30 minutes during a work day, and under no circumstances should they exceed 5 times the TLV-TWA, provided that the TLV-TWA is not exceeded.

A3; Confirmed animal carcinogen with unknown relevance to humans.

0.1 ppm as TWA; (skin); A3 (confirmed animal carcinogen with unknown relevance to humans).

0.1 ppm [1985]

skin absorption (H); carcinogen category: 2

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

CAUTION: For Acetyl bromide (UN1716), use CO2 or dry chemical only.

Small Fire

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

Large Fire

· Water spray, fog or alcohol-resistant foam.

· FOR CHLOROSILANES, DO NOT USE WATER; use alcohol-resistant foam.

· If it can be done safely, move undamaged containers away from the area around the fire.

· Avoid aiming straight or solid streams directly onto the product.

Fire Involving Tanks, Rail Tank Cars or Highway Tanks

· Fight fire from maximum distance or use unmanned master stream devices or monitor nozzles.

Dimethyl sulfate is a colorless oily liquid, odorless to a faint onion-like odor. It is very toxic by inhalation. It is a combustible liquid and has a flash point of 182 °F. It is slightly soluble in water and decomposed by water to give sulfuric acid with evolution of heat. It is corrosive to metals and tissue. It is a potent methylating agent.

CBI; Liquid

Colorless, oily liquid with a faint, onion-like odor; [NIOSH]

COLOURLESS OILY LIQUID.

Colorless, oily liquid with a faint, onion-like odor.

Colorless oily liquid

Essentially odorless

Faint, onion-like odor

About 370 °F (with decomposition) (EPA, 1998)

About 188 °C with decomposition

BP: 76 °C at 15 mm Hg

370 °F (decomposes)

370 °F (Decomposes)

-25.15 °F (EPA, 1998)

-31.7 °C

182 °F (EPA, 1998)

182 °F (83 °C) (open cup)

83 °C c.c.

3 % at 64 °F (NIOSH, 2024)

Sol in ether, dioxane, acetone, aromatic hydrocarbons.

Sparingly sol in carbon disulfide, aliphatic hydrocarbons.

Miscible in ethanol; soluble in ethyl ether, carbon tetrachloride and benzene; insoluble in carbon disulfide

Solubility in water 2.8 g/100 ml at 18 °C. Hydrolysis is rapid at or above this temperature.

In water, 2,8X10+4 mg/L at 18 °C

Solubility in water, g/100ml at 18 °C: 2.8

(64 °F): 3%

1.3283 at 68 °F (EPA, 1998) - Denser than water; will sink

1.3322 g/cu cm at 20 °C/4 °C

Relative density (water = 1): 1.3

1.3322 @ 20°C

4.35 (EPA, 1998) - Heavier than air; will sink (Relative to Air)

4.35 (Air = 1)

Relative vapor density (air = 1): 4.4

0.1 to 0.5 mmHg at 68 °F (EPA, 1998)

0.67 [mmHg]

0.677 mm Hg at 25 °C

Vapor pressure, Pa at 20 °C: 65

0.1 mmHg

0.677 [mm Hg] @25 °C

Stable at room temperature.

Water soluble.

Esters, Sulfate Esters, Phosphate Esters, Thiophosphate Esters, and Borate Esters

Water-Reactive

Pure DIMETHYL SULFATE and concentrated aqueous ammonia react extremely violently with one another, as is the case for tertiary organic bases, [NFPA 491M, 1991]. Dimethyl sulfate ignites in contact with unheated barium chlorite, due to the rapid formation of unstable methyl chlorite. The product of methylating an unnamed material at 110 °C was allowed to remain in a reactor for 80 min. before the reactor exploded. This involved a sulfur ester such as dimethyl sulfate, [MCA Case History No. 1786].

Can react with oxidizing materials.

The substance decomposes on heating or on burning producing toxic fumes including sulfur oxides. The solution in water is a medium strong acid. Reacts with water to produce sulfuric acid with evolution of heat. Reacts violently with concentrated aqueous ammonia, bases, acids and strong oxidants with risk of fire and explosion.

... Reacts explosively with concentrated aqueous ammonia.

The aqueous solution is a medium strong acid. Forms explosive mixture with air. Violent reaction with strong oxidizers, strong acids, strong alkalies, concentrated ammonia solutions with risks of fire and explosions. Reacts with water evolving heat and forming sulfuric acid. Attacks metals in the presence of moisture.

For more Hazardous Reactivities and Incompatibilities (Complete) data for DIMETHYL SULFATE (6 total), please visit the HSDB record page.

Strong oxidizers, ammonia solutions [Note: Decomposes in water to sulfuric acid; corrosive to metals.]

Dimethyl sulfate

Evaluation: There is inadequate evidence for the carcinogenicity in humans of dimethyl sulfate. There is sufficient evidence for the carcinogenicity in experimental animals of dimethyl sulfate. Overall evaluation: Dimethyl sulfate is probably carcinogenic to humans (Group 2A). In making the overall evaluation, the Working Group took into consideration that dimethyl sulfate is a potent genotoxic chemical which can directly alkylate DNA both in vitro and in vivo.

A3; Confirmed animal carcinogen with unknown relevance to humans.

Dimethyl Sulfate: reasonably anticipated to be a human carcinogen.

Group 2A: Probably carcinogenic to humans

Volume 4: (1974) Some Aromatic Amines, Hydrazine and Related Substances, N-Nitroso Compounds and Miscellaneous Alkylating Agents

Volume Sup 7: Overall Evaluations of Carcinogenicity: An Updating of IARC Monographs Volumes 1 to 42, 1987; 440 pages; ISBN 92-832-1411-0 (out of print)

Volume 71: (1999) Re-evaluation of Some Organic Chemicals, Hydrazine and Hydrogen Peroxide (Part 1, Part 2, Part 3)

NB Overall evaluation upgraded to Group 2A with supporting evidence from other relevant data

The substance can be absorbed into the body by inhalation of its vapour, through the skin and by ingestion.

inhalation, skin absorption, ingestion, skin and/or eye contact

Cough. Sore throat. Burning sensation. Shortness of breath. Headache. Symptoms may be delayed.

MAY BE ABSORBED! Redness. Pain. Blisters. Skin burns.

Redness. Pain. Burns. Permanent loss of vision.

Burns in mouth and throat. Burning sensation in the throat and chest. Abdominal cramps. Vomiting. Convulsions. Shock or collapse. Further see Inhalation.

irritation eyes, nose; headache; dizziness; conjunctivitis; photophobia (abnormal visual intolerance to light); periorbital (situated around the eye) edema; dysphonia, aphonia, dysphagia, productive cough; chest pain; dyspnea (breathing difficulty), cyanosis; vomiting, diarrhea; dysuria; analgesia; fever; proteinuria, hematuria (blood in the urine); eye, skin burns; delirium; [potential occupational carcinogen]

Eyes, skin, respiratory system, liver, kidneys, central nervous system

[in animals: nasal & lung cancer]

Occupational hepatotoxin - Secondary hepatotoxins: the potential for toxic effect in the occupational setting is based on cases of poisoning by human ingestion or animal experimentation.

Dermatotoxin - Skin burns.

Toxic Pneumonitis - Inflammation of the lungs induced by inhalation of metal fumes or toxic gases and vapors.

IARC Carcinogen - Class 2: International Agency for Research on Cancer classifies chemicals as probable (2a), or possible (2b) human carcinogens.

NTP Carcinogen - Reasonably anticipated to be a human carcinogen.

ACGIH Carcinogen - Confirmed Animal.

LC50 (rat) = 45 mg/m3/4 hr

LC50 Guinea pig inhalation 167 mg/cu m (32 ppm)/60 min.

LC50 Mouse inhalation 513 mg/cu m (98 ppm)/60 min.

LC50 Mouse inhalation 280 mg/cu m/4 hr.

LD50 Mouse ip 61 mg/kg bw

For more Non-Human Toxicity Values (Complete) data for DIMETHYL SULFATE (10 total), please visit the HSDB record page.

IN ALL CASES CONSULT A DOCTOR! INHALATION: Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer for medical attention. SKIN: Remove contaminated clothes. Rinse and then wash skin with water and soap. Refer for medical attention. EYES: First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then take to a doctor. INGESTION: Rinse mouth. Give plenty of water to drink. Refer for medical attention immediately.

ADVICE TO PHYSICIANS: In the event of suspected inhalation of vapor, even in the absence of any symptoms, patients should be kept resting quietly under clinical observation for at least 12 hours ... Eye irrigation should be repeated if any redness develops. Oxygen may be administered if there is breathing difficulty. Arrangements should be made for the possibly affected patient to be transferred to the nearest center equipped for the treatment of pulmonary edema, the support of patients with major organ failure, and circulatory collapse.

With inhalation exposure, the administration of high doses of methyl prednisolone (30 mg/kg body weight, by slow intravenous injection) or the administration of other steroids (e.g., beclomethasone dipropionate) by metered-dose aerosol has been reported to reduce the incidence of exudative pulmonary edema and subsequent pulmonary fibrosis. The prophylactic use of steroids after exposure, but before any signs and symptoms appear, may be of value in reducing pulmonary damage by dimethyl sulfate. An early chest X-ray may be useful for comparison with a later film in the event of the development of pulmonary edema. Oral or aerosol bronchodilators (e.g., salbutamol) may be of value if there is bronchospasm. Oxygen and humidification are the main lines of treatment for mild pulmonary edema; diuretics, opiates, and theophyllines do not have a role, since the condition is exudative rather than transudative. In extreme cases, intermittent positive-pressure ventilation may be necessary ...

Because of its delayed effects, early clinical monitoring and treatment during the first 24 to 72 hours are important. Patients exposed to dimethyl sulfate should be treated as a medical emergency. Induced emesis can be dangerous because of re-exposure of the esophagus to corrosive material and because of the danger of aspiration pneumonia and respiratory tract damage. Gastric lavage can be performed, preferably within 1 hour of ingestion with appropriate tracheal protection. Endoscopy determines the extent of esophageal and gastric injury. Oral exposure is managed as a corrosive acid ingestion. Eye exposure is treated with copious irrigation with water or normal saline for at least 20 to 30 minutes. For skin exposure, all contaminated clothing should be removed and exposed skin washed thoroughly with water or saline.

For more Antidote and Emergency Treatment (Complete) data for DIMETHYL SULFATE (7 total), please visit the HSDB record page.

/Protect from exposure/ workers with diseases of central nervous system, liver, and kidneys.

/SIGNS AND SYMPTOMS/ (...Inhalation, skin absorption, or ingestion.) immediate effects of vapor exposure are irritation and erythema of eyes progressing to lacrimation, blepharospasms, and chemosis. Cough, hoarseness, and edema of tongue, lips, larynx, and lung occur later. Ingestion or direct contact with mucous membranes causes corrosions equivalent to that from sulfuric acid. After absorption, pulmonary edema and injury to liver and kidneys... .

/SIGNS AND SYMPTOMS/ Dimethyl sulfate is classified as a hepatotoxin. Symptoms of hepatic disease include malaise, lethargy, nausea, vomiting, pruritus, right upper quadrant pain, and anorexia. Signs of hepatic disease include scleral icterus, hepatic enlargement and tenderness, dark urine, and light-colored, and loose stools. Complications of hepatic failure are portal hypertension (esophageal varices, prominent superficial abdominal veins, internal hemorrhoids), edema, spider angiomata, upper gastrointestinal bleeding, encephalopathy, electrolyte imbalance, and, occasionally, concomitant renal failure.

/SIGNS AND SYMPTOMS/ ... Corneal ulceration and severe inflammation of the eyes and eyelids with photophobia are commonly reported; these symptoms generally resolve satisfactorily, though irreversible loss of vision has been reported. Irritation of the mucous membranes of the mouth and respiratory tract may be severe with pulmonary edema; there may be hoarseness and oropharyngeal edema, which persist for several weeks. Genital and mucous membrane lesions have been reported following direct contact, generally with the vapor. Systemic effects can include convulsions, delirium, coma, analgesia, pyrexia, pulmonary edema, delayed renal and hepatic failure, and cardiac damage. ...

/SIGNS AND SYMPTOMS/ ... Poisoning in industrial workers ... signs and symptoms uniformly found after each exposure began with headache and giddiness ... photophobia ... /SRP: pressure or tightness/ of chest, difficult breathing and swallowing, vomiting, diarrhea, and scalding micturition. Dysuria ... reduction in visual fields for various colors. When death occurs, signs indicate circulatory failure.

LC50 Leuciscus idus (orfe) 14 mg/L/48 hr; static

LC50 Leuciscus idus (orfe) 14 mg/L/96 hr; static

LC50; Species: Lepomis macrochirus (Bluegill, length 33-75 mm); Conditions: freshwater, static, 23 °C, pH 7.6-7.9, hardness 55 mg/L CaCO3; Concentration: 7500 ug/L for 96 hr /99% purity/

LC50; Species: Menidia beryllina (Inland silverside, length 40-100 mm); Conditions: saltwater, static, 20 °C, pH 7.6-7.9, hardness 55 mg/L CaCO3; Concentration: 15000 ug/L for 96 hr /99% purity/

The substance is harmful to aquatic organisms.

Dimethyl sulfate's production and use as a methylating agent, stabilizer and chemical intermediate may result in its release to the environment through various waste streams. If released to air, a vapor pressure of 0.677 mm Hg at 25 °C indicates dimethyl sulfate will exist solely as a vapor in the atmosphere. Vapor-phase dimethyl sulfate will be degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 82 days. Vapor-phase dimethyl sulfate will be degraded in the atmosphere by reaction with water (estimated atmospheric lifetime of >2 days). Dimethyl sulfate does not contain chromophores that absorb at wavelengths >290 nm and therefore is not expected to be susceptible to direct photolysis by sunlight. If released to soil, dimethyl sulfate is expected to hydrolyze in moist soils. Adsorption and volatilization from soil are not expected to be important fate processes because of hydrolysis. If released into water, dimethyl sulfate is expected to hydrolyze with a half-life of 1.15 hours; methanol and sulfuric acid have been identified as hydrolysis products. Volatilization, adsorption to suspended solids and sediments, biodegradation, and bioconcentration are not expected to be important fate processes in aquatic systems because of hydrolysis. Occupational exposure to dimethyl sulfate may occur through inhalation and dermal contact with this compound at workplaces where dimethyl sulfate is produced or used. Monitoring data indicate that the general population may be exposed to dimethyl sulfate via inhalation of ambient air. (SRC)

Dimethyl sulfate's production and use as a methylating agent for amines and phenols(1,2), used with boron compounds to stabilize liquid sulfur trioxide(3) and in the preparation of a wide variety of intermediates and products, especially in the fields of dyes, agricultural chemicals, drugs, and other specialties(3) may result in its release to the environment through various waste streams(SRC).

TERRESTRIAL FATE: If released to moist soil, dimethyl sulfate is expected to hydrolyze rapidly as indicated by a measured rate constant in water of 1.66X10-4/sec at 25 °C(1), corresponding to a half-life of 1.15 hours at pH 7(SRC). Volatilization from water surfaces, adsorption to suspended solids and sediments, biodegradation, and bioconcentration are not expected to be important fate processes in moist terrestrial systems because of hydrolysis(SRC). Dimethyl sulfate may volatilize slightly from dry soil surfaces(SRC) based upon a vapor pressure of 0.677 mm Hg(2).

AQUATIC FATE: If released to water, dimethyl sulfate is expected to hydrolyze rapidly as indicated by a measured rate constant of 1.66X10-4/sec at 25 °C(1); this corresponds to a half-life of 1.15 hours at pH 7(SRC). The rate of hydrolysis will increase in both acidic and basic waters as the reaction is catalyzed under these conditions(2). Volatilization from water surfaces, adsorption to suspended solids and sediments, biodegradation, and bioconcentration are not expected to be important fate processes in aquatic systems because of hydrolysis(SRC).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), dimethyl sulfate, which has a vapor pressure of 0.677 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase dimethyl sulfate is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 84 days(SRC), calculated from its rate constant of 5.0X10-13 cu cm/molecule-sec at 25 °C(3). Vapor-phase dimethyl sulfate is degraded in the atmosphere by reaction with water (estimated atmospheric lifetime of >2 days)(4). Dimethyl sulfate is likely to become incorporated into fog and cloudwater, in which case it will hydrolyze to monomethyl hydrogen sulfate (and finally sulfuric acid) and methanol, with a half-life on the order of 30 to 60 min(4). Dimethyl sulfate does not contain chromophores that absorb at wavelengths >290 nm(5) and therefore is not expected to be susceptible to direct photolysis by sunlight(SRC).

The rate constant for the vapor-phase reaction of dimethyl sulfate with photochemically-produced hydroxyl radicals is 5.0X10-13 cu cm/molecule-sec at 25 °C(1). This corresponds to an atmospheric half-life of about 84 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). Experimental rate constants for the gas-phase reactions of dimethyl sulfate with ozone, <1.4X10-21 cu cm/molecule-sec; ammonia, <1.5X10-21 cu cm/molecule-sec; and water, <1.1X10-23 cu cm/molecule-sec translate to atmospheric lifetimes of >33 yr, >8 yr, and >2 days, respectively(2). A measured hydrolysis rate constant of 1.66X10-4/sec for dimethyl sulfate in water at 25 °C(3) corresponding to a half-life of 1.1 hrs at pH 7(SRC). The reaction is catalyzed under both acidic and basic conditions forming sulfuric acid and free methanol at pHs <7(4). The first methyl group is removed much more rapidly than the second with hydrolysis of the dimethyl sulfate being complete in a 24 hr period in water, dilute acid, or dilute base; the monomethyl species persists over a period of several weeks(5). The compound is hydrolyzed slowly in cold water(6). Dimethyl sulfate does not contain chromophores that absorb at wavelengths >290 nm(7) and therefore is not expected to be susceptible to direct photolysis by sunlight(SRC).

Based upon the hydrolysis of dimethyl sulfate in aqueous environments(1), bioconcentration is not expected to be a primary removal process in aquatic systems(SRC).

Based upon the hydrolysis of dimethyl sulfate in aqueous environments(1), adsorption to soil and leaching are not expected to be important processes(SRC).

Based upon the hydrolysis of dimethyl sulfate in aqueous environments(1), volatilization from water and moist soil surfaces is not expected to be important process(SRC). Dimethyl sulfate may volatilize slightly from dry soil surfaces(SRC) based upon a vapor pressure of 0.677 mm Hg(2).

Dimethyl sulfate was detected in airborne particulate matter from a coal-fired power plant (125 m from the stack and 30 m below the top of the stack) using low sulfur (0.5%), high ash (14%) coal - 0.07 to 0.34 umol/g, upper limit because of hydrolysis loss during extraction(1). Dimethyl sulfate was detected in emissions from a coal-fired and an oil-fired power plant at concentrations of 0.28, 0.21 and 0.95 mmol dimethyl sulfate/mol of total sulfur in the stack, at the top of the stack and in the plume of the coal-fired power plant, respectively, and 0.07, 0.08, and 3.1 mmol dimethyl sulfate/mol of total sulfur in the flue line, at the top of the stack, and in the plume of the oil-fired power plant, respectively(2).

RURAL/REMOTE: Dimethyl sulfate was detected in samples from Wallops Island, VA at a concentration of 58 parts per trillion(1).

URBAN/SUBURBAN: Using ion chromatography, dimethyl sulfate was found in both particles and in the gas phase(1). The concentration of gas-phase methyl sulfates was several mg/cu m(1). These species thus account for a significant fraction of the total sulfur budget in the Los Angeles Basin during the 3-day sample period in August 1983(1). Dimethyl sulfate was qualitatively detected in the atmosphere of the Netherlands(2).

NIOSH (NOES Survey 1981-1983) has statistically estimated that 10,481 workers (2,455 of these are female) are potentially exposed to dimethyl sulfate in the US(1). Occupational exposure to dimethyl sulfate may occur through inhalation and dermal contact with this compound at workplaces where dimethyl sulfate is produced or used. Monitoring data indicate that the general population may be exposed to dimethyl sulfate via inhalation of ambient air(SRC).

For the treatment and disposal of waste, the recommended methods are alkaline hydrolysis, incineration, and landfill. Do not use open burning (e.g., as a boiler fuel) or evaporation for waste disposal. For incineration, dimethyl sulfate should be dissolved in a combustible solvent and sprayed into a furnace with an afterburner and an alkali scrubber. Dimethyl sulfate may be decomposed by adding a dilute alkaline solution; the mixture should be stirred and then allowed to settle. The resulting solution is then neutralized by acid or alkali as appropriate and drained into a sewer. When rapid decomposition is needed the waste may be warmed. It may also be adsorbed on vermiculite, packed in drums, buried and covered immediately.

It has been reported that dimethyl sulfate (DMS) can be degraded with sodium hydroxide solution (1 mol/L), sodium carbonate solution (1 mol/L), or ammonium hydroxide solution (1.5 mol/L). ... Complete destruction of undiluted dimethyl sulfate (DMS) in solvents miscible with water (methanol, ethanol, DMSO, DMF, acetone) or solvents partially miscible or immiscible with water (toluene, p-xylene, benzene, 1-pentanol, ethyl acetate, chloroform, carbon tetrachloride, acetonitrile) could be obtained using any of the above methods. Reaction times were 15 min after homogeneity was obtained for undiluted DMS, 15 min for solutions in methanol, ethanol, DMSO, and DMF, one hour for solutions in acetone, three hours for acetonitrile, and one day for the other solvents listed above. The final reaction mixtures were tested for mutagenicity, and when the solutions were not cytotoxic, no mutagenic response was obtained. DMS in solution was determined by a colorimetric method. The products of the reactions were found to be methanol when NaOH and Na2CO3 were used and methylamine, dimethylamine, trimethylamine, and methanol when ammonium hydroxide was used. ...

Destruction procedures for dimethylsulfate (DMS), diethylsulfate (DES), methyl methanesulfonate (MMS), and ethyl methanesulfonate (EMS) have been investigated using treatment by 1 N NaOH, 1 N NH4OH, 1 M Na2CO3, and 1 M Na2S2O3. During the kinetic study of the destruction process, the determination of remaining concentrations of the alkylating agents was performed by the derivatization of p-nitrophenoxide to p-nitroanisole and p-nitrophenetole, which were separated by high performance liquid chromatography. The mutagenic activity of the destruction products was evaluated by the Ames test using Salmonella tester strains TA97, TA98, TA100, and TA102. The kinetics of destruction in every case followed a time-dependent exponential relationship. Solutions of 1 M Na2S2O3 showed the highest capacity for destruction of the four alkylating agents, half-lives of DMS, DES, MMS, and EMS being 0.14 min, 1.26 min, 0.60 min, and 5.26 min, respectively. No mutagenic activity was detected following complete destruction in 1 M Na2S2O3.

PRECAUTIONS FOR "CARCINOGENS": There is no universal method of disposal that has been proved satisfactory for all carcinogenic compounds & specific methods of chem destruction ... published have not been tested on all kinds of carcinogen-containing waste. ... Summary of avail methods & recommendations ... /given/ must be treated as guide only. /Chemical Carcinogens/

For more Disposal Methods (Complete) data for DIMETHYL SULFATE (11 total), please visit the HSDB record page.

If ... THERE IS NO FIRE, go directly to the Table of Initial Isolation and Protective Action Distances /(see table below)/ ... to obtain initial isolation and protective action distances. IF THERE IS A FIRE, or IF A FIRE IS INVOLVED, go directly to the appropriate guide /(see guide(s) below)/ and use the evacuation information shown under PUBLIC SAFETY.

Table: Table of Initial Isolation and Protective Action Distances for Dimethyl sulfate [Table#2469]

/GUIDE 156: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE/WATER-SENSITIVE)/ Fire or Explosion: 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.

/GUIDE 156: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE/WATER-SENSITIVE)/ Health: 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 which 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.

/GUIDE 156: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE/WATER-SENSITIVE)/ Public Safety: CALL Emergency Response Telephone Number ... . 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.

For more DOT Emergency Guidelines (Complete) data for DIMETHYL SULFATE (9 total), please visit the HSDB record page.

UN 1595; Dimethyl sulfate

IMO 6.1; Dimethyl sulfate

49 333 22; Dimethyl sulfate

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./

The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials.

The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article.

PRECAUTIONS FOR "CARCINOGENS": Procurement ... of unduly large amt ... should be avoided. To avoid spilling, carcinogens should be transported in securely sealed glass bottles or ampoules, which should themselves be placed inside strong screw-cap or snap-top container that will not open when dropped & will resist attack from the carcinogen. Both bottle & the outside container should be appropriately labelled. ... National post offices, railway companies, road haulage companies & airlines have regulations governing transport of hazardous materials. These authorities should be consulted before ... material is shipped. /Chemical Carcinogens/

PRECAUTIONS FOR "CARCINOGENS": When no regulations exist, the following procedure must be adopted. The carcinogen should be enclosed in a securely sealed, watertight container (primary container), which should be enclosed in a second, unbreakable, leakproof container that will withstand chem attack from the carcinogen (secondary container). The space between primary & secondary container should be filled with absorbent material, which would withstand chem attack from the carcinogen & is sufficient to absorb the entire contents of the primary container in the event of breakage or leakage. Each secondary container should then be enclosed in a strong outer box. The space between the secondary container & the outer box should be filled with an appropriate quantity of shock-absorbent material. Sender should use fastest & most secure form of transport & notify recipient of its departure. If parcel is not received when expected, carrier should be informed so that immediate effort can be made to find it. Traffic schedules should be consulted to avoid ... arrival on weekend or holiday ... /Chemical Carcinogens/

Poison Inhalation Hazard Corrosive

Unbreakable packaging. Put breakable packaging into closed unbreakable container. Do not transport with food and feedstuffs.

Symbol: T+; R: 45-25-26-34-43-68; S: 53-45; Note: E

UN Hazard Class: 6.1; UN Subsidiary Risks: 8; UN Pack Group: I