GLYCOL ETHERS

Glycol ethers are federal hazardous air pollutants and were identified as toxic air contaminants in April 1993 under AB 2728.

CAS Registry Numbers: See Table I

Molecular Formulas: See Table I

Glycol ethers, as defined in the federal Clean Air Act Section 112(b) and listed as “Must Be Quantified for Emissions Inventory” for the Air Toxics “Hot Spots” Program (AB 2588), are diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monopropyl ether, and triethylene glycol dimethyl ether (CAPCOA, 1993). Currently, the inclusion of propylene glycol ethers in the definition of glycol ethers is being debated within the United States Environmental Protection Agency (U.S. EPA), but no decisions have been made.

PHYSICAL PROPERTIES OF GLYCOL ETHERS

The physical properties and characteristics of glycol ethers are described in Tables I and II (Howard, 1990; Merck, 1989; Sax, 1989; U.S. EPA, 1994a).

SOURCES AND EMISSIONS

A. Sources

Glycol ethers are mainly used as solvents (HSDB, 1993). The primary stationary sources that have reported emissions of glycol ethers in California are described in Table III (ARB, 1997b).

Ethylene glycol monobutyl ether (2-butoxyethanol) is registered as an adjuvant for agricultural products; it is used to facilitate the application of other agricultural products. The licensing and regulation of pesticides for sale and use in California are the responsibility of the Department of Pesticide Regulation (DPR). Information presented in this fact sheet regarding the permitted pesticidal uses of ethylene glycol monobutyl ether has been collected from pesticide labels registered for use in California and from DPR's pesticide databases. This information reflects pesticide use and permitted uses in California as of October 15, 1996. For further information regarding the pesticidal uses of this compound, please contact the Pesticide Registration Branch of DPR (DPR, 1996).

B. Emissions

The total emissions of glycol ethers from stationary sources in California are estimated to be at least 4.2 million pounds per year, based on data reported under the Air Toxics "Hot Spots" Program (AB 2588). Emissions for some individual glycol ethers are listed in Table III. Of the 4.2 million pounds per year total emissions reported, 2.9 million pounds per year emissions were not specified individually, and were reported under the general group, glycol ethers. This was based on data reported under the Air Toxics "Hot Spots" Program (ARB, 1997b).

C. Natural Occurrence

No information about the natural occurrence of the glycol ethers was found in the readily-available literature.

AMBIENT CONCENTRATIONS

No Air Resources Board data exist for ambient measurements of glycol ethers.

INDOOR SOURCES AND CONCENTRATIONS

Potential sources of glycol ethers in indoor air include paints and other coatings, inks, adhesives, nail polishes, cosmetics, household cleaning products, and other consumer products (Hodgson and Wooley, 1991). Indoor data on glycol ethers is very limited. Sheldon et al. (1988b) measured ethyoxyethyl acetate (ethylene glycol monoethyl ether acetate) levels in six public buildings located in the eastern United States. Ethyoxyethyl acetate was present in measurable levels in four of the buildings at concentrations ranging from 1.31 to 9.58 micrograms per cubic meter. Corresponding outdoor levels were below the limits of detection.

ATMOSPHERIC PERSISTENCE

Glycol ethers exist in the atmosphere in the gas phase. The dominant atmospheric loss process for the glycol ethers is by reaction with the hydroxyl radical. Based on this reaction, the atmospheric half-life and lifetime of 2-butoxyethanol, 2-ethoxyethanol, 1-acetoxy- 2-ethoxyethane, and 2-methoxyethanol are in the ranges of 0.6 to 0.9 days and 0.8 to 1.3 days, respectively (Atkinson, 1989, 1994). Its reaction products include hydroxyesters, hydroxyacids, hydroxycarbonyls, peroxyacyl nitrates, and formaldehyde (Kao, 1994).

AB 2588 RISK ASSESSMENT INFORMATION

The Office of Environmental Health Hazard Assessment reviews risk assessments submitted under the Air Toxics "Hot Spots" Program (AB 2588). Of the risk assessments reviewed as of December 1996, for non-cancer health effects, glycol ethers contributed to the total hazard index in 31 of the approximately 89 risk assessments reporting a total chronic hazard index greater than 1, and presented an individual hazard index greater than 1 in 4 of these risk assessments. Glycol ethers also contributed to the total hazard index in 18 of the approximately 107 risk assessments reporting a total acute hazard index greater than 1, and presented an individual hazard index greater than 1 in 9 of these risk assessments (OEHHA, 1996b).

HEALTH EFFECTS

This section discusses the glycol ethers for which there is the most toxicological information.

Possible routes of human exposure to glycol ethers are inhalation, ingestion, and dermal contact.

Non-Cancer: Acute exposure to high levels of the glycol ethers in humans results in narcosis, pulmonary edema, and severe liver and kidney damage. Acute exposure to lower levels of glycol ethers in humans causes conjunctivitis, temporary corneal clouding, and upper respiratory tract irritation. Chronic exposure to the glycol ethers in humans results in fatigue, lethargy, nausea, anorexia, tremor, and anemia (U.S. EPA, 1994a). Some studies have shown that propylene glycol ethers may be safer replacements for ethylene glycol ethers (ARCO, 1996).

Acute and chronic non-cancer Reference Exposure Levels (REL) for the following glycol ethers are listed in the California Air Pollution Control Officers Association Air Toxics "Hot Spots" Program, Revised 1992 Risk Assessment Guidelines. The toxicological endpoints considered are also indicated (CAPCOA, 1993).

ACUTE DATA

Name REL(µg/m3)Toxicological Endpoint CAS #
Ethylene glycol monobutyl ether 1.5 x 103 Blood 111-76-2
Ethylene glycol monoethyl ether 3.7 x 102Reproductive/developmental110-80-5
Ethylene glycol monoethyl ether acetate1.6 x 103Reproductive/developmental111-15-9
Ethylene glycol monomethyl ether3.2 x 102Reproductive/developmental109-86-4

CHRONIC DATA

NameREL(µg/m3)Toxicological EndpointCAS #
Ethylene glycol monobutyl ether2.0 x 101Reproductive/Respiratory111-76-2
Ethylene glycol monoethyl ether 2.0 x 102Reproductive/Respiratory110-80-5
Ethylene glycol monoethyl ether acetate6.4 x 101Reproductive/Respiratory111-15-9
Ethylene glycol monomethyl ether2.0 x 101Reproductive/Respiratory109-86-4
Ethylene glycol monomethyl ether acetate5.7 x 101Reproductive/Respiratory110-49-6

The United States Environmental Protection Agency (U.S. EPA) has established a Reference Concentration (RfC) for ethylene glycol monomethyl ether of 0.02 milligrams per cubic meter (mg/m3) based on testicular effects in rabbits. The U.S. EPA estimates that inhalation of this concentration or less, over a lifetime, would not likely result in the occurrence of chronic non-cancer results. The oral Reference Dose (RfD) is under review, and the provisional RfD is calculated to be 0.001 milligrams per kilogram per day (mg/kg/d). The U.S. EPA estimates that consumption of this dose or less, over a lifetime, would not likely result in the occurrence of chronic non-cancer effects. The U.S. EPA has established a RfC for ethylene glycol monoethyl ether of 0.2 mg/m3 based on decreased testis weight, seminiferous tubule degeneration, and decreased hemoglobin in rabbits, but has not established an oral RfD. However, a provisional oral RfD has been calculated to be 0.4 mg/kg/d.

No information is available on the reproductive or developmental effects of the glycol ethers in humans. Inhalation and oral exposure to several specific glycol ethers has been reported to result in testicular damage, reduced fertility, maternal toxicity, early embryonic death, birth defects, and delayed development in animal studies (U.S. EPA, 1994a). The State of California has determined under Proposition 65 that ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether acetate are male reproductive and developmental toxicants (CCR, 1996).

Cancer: No information is available on the carcinogenic effects of the glycol ethers in humans. No increase in tumors was reported in rats and mice exposed to ethylene glycol monoethyl ether by gavage. The U.S. EPA has not classified the glycol ethers for carcinogenicity (U.S. EPA, 1994a). The International Agency for Research on Cancer has not classified the glycol ethers as to human carcinogenicity (IARC, 1987a).

TABLE I - PHYSICAL PROPERTIES OF GLYCOL ETHERS

Molecular Formula, Substance Name, & CAS Registry No.

 

Synonyms

Molecular

Weight

Boiling Point

Melting Point

 

Flash Point

Vapor

Density

Vapor Pressure

Density/

Specific Gravity

Log

Octanol/Water

Partition Coefficient

C6H14O3

Diethylene glycol

dimethyl ether

CAS No: 111-96-6

bis(2-methoxyethyl) ether;

diglyme; diglycol methyl ether; 1,1'-oxybis(2-methyoxyethane)

134.18

162 oC

-68 oC

158 oC

---

2.96 mm Hg

at 25 oC

0.9451

at 20/20 oC

-0.06 (est.)

C8H18O3

Diethylene glycol

monobutyl ether

CAS No: 112-34-5

2-(2-butoxyethoxy)-ethanol; butyl digol

162.23

230.6 oC

-68.1 oC

172 oF

5.58

0.02 mm Hg

at 25 oC

0.9536

at 20/20 oC

0.91 (est.)

C6H14O3

Diethylene glycol

monoethyl ether

CAS No: 111-90-0

2-(2-ethoxyethoxy)-ethanol; diethylene glycol ethyl ether; diglycol monoethyl ether

134.18

195 - 202 oC

---

201 oF

4.62

(air = 1)

0.13 mm Hg

at 25 oC

0.9855

at 20/4 oC

-0.15 (est.)

C5H12O3

Diethylene glycol

monomethyl ether

CAS No: 111-77-3

2-(2-methoxyethoxy)-ethanol; methyl digol; methoxyethoxy ethanol; diethylene glycol methyl ether; diglycol monomethyl ether

120.15

193 oC

<-84 oC

200 oF

4.14

(air = 1)

0.20 mm Hg

at 25 oC

1.035

at 20/4 oC

-0.68 (est.)

C6H14O2

Ethylene glycol

diethyl ether

CAS No: 629-14-1

1,2-diethoxyethane;

ethyl glyme

118.18

121.4 oC

-74 oC

95 oC

(open cup)

4.07

(air = 1)

9.4 mm Hg

at 20 oC

0.8417

at 20/20 oC

---

C4H10O2

Ethylene glycol

dimethyl ether

CAS No: 110-71-4

1,2-dimethoxyethane; glycol dimethyl ether; glyme; monogiyme; dimethaxyethane; 2.5-dioxahexane; ethylene dimethyl ether; monoethylene glycol dimethyl ether

90.12

82 - 83 oC

-58 oC

(also reported at

-71 oC)

4.5 oC

3.1

(air = 1)

48 mm Hg

at 20 oC

0.86285

at 20/4 oC

---

(Howard, 1990; Merck, 1989; Sax, 1989; U.S. EPA 1994)

TABLE I - PHYSICAL PROPERTIES OF GLYCOL ETHERS (CONTINUED)

Molecular Formula, Substance Name, & CAS Registry No.

 

Synonyms

Molecular Weight

Boiling

Point

Melting

Point

Flash

Point

Vapor

Density

Vapor

Pressure

Density/

Specific Gravity

Log

Octanol/Water

Partition Coefficient

C6H14O2

Ethylene glycol monobutyl ether

CAS No.: 111-76-2

2-butoxyethanol; ethylene glycol-n-butyl ether; butyl glycol; glycol butyl ether; glycol monobutyl ether; monobutyl glycol ether

118.18

171-172 oC

-70 oC

141oF

(closed cup)

4.1

0.76 mm Hg at 20 oC

0.912

at 20/4 oC

0.83

C4H10O2

Ethylene glycol monoethyl ether

CAS No.: 110-80-5

2-ethoxyethanol; ethylene glycol ethyl ether; glycol ethyl ether; glycol monoethyl ether; hydroxy ether

90.12

135 oC

-70 oC

120 oF

(open cup)

3.1

5.5 mm Hg

at 25 oC

0.931

at 20/20 oC

-0.1

C6H12O3

Ethylene glycol monoethyl ether acetate

CAS No.: 111-15-9

1-acetoxy-2-ethoxyethane;

2-ethoxyethyl acetate;

2-ethyoxethanol acetate

132.16

156 oC

-61.7 oC

134 oF

(open cup)

4.72

1.6 mm Hg

at 20 oC

0.975

at 20/20 oC

0.65

(est.)

C3H8O2

Ethylene glycol monomethyl ether

CAS No.: 109-86-4

2-methoxyethanol

76.09

124.5 oC

-85.1 oC

115 oF

2.62

(air = 1)

9.5 mm Hg

at 25 oC

0.9663

at 20/4 oC

-0.77

C5H10O3

Ethylene glycol monomethyl ether acetate

CAS No.: 110-49-6

ethylene glycol methyl ether accetae; glycol monomethyl ether acetate; 2-methoxyethanol acetate

118.13

145 oC

-65.1 oC

55.6 oC

(open cup)

4.1

(air = 1)

2.0 mm Hg

at 20 oC

1.0067

at 20/20 oC

---

C5H12O2

Ethylene glycol monopropyl ether

CAS No.: 2807-30-9

monopropyl ether of ethylene glycol; 2-propoxyethanol

104.15

150-152 oC

---

---

---

2.9 mm Hg

at 25 oC

0.9112

at 20/4 oC

---

CHO

Triethylene glycol dimethyl ether

CAS No.: 112-49-2

triglyme;

2,5,8,11-tetraoxadodecane

178.22

216. oC

-45 oC

111 oC

---

---

0.990

at 20/4 oC

---

(Howard, 1990; Merck, 1989; Sax, 1989; U.S. EPA 1994)

TABLE II - PHYSICAL CHARACTERISTICS OF GLYCOL ETHERS

Glycol Ether

Physical Characteristics

Solubility

Other Characteristics

Glycol Ether

Physical Characteristics

Solubility

Other

Characteristics

Diethylene glycol

dimethyl ether

Colorless liquid; Mild odor

Miscible with water hydrocarbon solvents, alcohol, and ether

Readily forms explosive peroxides upon exposure to air, light, or heat

Ethylene glycol

monoethyl ether

Colorless liquid; Practically odorless; Slightly bitter taste

Miscible with water, hydrocarbons, ether, acetone, alcohol, and liquid esters

Solidifies at -70 oC;

Dissolves many oils, resins, and waxes

Diethylene glycol monobutyl ether

Colorless liquid; Faint butyl odor

Soluble in alcohol, ether, acetone, oils, benzene, water, and organic solvents

Can react with oxidizing materials

Ethylene glycol monoethyl ether acetate

Colorless liquid; Mild ester-like odor

Miscible with aromatic hydrocarbons;

Slightly miscible with ether

---

Diethylene glycol

monoethyl ether

Colorless liquid; Pleasant odor; Bitter taste

Miscible with water, acetone, chloroform, benzene, ethanol, ether, and pyridine

Hygroscopic;

Slightly viscous;

Stable

Ethylene glycol

monomethyl ether

Colorless liquid;

Mild agreeable odor

Miscible with water, benzene, alcohols, ketones, glycols, hydrocarbons, and dimethylformamide

Derived from ethylene oxide;

Lowest boiling point and greatest rate of evaporation of all available glycol ethers

Diethylene glycol

monomethyl ether

Colorless liquid; Pleasant odor; Bitter taste

Miscible with water, alcohol, glycerol, ether, acetone, dimethylformamide

Hygroscopic;

Can react with oxidizing materials

Ethylene glycol monomethyl ether acetate

Colorless liquid;

Pleasant odor

Miscible with water, oils, and most organic solvents

Stable;

Solidifies at

-70 oC

Ethylene glycol

diethyl ether

Colorless liquid; Sweetish odor; Bitter taste

Immiscible with water;

Soluble in oils, alcohol, ether, acetone, benzene, and organic solvents

Aprotic solvents (a type of solvent which neither donates or accepts protons)

Ethylene glycol monopropyl ether

Volatile liquid;

Mild ethereal odor;

Bitter taste

Soluble in water, alcohol, and ether

---

Ethylene glycol

dimethyl ether

Colorless liquid; Sharp ethereal odor

Miscible with water, alcohol;

Soluble in hydrocarbon solvents, chloroform, ether

---

Triethylene glycol dimethyl ether

Water-white liquid;

Mild ether odor

Miscible with water and hydrocarbon solvents;

Completely soluble in water and hydrocarbons at 20oC

May contain peroxides

Ethylene glycol

monobutyl ether

Colorless liquid; Pleasant odor; Mobile liquid

Soluble in water, organic solvents, and mineral oils;

Mixes with acetone, benzene, carbon tetrachloride, ethyl ether, n-heptane, ketones, ethers, alcohols, aromatic paraffin, and halogenated hydrocarbons

High dilution ratio with petroleum hydrocarbons

---

---

---

---

(Howard, 1990; Merck, 1989; Sax, 1989; U.S. EPA 1994)

TABLE III - SOURCES, USES, AND EMISSIONS OF GLYCOL ETHERS

Glycol

Ether

California

Emission Estimates (Lbs/Yr)

Major

Uses

Glycol

Ether

California

Emission Estimates (Lbs/Yr)

Major

Uses

Diethylene glycol

dimethyl ether

260

Solvent: Anhydrous reaction medium for organo-metallic synthesis

Ethylene glycol monomethyl ether

30,000

Solvent: Jet fuel anti-icing additive; Chemical intermediate; Plasticizer; In liquid soaps, cosmetics, painting plasters, hydraulic fluids, and cleaning compounds

Diethylene glycol

monoethyl ether

5,500

Solvent: Plasticizer intermediate; Brake fluid diluent

Ethylene glycol

monomethyl ether

acetate

3,100

Solvent: In textile printing, photographic film, and silk-screening inks

Diethylene glycol

monobutyl ether

26,000

Solvent: In textile printing;

Brake fluid diluent; Chemical

intermediate

Ethylene glycol

monopropyl ether

12,000

---

Diethylene glycol

monomethyl ether

6,500

Solvent: Chemical intermediate; Brake fluid diluent; Coupling agent

Triethylene glycol

dimethyl ether

2,800

Solvent: Coupling agent

Ethylene glycol

diethyl ether

No emissions reported

Inert reaction medium; Solvent: Organic synthesis;

Apriotic solvent; Detergent diluent

Ethylene glycol

dimethyl ether

9,700

Solvent: Extractant; Additive in diesel fuel, lubricants, and pesticides

Ethylene glycol

monobutyl ether

430,000

In hydraulic fluids; Solvent; Household cleaners; Chemical intermediate; Coupling agent

Ethylene glycol

monoethyl ether

320,000

Solvent; Anti-icing agent;

Chemical intermediate

Ethylene glycol

monoethyl ether acetate

150,000

Solvent; Automobile lacquers

     

(Howard, 1990; Merck, 1989; Sax, 1989; U.S. EPA 1994)