ACROLEIN

O CH2 Note: Acrolein is normally inhibited with 0.1-0.25 wt % hydroquinone to prevent polymerization during storage and transport. May contain water (3 wt %), propanal and acetone (≤ 1.5 wt %). CASRN: 107-02-8; DOT: 1092 (inhibited), 2607 (stabilized dimer); DOT label: Flammable liquid and poison; molecular formula: C3H4O; FW: 56.06; RTECS: AS1050000; Merck Index: 12, 130 Physical state, color, and odor: Colorless to yellow, clear, watery liquid imparting a very sharp, acrid, pungent, or irritating odor. Odor threshold concentrations reported were 0.11 mg/kg by Guadagni et al. (1963), 0.21 ppmv by Leonardos et al. (1969), and 36 ppbv by Nagata and Takeuchi (1990). In addition, Katz and Talbert (1930) reported an experimental detection odor threshold concentration of 4.1 mg/m3 (1.8 ppmv). Melting point (°C): -86.9 (Weast, 1986) Boiling point (°C): 52.7 (quoted, Standen, 1963) Density (g/cm3): 0.8410 at 20 °C (Weast, 1986) 0.8389 at 25 °C (quoted, Riddick et al., 1986) Diffusivity in water (x 10-5 cm2/sec): 1.12 at 20 °C using method of Hayduk and Laudie (1974) Flash point (°C): -26 (Acros Organics, 2002) -18 (open cup, Aldrich, 1990) Lower explosive limit (%): 2.8 (NIOSH, 1994) Upper explosive limit (%): 31 (NIOSH, 1994) Henry’s law constant (x 10-6 atm⋅m3/mol at 25 °C): 135 (Snider and Dawson, 1985) Interfacial tension with water (dyn/cm): 35 at 20 °C (estimated, CHRIS, 1984) Ionization potential (eV): 10.11 ± 0.01 (Lias, 1998)

2.54 (bluegill sunfish, Veith et al., 1980) Soil organic carbon/water partition coefficient, log Koc: Although experimental methods for estimation of this parameter for unsaturated aldehydes are lacking in the documented literature, an estimated value of -0.588 was reported by Ellington et al. (1993). Its high solubility in water and low Koc, and Kow values suggest that acrolein adsorption to soil will be low (Lyman et al., 1982). Octanol/water partition coefficient, log Kow: -0.01 (quoted, Sangster, 1989) 0.90 (Veith et al., 1980) Solubility in organics: Soluble in ethanol, ether, and acetone (U.S. EPA, 1985) Solubility in water (wt %): 19.7 at 0 °C, 20.9 at 10.0 °C, 22.9 at 20.0 °C, 23.0 at 30 °C, 24.2 at 40.0 °C, 24.5 °C at 53.0 °C (shake flask-GC, Stephenson, 1993c) Vapor density: 2.29 g/L at 25 °C, 1.94 (air = 1) Vapor pressure (mmHg): 210 at 20 °C (NIOSH, 1997) 265 at 25 °C (quoted, Howard, 1989) 273 at 25 °C (Banerjee et al., 1990) Environmental fate: Biological. Microbes in site water converted acrolein to β-hydroxypropionaldehyde (Kobayashi and Rittman, 1982). This product also forms when acrolein is hydrated in distilled water (Burczyk et al., 1968) which can revert to acrolein. This suggests water, not site microbes, is primarily responsible for the formation of the aldehyde. When 5 and 10 mg/L of acrolein were statically incubated in the dark at 25 °C with yeast extract and settled domestic wastewater inoculum, complete degradation was observed after 7 d (Tabak et al., 1981). Activated sludge was capable of degrading acrolein at concentrations of 2,300 ppm but no other information was provided (Wierzbicki and Wojcik, 1965). The half-life of acrolein in unsterilized supply water samples from an irrigation area was 29 h versus 43 h in thymol-treated water. A half-life of 43 h was also reported for acrolein in buffered distilled water at identical pH. These data suggest that biotransformation occurred in these aquatic systems. At higher aqueous concentrations (6.0 to 50.5 mg/L), the marked decrease in pH suggests that carboxylic acids were formed as end products (Bowmer and Higgins, 1976). Bridié et al. (1979) reported BOD and COD values of 0.00 and 1.72 g/g using filtered effluent from a biological sanitary waste treatment plant. These values were determined using a standard dilution method at 20 °C for a period of 5 d. The ThOD for acrolein is 2.00 g/g. Surface Water. In canal water, the initial acrolein concentration of 100 µg/L was reduced to 90, 50 and 30 µg/L at 5, 10, and 15 miles downstream. No explanation was given for the decrease in concentration, e.g., volatilization, chemical hydrolysis, dilution, etc. (Bartley and Gangstad, 1974). Photolytic. Photolysis products include carbon monoxide, ethylene, free radicals, and a polymer (Calvert and Pitts, 1966). Anticipated products from the reaction of acrolein with ozone or OH radicals in the atmosphere are glyoxal, formaldehyde, formic acid, and carbon dioxide (Cupitt,

formaldehyde with a trace of glyoxal (Altshuller, 1983). Osborne et al. (1962) reported that acrolein was stable at 30 °C and UV light (λ = 313 nm) in the presence and absence of oxygen. Rate constants of 1.90-2.53 x 10-13 cm3/molecule⋅sec (Atkinson, 1985), 1.99 x 10-11 cm3/molecule⋅sec (Atkinson, 1990), and 2.29 x 10-11 cm3/molecule⋅sec (Sabljić and Güsten, 1990) were reported for the gas-phase reaction of acrolein and OH radicals. Acrolein reacts with ozone and NO3 radicals in gas-phase at rates of 6.4 x 10-19 cm3/molecule⋅sec (Atkinson and Carter, 1984) and 1.15 x 10-15 cm3/molecule⋅sec, respectively (Sabljić and Güsten, 1990). Chemical/Physical. Wet oxidation of acrolein at 320 ºC yielded formic and acetic acids (Randall and Knopp, 1980). May polymerize in the presence of light and explosively in the presence of concentrated acids (Worthing and Hance, 1991) forming disacryl, a white plastic solid (Humburg et al., 1989; Windholz et al., 1983). In distilled water, acrolein is hydrolyzed to β-hydroxypropionaldehyde (Burczyk et al., 1968; Reinert and Rodgers, 1987; Kollig, 1993). The estimated hydrolysis half-life in water is 22 d (Burczyk et al., 1968). Bowmer and Higgins (1976) reported a disappearance half-life of 69 and 34 d in buffered water at pH values of 5 and 8.5, respectively. In a large tank containing nonturbulent water, acrolein disappeared at a first-order rate constant of 0.83/d which corresponds to a half-life of 0.83 d (Bowmer et al., 1974). At an influent concentration of 1,000 mg/L, treatment with GAC resulted in an effluent concentration of 694 mg/L. The adsorbability of the carbon used was 61 mg/g carbon (Guisti et al., 1974). Similarly, at influent concentrations of 10, 1.0, 0.1, and 0.01 mg/L, the GAC adsorption capacities were 5.2, 1.2, 0.26, and 0.06 mg/g, respectively (Dobbs and Cohen, 1980). Exposure limits: NIOSH REL: TWA 0.1 ppm (0.25 mg/m3), STEL 0.3 ppm (0.8 mg/m3), IDLH 2 ppm; OSHA PEL: TWA 0.1 ppm; ACGIH TLV: TWA 0.1 ppm, STEL 0.3 ppm. Symptoms of exposure: Strong lachrymator and nasal irritant. Eye contact may damage cornea. Skin contact may cause delayed pulmonary edema (Patnaik, 1992). An irritation concentration of 1.25 mg/m3 in air was reported by Ruth (1986). Inhalation of acrolein at a concentration of 153 ppm for 10 min resulted in death (quoted, Verschueren, 1983). Toxicity: LC50 (96-h) for bluegill sunfish 90 µg/L (Spehar et al., 1982). LC50 (48-h) for oysters 560 µg/L, shrimp 100 µg/L (Worthing and Hance, 1991), Daphnia magna 83 µg/L (LeBlanc, 1980). LC50 (24-h) for bluegill sunfish 79 µg/L, brown trout 46 µg/L (Burdick et al., 1964), Daphnia magna 23 µg/L (LeBlanc, 1980), rainbow trout 150 µg/L, mosquito fish 390 µg/L, shiners 40 µg/L (Worthing and Hance, 1991). LC50 (4-h inhalation) for Sprague-Dawley rats (combined sexes) 8.3 ppm (Ballantyne et al., 1989a). LC50 (1-h inhalation) for Sprague-Dawley rats (combined sexes) 26 ppm (Ballantyne et al., 1989a). Acute oral LD50 for rats 46 mg/kg (Ashton and Monaco, 1991), 25.1 mg/kg, mice 40 mg/kg, rabbits 7 mg/kg (quoted, RTECS, 1985), bobwhite quail 19 mg/kg, mallard ducks 9.1 mg/kg (Worthing and Hance, 1991). LD50 (inhalation) for mice 66 ppm/6-h, rats 300 mg/m3/30-min (quoted, RTECS, 1985). Acute percutaneous LD50 for rats 231 mg/kg (Worthing and Hance, 1991). In 90-d feeding trials, the NOEL in rats is 5 mg/kg daily (Worthing and Hance, 1991). Source: Reported in cigarette smoke (150 ppm) and gasoline exhaust (0.2 to 5.3 ppm) (quoted, Verschueren, 1983). May be present as an impurity in 2-methoxy-3,4-dihydro-2H-pyran

Acrolein was detected in diesel fuel at a concentration of 3,400 µg/g (Schauer et al., 1999). Gas-phase tailpipe emission rates from California Phase II reformulated gasoline-powered automobiles with and without catalytic converters were 0.06 and 3.8 mg/km, respectively (Schauer et al., 2002). Schauer et al. (2001) measured organic compound emission rates for volatile organic compounds, gas-phase semi-volatile organic compounds, and particle phase organic compounds from the residential (fireplace) combustion of pine, oak, and eucalyptus. The gas-phase emission rates of acrolein were 63 mg/kg of pine burned, 44 mg/kg of oak burned, and 56 mg/kg of eucalyptus burned. Uses: Intermediate in the manufacture of many chemicals (e.g., glycerine, 1,3,6-hexanediol, βchloropropionaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, β-picoline, nicotinic acid), pharmaceuticals, polyurethane, polyester resins, liquid fuel, slimicide; herbicide; anti-microbial agent; control of aquatic weeds in irrigation canals and ditches; warning agent in gases.