Sampling and Laboratory Analysis for Solvent Stabilizers - Environmental Investigation and Remediation - page 222

probably equivalent to several hand grenades, according to the reported explosive power of other
peroxidizable materials such as ethyl ether and isopropyl ether. 1,4-Dioxane is also known to form
explosive mixtures with nitromethane, sulfur trioxide, silver perchlorate, and decaborane (NICNAS,
1998). Laboratory standards used for instrument calibration and quality control are generally low
concentration and unlikely to form peroxides.
Unstabilized 1,4-dioxane may also form toxic and hazardous formate esters of 1,2-ethanediol
over long periods of storage. The mono- and diformates of 1,2-ethanediol are formed by peroxide
intermediates and have been found at concentrations as high as 1.8 M in partially consumed bottles
of 1,4-dioxane. Purging containers of 1,4-dioxane with nitrogen each time they are opened, keeping
containers away from light, and refrigerating 1,4-dioxane can prevent the possible health hazard
caused by contamination with peroxide and formate ester (Jewett and Lawless, 1980). As described
in Chapter 3, photo-oxidation of 1,4-dioxane in the atmosphere produces ethylene-1,2-diformate.
As discussed in Chapter 2, 1,4-dioxane can be stabilized to prevent peroxide and formate
ester formation. Stabilizers include stannous chloride, ferrous sulfate, 2,6- tert -butyl- p -cresol, or
butyl hydroxy toluene (BHT) (BASF, 1986, 2005; European Chemicals Bureau, 2002). Peroxide
formation can also be prevented by i lling the container headspace with nitrogen. When stabi-
lized and stored under nitrogen in original containers, 1,4-dioxane has a shelf life of 24 months
(BASF, 2005).
Absence of 1,4-dioxane to stabilize methyl chloroform has also created laboratory safety prob-
lems. A common method for cleaning parts of mass spectrometers is sonication (ultrasound clean-
ing) in a solvent bath. Before the use of methyl chloroform was banned by the Montreal Protocol, it
was commonly used in laboratory cleaning operations. At Purdue University, a laboratory techni-
cian performed a routine sonication cleaning operation that involved placing aluminum mass spec-
trometer parts in a beaker with methyl chloroform. On this occasion, the technician used a new
bottle of methyl chloroform. The methyl chloroform in the beaker began “boiling,” became dark,
and began producing a sharp odor that i lled the laboratory, forcing evacuation. The mass spect-
rometer part was ruined. Most mass spectrometer parts are made from stainless steel. In this
instance, the ion source from a Hewlett Packard (Agilent) 5970, 5992, 5995, or 5996 Series GC-MS
was made of aluminum and reacted with the methyl chloroform (Purdue University, 2003). It is
likely that the particular grade of methyl chloroform used was not intended for cleaning aluminum
parts and was therefore not stabilized with 1,4-dioxane.
ACKNOWLEDGMENTS
The critical reviews and helpful comments on this chapter by Carl Isaacson, a recent doctoral stu-
dent at OSU now with the USEPA in Athens, Georgia, and Bart Simmons, retired Director of the
California Department of Toxic Substances Control Hazardous Materials Laboratory, are gratefully
acknowledged.
BIBLIOGRAPHY
Anderson, H., 2005, Memo to D. Easley, U.S. EPA Region VII, from Gore Survey Products. EPA Region VII.
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Soda-Fabrik).
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Soda-Fabrik).
Black, L. and Fine, D., 2001, High levels of monoaromatic compounds limit the use of solid-phase micro-
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