The specific activity (
S
) and radiopurity (
R
) of tritium
labeled 2,3,7,8-tetrachlorodibenzo-p-dioxin, [3H]TCDD, were
measured by gas chromatography/mass spectrometry (GC/MS) while attempting to accurately characterize TCDD
doses received by invertebrates, fish, and fish embryos
during several toxicology studies conducted over a 3 year
period. The [3H]TCDD sample was found to consist of six
TCDD analogues involving hydrogen, deuterium, and tritium
substitution at the 1,6-dibenzo-p-dioxin carbon positions
and a complex mixture of impurities (with and without tritium
labels). Planar aromatic impurities were identified as tolyl-TCDD adducts and appeared to result from the decay
of 3H radiolabels to produce TCDD carbocations which
reacted with the solvent, toluene. Formation of TriCDD and
tolyl-TriCDDs, from both TCDD and tolyl-TCDDs, probably
resulted from radiolysis-induced loss of a chlorine to form
TriCDD free radicals which reacted with toluene. The
measurement of
S
for [3H]TCDD by GC/MS was accurate
and precise (±3%) because relative, rather than absolute,
amounts of the analogues were determined. Changes in
S
over time were accurately modeled as a function of the
conversion of each [3H]TCDD analogue to a solvent-TCDD analogue at a rate determined by 3H loss due to
decay. Storage, purification, and use of tritiated chemicals
for toxicology studies requires consideration of the 3H decay-related phenomena. For example, hydroxylated TCDD is
an expected decay reaction product of [3H]TCDD in tissues
and may be misidentified as a metabolite.