1,2,4-Trioxolanes, known as secondary ozonides (SOZs),
are key
products of ozonolysis of biogenic terpenoids. Functionalized terpenoid-derived
SOZs are readily taken up into atmospheric aerosols; however, their
condensed-phase fates remain unknown. Here, we report the results
of a time-dependent mass spectrometric investigation into the liquid-phase
fates of C
10
and C
13
SOZs synthesized by ozonolysis
of a C
10
monoterpene alcohol (α-terpineol) in water:acetone
(1:1 = vol:vol) mixtures. Isomerization of Criegee intermediates and
bimolecular reaction of Criegee intermediates with acetone produced
C
10
and C
13
SOZs, respectively, which were detected
as their Na
+
-adducts by positive-ion electrospray mass
spectrometry. Use of CD
3
COCD
3
, D
2
O, and H
2
18
O solvents enabled identification
of three types of C
13
SOZs (aldehyde, ketone, and lactol)
and other products. These SOZs were surprisingly stable in water:acetone
(1:1) mixtures at
T
= 298 K, with some persisting
for at least a week. Theoretical calculations supported the high stability
of the lactol-type C
13
SOZ formed from the aldehyde-type
C
13
SOZ via intramolecular rearrangement. The present results
suggest that terpenoid-derived SOZs can persist in atmospheric condensed
phases, potentially until they are delivered to the epithelial lining
fluid of the pulmonary alveoli via inhaled particulate matter, where
they may exert hitherto unrecognized adverse health effects.