spectrum. The structure shown in Figure 5 was proposed
based on several analytical studies reported in detail by Fujita
et al. (44), including (i) manual interpretation of EI and CI
spectra; (ii) high resolution mass spectrometry (HRMS); (iii)
confirmation of the presence of nitrogen with a chemilu-
minescent nitrogen-specific detector; (iv) selective deriva-
tizations with diazomethane and acetic anhydride; (v) ether
cleavage with hydrobromic acid; (vi) hydrogenation of the
compound with palladium catalyst; and (vii) EI MS/ MS
analyses of selected ions.
(2) Talmage, S. Environmental and Human Safety of Major Sur-
factants. Alcohol Ethoxylates and Alkylphenol Ethoxylates; Lewis
Publishers: Ann Arbor, MI, 1994.
(
(
(
3) Ahel, M.; Giger, W.; Koch, M. Water Res. 1994, 28, 1131.
4) Schr o¨ der, H. F. J. Chromatogr. 1993, 647, 219.
5) Kubeck, E.; Naylor, C. G. J. Am. Oil Chem. Soc. 1990, 67, 400.
(6) Ball, H. A.; Reinhard, M. In Water Chlorination. Chemistry,
Environmental Impact, and Health Effects; Jolley, R. L., Bull, R.
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Lewis Publishers, Inc.: Chelsea, MI, 1984; Vol. 5, pp 1505-1514.
(
7) Ding, W.-H.; Wu, J.; Semadeni, M.; Reinhard, M. Manuscript in
preparation.
The proposed structure for the nitrogen-containing me-
tabolite AMeBrOP, indicating the addition of an amine group
during biotransformation, is unusual and appears to be
without precedent. No references to similar observations
were found in the literature. Advancing a hypothesis for its
formation merits further research.
Semi-quantitation of the detected intermediates was
performed for extracts of samples taken at days 0, 6, 9, 13,
and 35 of the BrOP1EC transformation experiment. Because
authentic standards were not available, concentrations were
estimated assuming a similar GC/ MS response factor for the
major EI ions of 2,4,4-trimethyl-1-pentanol (m/z 57) and 2,4,4-
trimethyl-2-pentanol (m/z 59) and for methylated BrOP1EC
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994, 28, 850.
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(
6
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(
(
(
2
7, 273.
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(
(
m/z 285), brominated octylphenol (m/z 213), and AMeBrOP
m/z 258). The average estimated concentrations (1 standard
Pollut. 1990, 64, 107.
(
(
17) Soto, A. M.; Justicia, H.; Wray, J. W.; Sonnenschein, C. Environ.
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1964, 41, 804.
deviation are presented in Table 3, along with the cumulative
OP1EC and BrOP1EC consumed.
The correspondence of the OP1EC consumption and the
2
,4,4-trimethyl-2-pentanol appearance suggests quantitative
formation and stability of the alcohol. As for the brominated
intermediates, by day 35, approximately 48% of the removed
BrOP1EC could be accounted for by the combined interme-
diates. This figure includes brominated octylphenol that was
recovered by solvent rinsing of the glass bottles at the
conclusion of the experiment. Whether the rest of the
unaccounted BrOP1EC was transformed into other unde-
tected products or mineralized is unknown, and it cannot be
discerned from the data whether some of the 2,4,4-trimethyl-
(
(
(
21) Osburn, Q. W.; Benedict, J. H. J. Am. Oil Chem. Soc. 1966, 43,
41.
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1
1
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1
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25) Maki, H.; Masuda, N.; Fujiwara, Y.; Ike, M.; Fujita, M. Appl.
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2
-pentanol was derived from the BrOP1EC.
(
The results of these experiments suggest that OP1EC can
be biologically degraded at concentrations at least 3 orders
of magnitude greater than in the environment, and aerobic
groundwater microorganisms can utilize OP1EC as a sole
source of carbon for growth. However, the entire molecule
of OP1EC does not appear to be available as a carbon and
energy source. The branched tert-octyl structure of the alkyl
group is resistant to microbiological attack, and under the
conditions of this study, the alkyl chain persists in the form
of the tertiary alcohol. Additional tests should be performed
to determine whether the experimental observations for
OP1EC are applicable under environmental conditions and
whether similar behavior is observed with residues of the
more common branched nonylphenol polyethoxylates. Fur-
ther studies on the fate of disinfection byproducts such as
BrOP1EC are also recommended, because their transforma-
tion may result in the production of additional persistent
and unexpected metabolites formed by pathways that are as
yet unknown.
(27) Cain, R. B. In Microbial Degradation of Xenobiotics and
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Acknowledgments
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36) Fales, H. M.; Jaouni, T. M.; Babashak, J. F. Anal. Chem. 1973, 45,
The authors are grateful to Dr. Wang-Hsien Ding for
performing the CI-MS analyses. Dr. Alfred Spormann
provided valuable discussion regarding the metabolites.
Funding for this project was provided by the Orange County
Water District, Orange County, California.
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