Physical and chemical properties of BFRs
Environ. Toxicol. Chem. 21, 2002
1809
Table 3. Octanol–water partition coefficients (
K
OWs) of brominated
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diphenyl ether (BDE) congeners based on polychlorinated diphenyl
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constants of Br and Cl
Congener
KOW CDEa
KOW BDEb
3
15
28
47
66
77
85
99
100
138
153
154
183
190
4.70
5.25
5.53
5.95
6.13
6.36
6.28
6.38
6.11
7.01
6.72
6.49
NDc
7.31
4.85
5.55
5.98
6.55
6.73
6.96
7.03
7.13
6.86
7.91
7.62
7.39
ND
8.36
a Experimental values from Kurz and Ballschmiter [19].
b Calculated with the equation KOW (BDE no. z)
KOW (CDE no. z)
no. Br (or no. Cl atoms) (fBr fCl), where z is the congener
number and fBr and fCl are the fragment constants for Br (1.09) and
Cl (0.94), respectively [6]. For example, KOW (BDE-85) 6.28
(1.09 0.94) 7.03.
not determined; the KOW for this CDE congener was not
ϭ
ϩ
ϫ
Ϫ
ϭ
ϩ
10. Hinckley DA, Bidleman TF, Foreman WT, Tuschall JR. 1990.
5
ϫ
Ϫ
ϭ
Determination of vapor pressures for nonpolar and semipolar or-
c ND
ϭ
ganic compounds from gas chromatographic retention data.
J
determined by Kurz and Ballschmiter [19].
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bilities, Henry’s law constants, partition coefficients between gas/
model suggests that these compounds would be present mainly
in relatively immobile environmental media such as soil and
sediment. The relatively recent and short period of use of these
BFRs may also contribute to the localization of their distri-
butions around sources.
The fact that PBDEs have been detected in the Arctic en-
vironment [27,28] might seem to contradict the results of the
model. However, like PCBs, in which many congeners over-
whelmingly partition into soil and sediment compartments, if
minor amounts of PBDEs were released or partition into the
atmosphere, the likelihood exists for them to become particle-
bound or to exist in the gaseous phase [17] and undergo long-
range transport. Also, the model predicts relative amounts of
the chemicals in various compartments at equilibrium and does
not include the time to reach equilibrium. Other physicochem-
ical data, such as hydrolysis, photolysis, and other degradation
rates, plus the presence of biomass and organisms, are needed
to construct more sophisticated higher level models. At this
point, such data are not available.
The variations in physical properties observed with changes
in bromine content of PBDEs indicate that differences would
occur in their distribution and fate between homologue groups.
The lower brominated congeners would have a more wide-
spread distribution because of higher vapor pressures, solu-
water (KGW), n-octanol/water (KOW) and gas/n-octanol (KGO) of
106 polychlorinated diphenyl ethers (PCDE). Chemosphere 38:
573–586.
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1984. Aqueous solubilities, octanol/water partition coefficients,
and entropies of melting of chlorinated benzenes and biphenyls.
J Chem Eng Data 29:184–190.
bilities, and lower
KOWs. Therefore, this change in behavior
with bromine content demonstrates that debromination reac-
tions [29] will have an impact on the fate and distribution of
PBDEs and other BFRs.
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ubilities and partition coefficients of PCBs, and the mathematical
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aqueous solubilities for nonortho and mono-ortho substituted po-
lychlorinated biphenyls. Chemosphere 31:4549–4557.
23. Burkhard LP, Armstrong DE, Andren AW. 1985. Henry’s law
constants for the polychlorinated biphenyls. Environ Sci Technol
19:590–596.
Acknowledgement—We would like to thank Brock Chittim (Welling-
ton Laboratories) for help in obtaining BFR compounds and standards.
We also thank John Westmore (University of Manitoba), Eric Brae-
kevelt (Freshwater Institute), and Jason Duffe (National Wildlife Re-
search Centre) for their helpful discussions.
24. Mackay D, Di Guardo A, Paterson S, Cowan CE. 1996. Evalu-
ating the environmental fate of a variety of types of chemicals
using the EQC model. Environ Toxicol Chem 15:1627–1637.
25. Karickhoff SW. 1981. Semi-empirical estimation of sorption of
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