DISCUSSION AND REPLY

Age significance of Minnesota (Hostettler and Kvenvolden, 2002). The main

body of the spilled oil lies on top of the water table in a
n-C17/Pr ratios in forensic shallow sand and gravel aquifer. The analytical data dem-
onstrate that ‘‘the rate of degradation of the aliphatic
investigations of refined hydrocarbons at different sites within the oil body is
variable, most likely related to the availability of water
product and crude oil and oil saturation’’ (Hostettler and Kvenvolden, 2002,
p. 295). Of particular interest are the measured n-C17/
releases: Discussion Pr ratio values for samples collected within the spill oil
body at different dates. The initial value of this ratio
(n-C17/Pr)0 is equal to 1.3 (sample BE-31). One sample
Yakov Galperin1 and Isaac R. Kaplan2
collected in 1996 (approximately 17 yr after the spill)
exhibits the same value of 1.3 (sample BE-20), which
We wish to add our opinion to the recent discussion of
attests to a negligible rate of alkane degradation at this
the middle distillate degradation (MDD) model (Hurst
location. A series of samples collected in 1997 and 2001
and Schmidt, 2005) in this journal (Oudijk, 2007; Hurst
demonstrate that the alkane degradation rate at the soil-
and Schmidt, 2007). The MDD model was proposed
oil interface is measurably greater (n-C17/Pr = 0) than
as an extension of the Christensen and Larsen (1993)
that in the body of the spilled oil (n-C17/Pr ratio values
method, which, in addition to hydrocarbon-contaminated
span the range from 0.33 to 1.1).
soil, includes separate phase petroleum products and a
These two examples clearly demonstrate that the
broad range of environmental settings. In our opinion,
Hurst and Schmidt (2005) assumption of the uniform
such an extension contradicts the body of information
rate of alkane biodegradation, regardless of the site-
accumulated in the literature on biodegradation of pe-
specific conditions, is incorrect.
troleum hydrocarbons. The following examples reveal
Furthermore, in their attempt to explain the effect
fundamental flaws of the MDD model.
of the initial (n-C17/Pr)0 ratio on the calculated value of
The first example demonstrates that the rate of
the age of release, Hurst and Schmidt (2005, p. 185)
hydrocarbon degradation can change within a single en-
state that ‘‘to adjust the MDD model regression for
vironmental setting. Figure 1 (Parsons Engineering Sci-
variations in (n-C17/Pr)0 while maintaining the slope at
ence, 1999) shows gas chromatograms of soil samples
9.76, we use the relationship between T o and (n-C17/
collected from different depths at the site impacted by a
Pr)0 to calculate a new value for T o. The value of T o
single jet fuel JP-4 release that occurred approximately
sets the upper limit to the oldest release that can be
20 yr ago. These chromatograms clearly demonstrate
dated for a given value of (n-C17/Pr)0. For example, if
that alkane degradation rates are significantly greater in
(n-C17/Pr)0 of a release is known to be 1.5, T o will
near-surface samples (most of n-alkane are depleted at
equal 14.6 years; for an (n-C17/Pr)0 ratio of 4, T o equals
3.5, 5.5, and 7.5 ft [1.06, 1.67, and 2.28 m]) compared
39 years. The latter example is interesting in that it
to those at deeper soil samples (n-alkanes are readily
suggests that the age of hydrocarbon releases grater than
identified at 9.5 and 11 ft [2.89 and 3 m]).
20 years old might be modeled in cases where (n-C17/
Another example is related to the investigation of the
Pr)0 of a release exceeds that of the MDD model (i.e.,
1979 crude oil spill from a ruptured pipeline in Bemidji,
2.12; Table 1).’’ This statement is incorrect as written
because it implies that the rate of n-C17 degradation
could depend on the Pr concentration. For example, ac-
Copyright #2008. The American Association of Petroleum Geologists/Division of cording to Hurst and Schmidt’s (2005) interpretation,
Environmental Geosciences. All rights reserved.
1
if the initial concentration of n-C17 is 1000 ppm and the
Environmental Geochemistry Consulting, 13543 Bear Valley Road, Moorpark,
California, 93021; ygalperin@geochemconsulting.com
initial concentration of Pr is 472 ppm [(n-C17/Pr)0 = 2.2],
2
University of California, Los Angeles, 595 Charles Young Drive, Los Angeles, the complete degradation of n-C17 will take approx-
California, 90094; irkaplan@ucla.edu, IGPP publication No. 6384. imately 20 yr, whereas if the initial concentration of
DOI:10.1306/eg.01150807014 n-C17 is 1000 ppm but the initial concentration of Pr is

Environmental Geosciences, v. 15, no. 2 (June 2008), pp. 85 – 86 85

Figure 1. JP-4 impacted soil
chromatogram results with depth.
Defense Fuel Supply Point-Charleston,
South Carolina, fuel weathering
study (Parsons Engineering Science,
1999).
250 ppm [(n-C17/Pr)0 = 4], it will take close to 40 yr to
completely degrade n-C17.
Evaluation of the MDD model reveals inconsis-
tencies in its experimental base and theoretical premise.
The linear correlation proposed by Hurst and Schmidt
(2005) between the age of petroleum release and n-C17/
Pr ratio, regardless of the initial product composition and
site-specific conditions, contradicts published analytical
data and the body of information accumulated in the lit-
erature on the biodegradation of petroleum hydrocarbons.
REFERENCES CITED
Christensen, L. B., and T. H. Larsen, 1993, Method for determining
the age of diesel oil spills in the soil: Ground Water Monitoring
and Remediation, Fall, p. 142 – 149.
86 Discussion and Reply
Hostettler, F. D., and K. A. Kvenvolden, 2002, Alkylcyclohexanes
in environmental geochemistry: Environmental Forensics, v. 3,
p. 293 – 301.
Hurst, R. W., and G. W. Schmidt, 2005, Age significance of nC17/
Pr ratios in forensic investigations of refined product and crude
oil releases: Environmental Geosciences, v. 12, no. 3, p. 177 –
192.
Hurst, R. W., and G. W. Schmidt, 2007, Age significance of nC17/Pr
ratios in forensic investigations of refined product and crude oil
releases: Reply: Environmental Geosciences, v. 14, no. 2, p. 111 –
112.
Oudijk, G., 2007, Age significance of nC17/Pr ratios in forensic
investigations of refined product and crude oil releases: Dis-
cussion: Environmental Geosciences, v. 14, no. 2, p. 110 –
111.
Parsons Engineering Science, 1999, Light nonaqueous-phase liquid
weathering at various fuel release sites. Report to Air Force
Center for Environmental Excellence Technology Transfer Divi-
sion, Brooks Air Force Base, San Antonio, Texas: http:// www
.afcee.brooks.af.mil/products/techtrans/download/fuelweather-
ingreport.pdf (accessed September 8, 2006).