Zero-Order Kinetics Model for the

Christensen-Larsen Method for Fugitive

Fuel Age Estimates
by Yakov Galperin and Isaac R. Kaplan*

Abstract
Estimating time of a middle distillate fuel release in soil can be performed under certain restricting environmental condi-
tions using the Christensen-Larsen method (CLM). This method is based on the linear correlation between the time since
a diesel fuel release and the corresponding value of n-heptadecane to pristane ratio (n-C17/Pr) but requires knowledge of the
initial ratio value. The empirical nature of this method does not, however, allow accounting for variance in the initial fuel
ðn-C017 Þ=ðPr0 Þ value used by CLM. Based on the zero-order approximation of the Monod model, we have deduced a general-
ized equation that can be used for estimating release ages of middle distillate fuels with different initial ðn-C017 Þ=ðPr0 Þ val-
ues. When combined with other site-specific factors, this equation provides a useful tool for the time of release estimates.

Introduction
Because legal and financial responsibility for hydrocar-
bon contamination is often decided based on the date of
a fuel release, the importance of reliable tools for deter-
mining residence time of fuel in the subsurface environ-
ment is undisputable. One of the age-dating approaches
uses a linear correlation between the time since occurrence
of a diesel fuel release (in years) and the corresponding
values of n-heptadecane (n-C17) to pristane (Pr) ratio
(Christensen and Larsen 1993), which can be approximated
(Hurst and Schmidt 2005) as follows:
T =
9:47 ðn-C17 =PrÞ þ 20:5
The observed decrease in the n-C17/Pr ratio over a time
period of approximately 20 years follows a well-estab-
lished path of the preferential biodegradation of n-alkanes
relative to isoalkanes (Atlas 1981; Kennicutt 1988; Glazer
1991). Statistical analysis of 13 data points led Christensen
and Larsen (1993) to conclude that for a specified set of
environmental conditions (e.g., geographic location, hydro-
carbon concentration, sampling depth, and paved soil), the
age of a diesel fuel spill in soil up to 20 years in age can be
estimated with an accuracy of 62 years at a 95% confi-
dence level.
The applicability of this correlation for estimating the
age of petroleum product releases has been extensively
discussed in the scientific literature (Kaplan et al. 1996;
Copyright ª 2008 The Author(s)
Journal compilation ª 2008 National Ground Water Association.
Wade 2002; Stout et al. 2002; Kaplan 2003; Oudijk et al.
2006). This age-dating approach can be a useful tool but
should be restricted to sites where a sudden, single release
of fuel has occurred. A slow continuous fuel release or con-
secutive fuel releases at the same area will invalidate the
method (Christensen and Larsen 1993; Stout et al. 2002).
Among other parameters affecting applicability of the
age-dating approach are selected soil characteristics, site
hydrology, temperature, moisture content, and availability
of oxygen and nutrients (Singer and Finnerty 1984; Foght
and Westlake 1987; Atlas and Bartha 1992; Yang et al.
1995; Coates et al. 1997; Kaplan et al. 1997). In some envi-
(1)
ronments, these parameters will favor fuel preservation; in
others, local environmental conditions will strongly pro-
mote weathering of the fuel and cause it to degrade at
a higher rate. In this case, n-C17 will be completely de-
pleted faster or slower than the 20.5 years predicted by
Christensen-Larsen method (CLM). In most environmental
investigations, the uncertainties in these parameters typi-
cally allow for only semiquantitative estimating age of
a fuel release.
In addition to the site-specific environmental condi-
tions, application of the CLM is confounded by uncertain-
ties introduced by variability of the initial ðn-C017 Þ=ðPr0 Þ
ratio. As stated in Christensen and Larsen (1993), the origi-
nal linear regression is based on the low variability of this
ratio in dispensed diesel fuels sold in northern Europe dur-
ing the early 1970s through the early 1990s. They have not,
however, attempted to extend applicability of the method to
fuels from different countries and continents that exhibit

94 Ground Water Monitoring & Remediation 28, no. 2/ Spring 2008/pages 94–97
a broad range of ðn-C017 Þ=ðPr0 Þ values. To evaluate the where (n-C17) and (Pr) are concentrations of n-C17 and Pr
effect of the ðn-C017 Þ=ðPr0 Þ variance on the calculation of at time t, respectively; (n-C017 ) and (Pr0) are initial concen-
the age of a fuel release, we developed a zero-order kinet- trations of n-C17 and Pr at time t ¼ 0, respectively.
ics model and a generalized equation that can be applied Because lmax17 >> lmaxPr , we assume that lmaxPr = 0, so
for any value of the initial ðn-C017 Þ=ðPr0 Þ ratio within the that
environmental constrains set by the CLM.
ðn-C17 Þ ðn-C017 Þ ðn-C017 Þ
=
lmax17 a17 t: (6)
ðPrÞ ðPr0 Þ ðPr0 Þ
Development of the Zero-Order Kinetics Model
Solving Equation 6 for t, we obtain:
To examine biochemical processes that could justify
the linear correlation represented by Equation 1, we con- ðPr0 Þ ðn-C17 Þ 1
t=

 þ (7)
sider the following basic model. Biodegradation of hydro- lmax17 a17 n-C017 ðPrÞ lmax17 a17
carbon fuel in a soil system is an enzyme-catalyzed
transformation of the fuel components. The rate of this cat- The parameters of Equation 7 can be estimated using
alytic reaction can be described by the Monod equation as the following coefficients of the Christensen and Larsen
follows (Alexander 1994): (1993) linear regression (Table 1 in Hurst and Schmidt
2005):
dS lmax SM t

= (2) ðn-C017 Þ=ðPr0 Þ = 2:16 (8)
dt Ks þ S
where S is contaminant concentration, Mt is total active 1
microbial cells concentration, lmax is maximum specific t0 = = 20:5
lmax17 a17
contaminant utilization rate, and Ks is Monod constant
(contaminant concentration when l = 12lmax ).
Experimental data in Christensen and Larsen (1993) so that Equation 7 is reduced to:
show that biodegradation of n-C17 relative to Pr can be ðn-C17 Þ
approximated by a linear equation. This is typical of micro- t =
9:49 þ 20:5 (9)
ðPrÞ
bial degradation of long-chain hydrocarbons (>C12) in dis-
solved phase. Unlike the more soluble organic substrates, which is equivalent to the Christensen and Larsen method
biodegradation rates of these low water soluble (<0.01 mg/ in Equation 1 shown previously.
L) hydrocarbons do not display the dependence on concen- Further, to account for deviations from the initial
tration (Leahy and Colwell 1990; Atlas and Bartha 1992; ðn-C017 Þ=ðPr0 Þ = 2:16, new initial values ðn-C#017 Þ=ðPr#0 Þ
Scow 1993), which is indicative of zero-order kinetics. can be expressed through the coefficient q as follows:
Zero-order kinetics imply excess of substrate, or in terms    
of the Monod equation, S >> Ks. The Christensen and n-C#017 ðn-C Þ n-C#017
017
q= = = =2:16 (10)
Larsen (1993) data also show that the time required for ðPr#0 Þ ðPr 0 Þ ðPr#0 Þ
complete depletion of n-C17 in a soil system is independent
of its initial concentration. This means that shortly after the so that Equation 7 can now be presented as:
hydrocarbon release into the soil system, the cell density of 9:49ðn-C17 Þ
the n-alkane degraders reaches its specific level pro- t=
þ 20:5 (11)
q ðPrÞ
portional to the initial concentration of hydrocarbon, Mt ¼
aS0 (a is the proportionality constant), and remains con- This is a generalized equation that can be applied for
stant afterward. This interpretation is consistent with the any value of the initial ðn-C017 Þ=ðPr0 Þ ratio, provided that
Monod model assumption that in certain conditions, the the CLM stated environmental conditions pertain.
yield of active microorganisms per unit amount of substrate
transformed does not vary with time and substrate concen-
tration (Simkins and Alexander 1984, 1985). Under these
Uncertainties Related to Variation of the Initial
conditions, Equation 2 can be reduced to: n-C17/Pr Ratio
Using a broader data base (35 data points), Hurst
dS

= lmax aS0 (3) and Schmidt (2005) proposed the middle distillate degrada-
dt tion (MDD) model and obtained a slightly different linear
or in integrated form, correlation:
S = S0
lmax aS0 t (4) T =
9:76 ðn-C17 =PrÞ þ 20:7; (12)
Now, for the biodegradation of n-C17 and Pr, we can corresponding to a new value for the initial ratio
write: ðn-C017 Þ=ðPr 0 Þ = 2:12. In addition, Hurst and Schmidt
8 (2005) stated that a deviation of the ðn-C017 Þ=ðPr 0 Þ ratio
< ðn-C17 Þ = ðn-C017 Þ
lmax a17 ðn-C017 Þt
(5) value from 2.12 will cause a proportional change in the
:


 intercept of the Equation 12 and, therefore, in the time re-
Pr = Pr 0
lmaxPr aPr Pr 0 t
quired for the complete removal of n-C17. This interpretation

Y. Galperin and I.R. Kaplan/ Ground Water Monitoring & Remediation 28, no. 2: 94–97 95
 45

40

35

Age of release (years)

30

25 t=-
9.7
6(n
-C
20 17 )
/(P
r)+
39
, eq
15 t=- t=-5 .14
t= 9.4 .13(
-1 n-C
t=- 3. 9(n 17 )/(P
9.7 75 -C r)+2
6(n (n 17 )/ 0.5,
10 -C -C (Pr eq.1
)+2 3
17 )/ 17 )
(P /(P 0.5
r)+ r)+ ,e
14 q.9
5 .6, 20
eq .5
.16 ,e
q.
15
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
(n-C17)/(Pr)

Figure 1. Plots demonstrating effect of variation of the initial ðn-C017 Þ=ðPr0 Þ on the age of release equation. Solid lines (Equations
9, 13, and 15) correspond to generalized Equation 11 with initial ratio ðn-C017 Þ=ðPr0 Þ values of 2.16, 4.0, and 1.5, respectively. Dash-
ed lines (Equations 14 and 16) correspond to Hurst and Schmidt (2005) interpretation for initial ratio values of 4.0 and 1.5, respec-
tively.

is incorrect as shown by applying the generalized Equation
11 to evaluate two examples discussed in Hurst and Schmidt
(2005), when ðn-C017 Þ=ðPr 0 Þ equals 4.0 and 1.5, respectively.
In the first example, ðn-C017 Þ=ðPr0 Þ = 4:0, q ¼ 1.85, and
ðn-C17 Þ
t =
5:13
ðPrÞ
which differs by both the slope and the intercept from
Equation 14 suggested by the MDD model (Hurst and
Schmidt 2005) as follows:
ðn-C17 Þ
t =
9:76
ðPrÞ
In the second example, ðn-C017 Þ=ðPr0 Þ ¼ 1.5, q ¼ 0.69,
and
ðn-C17 Þ
t =
13:75
ðPrÞ
which again differs by both the slope and the intercept
from the equation suggested by Hurst and Schmidt (2005):
ðn-C17 Þ
t =
9:76
ðPrÞ
For illustration, Equation 9 and Equations 13–16 are
plotted in Figure 1. The Hurst and Schmidt (2005) in-
terpretation suggests dependence between the initial con-
centrations of alkanes and the time required for their
biodegradation. However, the linearity of the CLM plot
demonstrates the independence of these parameters, which
is characteristic of zero-order kinetics.
Conclusions
The empirical linear relationship between the time
since the diesel fuel release in the subsurface and the
corresponding values of n-C17/Pr can be explained in terms
of the Monod model. Using the zero-order kinetics approx-
imation and the slope and intercept coefficients derived
from the Christensen and Larsen (1993) data, we estab-
lished a generalized equation that can be used for any value
þ 20:5 (13) of the initial ðn-C017 Þ=ðPr0 Þ ratio. The fact that depletion of
n-C17 in a soil system follows the Monod model with zero-
order kinetics is a result of microbial degradation of a low-
solubility substrate in dissolved phase.
The application of this equation is limited to certain
environmental conditions of soil contamination by a sud-
den, single release of a middle distillate fuel and can be
þ 39 (14)
used for approximation of age of a fuel release with the
caveat that the n-C17/Pr ratio is only one of many other
factors that typically need to be reconciled for a reliable
estimate of a fuel release age at a given site.
þ 20:5 (15)
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Biographical Sketches
Yakov Galperin, corresponding author, received an
engineering degree in chemistry (1972) and Ph.D. in physi-
cal organic chemistry (1975) from Leningrad Institute of
Technology, Russia. His current efforts are directed to
development and application of forensic geochemical
methods. He can be reached at Environmental Geochem-
istry Consulting, 13543 Bear Valley Road, Moorpark, CA
93021; (805) 529-4423; fax (805) 523-2074; ygalperin@
geochemconsulting.com.
Isaac (Ian) R. Kaplan, received his B.S. and M.S.
degrees in chemistry from Canterbury University, New
Zealand, and a Ph.D. in biogeochemistry from the Uni-
versity of Southern California in 1961. Dr. Kaplan received
a faculty appointment at University of California, Los
Angeles, in 1965 and is currently professor emeritus. He
can be reached at the Department of Earth & Space Scien-
ces and Institute of Geophysics & Planetary Physics,
University of California, 595 Charles Young Drive, Los
Angeles, CA 90094; irkaplan@ucla.edu.
*IGPP contribution 6301.
97