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Environmental Forensics
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On Methods for Age-Dating Diesel Fuel Released in the Near-Surface

Yakov Galperina; Isaac R. Kaplanb
Environmental Geochemistry Consulting, Moorpark, CA, USA b Institute of Geophysics and
Planetary Physics, University of California, Los Angeles, CA, USA

Online publication date: 16 March 2011

To cite this Article Galperin, Yakov and Kaplan, Isaac R.(2011) 'On Methods for Age-Dating Diesel Fuel Released in the
Near-Surface Environment', Environmental Forensics, 12: 1, 3 — 4
To link to this Article: DOI: 10.1080/15275922.2011.547436


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Environmental Forensics, 12:3–4, 2011
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ISSN: 1527–5922 print / 1527–5930 online

DOI: 10.1080/15275922.2011.547436

On Methods for Age-Dating Diesel Fuel Released in the

Near-Surface Environment
Yakov Galperin1 and Isaac R. Kaplan2
Environmental Geochemistry Consulting, Moorpark, CA, USA
Institute of Geophysics and Planetary Physics, University of California, Los Angeles, CA, USA

The editorial by Oudijk and Wade in this issue of the journal (2005) assumes the uniform rate of alkane biodegradation un-
demonstrates that confusion still exists regarding the applica- der typically aerobic conditions in vadose zone soil and un-
bility of Christensen and Larsen (1993) method (C&L) for age- der predominantly anaerobic conditions of the separate-phase
dating middle-distillate fuels in the near-surface environment. product, which contradicts published analytical data and the
Downloaded By: [Galperin, Yakov] At: 20:58 16 March 2011

The general comments in the editorial suggest a misunderstand- body of information accumulated in the literature on biodegra-
ing regarding a fundamental difference between the approach to dation of petroleum hydrocarbons. Due to the lack of a ba-
this method developed by Hurst and Schmidt (2005), which they sic model for hydrocarbon biodegradation in the near-surface
called the middle distillate degradation (MDD) model, and our environment, Hurst and Schmidt (2005) also misinterpret the
interpretation based on the basic Monod model for microbial effect of the initial (n-C017 )/(Pr0 ) values on the release age
substrate utilization kinetics (Galperin and Kaplan, 2008). calculation.
The C&L method established an empirical linear correlation The Galperin and Kaplan (2008) approach describes the em-
between the time since occurrence of a diesel fuel release and pirical linear correlation established by C&L in terms of the
the corresponding values of n-C17 /Pr ratio. This correlation was Monod model with zero-order kinetics. This model accounts for
ascertained for vadose (unsaturated) zone soil contamination variations in the initial (n-C017 )/(Pr0 ) values and allows for de-
occurring from a sudden fuel release at sites with specified sets veloping criteria for evaluating applicability of this age-dating
of environmental conditions (e.g., geographic location, hydro- method in different environmental settings. For example, be-
carbon concentration, sampling depth). Because of the empir- cause the Monod model relates the rate of substrate metabolism
ical nature of this correlation and the absence of descriptions to the concentration of a single growth-controlling substrate
of certain environmental parameters, no objective criteria can (Alexander, 1994), it implies an adequate supply of oxygen and
be developed on acceptable values of these parameters (i.e., soil nutrients, so that they do not limit bacterial metabolism. Accord-
characteristics, site hydrology, moisture content, and availability ingly, the C&L approach can only be applied to hydrocarbon
of oxygen and nutrients) for establishing the applicability limits contamination in the vadose zone soil where the availability of
of the C&L age-dating approach. An attempt to account for dif- sufficient concentration of O2 favors aerobic biodegradation. In
ferent environmental conditions through the matrix of “weath- contrast, a much slower degradation occurs under predominantly
ering regimes” (Oudijk, 2009) is based on subjective values and anaerobic conditions that commonly develop in the groundwa-
therefore is unreliable. In addition to the absence of criteria for ter (saturated) zone or in a body of non-aqueous phase liquid
site-specific environmental conditions, application of the C&L (NAPL).
approach is confounded by uncertainties introduced by variabil- The unsaturated zone soil water content is also a major fac-
ity of the initial n-heptadecane to pristane ratio, (n-C017 )/(Pr0 ). tor affecting hydrocarbon biodegradation. The degree to which
The MDD model (Hurst and Schmidt, 2005) was proposed the soil pore space is filled with water affects the exchange of
as an extension of the empirical C&L correlation, which in gases through the soil. The optimal water saturation is typically
addition to hydrocarbon-contaminated soil, includes separate- assumed to range from 30% to 70% of the total soil porosity,
phase petroleum products and a broad range of environmental depending on the soil texture. In practice, however, soil water
settings. Evaluation of the MDD model reveals inconsistencies content has been found to directly limit biodegradation rates only
in its experimental base and theoretical premise (Galperin and in very dry desert environments. A more common influence, is
Kaplan, 2008a). The extension proposed by Hurst and Schmidt that excess of soil water has led to significant reductions in soil
gas permeability and therefore deficiency of O2 required for
Address correspondence to Yakov Galperin, Environmental Geo- hydrocarbon mineralization. As in the case with water, the pore
chemistry Consulting, 13543 Bear Valley Road, Moorpark, CA, 93021, space can be filled with NAPL, which will also restrict the move-
USA. E-mail: ment of gases, so that O2 can be rapidly depleted and aerobic
4 Y. Galperin and I. R. Kaplan

degradation is severely inhibited. Residual NAPL concentration References

in the vadose zone soil should be considered as being close to the Alexander, M. 1994. Biodegradation and bioremediation. New York: Aca-
upper concentration limits of applicability of the model. In order demic Press.
to sustain microbial growth, certain nutrients must be available Christensen, L. B., and Larsen, T. H. 1993. Method for determining the age
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to be limiting, whereas the rest are considered micronutrients Christensen-Larsen method for fugitive fuel age estimates. Ground Water
and generally are available in excess in soil. However, because Monitoring and Remediation 28(2): 94–97.
Galperin, Y., and Kaplan, I. R. 2008a. Age significance of n-C17 /Pr ra-
nutrients are not destroyed, but recycled in an ecosystem, un-
tios in forensic investigations of refined product and crude oil releases:
like O2 , a steady input of nutrients is not required (Leeson and Discussion. Environmental Geosciences 15(2): 85–86.
Hinchee, 1996). Hurst, R. W., and Schmidt, G. W. 2005. Age significance of nC17 /Pr ra-
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main parameters affecting the rate of biodegradation typically Oudijk, G. 2009. Age dating heating-oil releases, Part 2. Assessing weath-
allow for only semi-quantitative estimating age of a fuel release ering and release time frames through chemistry, geology and site history.
(typically within ±5-year intervals). It is also widely accepted Environmental Forensics 10(2): 120–131.
Stout, S. A., Uhler, A. D., McCarthy, K. J., and Emsbo-Mattingly, S. D.
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that because of the multiple variables involved, the n-C17 /Pr

2002. Invited commentary on the Christensen and Larsen technique. En-
ratio is only one of many factors that typically need to be rec- vironmental Forensics 3(1): 9–11.
onciled for a reliable estimate of a fuel release age (Kaplan, Wade, M. J. 2002. Invited commentary on the Christensen and Larsen
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