Hydrocarbon fingerprinting, sometimes referred to as hydrocarbon
characterization, is a forensic geochemistry technique that is useful
for evaluating releases of petroleum and petroleum products. The
primary source of information for this technique
is high resolution capillary gas chromatography with a flame ionization
detector which gives detailed information not available from routine
EPA methods. This analysis can be done using free product samples,
extracts from soils, and extracts from water samples.
Four main questions can usually be answered using
1) What type or types of petroleum have been released
2) What type and degree of weathering has the petroleum experienced
3) In some cases, when was the product released
4) How do nearby samples compare to each other
Type of Product
Interpreting the type of product or products present in a sample
using gas chromatography data is primarily a process of visual examination
and comparison with chromatograms of known products. There have
been some advances in using statistical and numerical techniques
to evaluate the data, but these should only be considered tools
to assist in the interpretation and not a means to the final answer.
During the evaluation the interpreter must always be vigilant for
the effects of weathering and mixing of two or more products. Weathering,
discussed in more detail latter, can alter the chemistry of a product,
which in turn effects the appearance of the chromatogram and so
must be taken in to account when interpreting the gas chromatograms.
Click here to see examples of Chromatograms.
[Top of Page]
There are three primary types of weathering that may effect
the chemistry and thus the character of the gas chromatogram of
released products. Evaporation reduces the amount of the
most volatile compounds in a product. This is especially noticeable
in gasolines or products with compounds in the gasoline range. Biodegradation
will selectively remove certain types of hydrocarbons from a product.
The bacteria prefer normal paraffins, but when the normal paraffins
are gone the bacteria will start to remove other types of hydrocarbons.
Water washing (dissolution) preferentially removes the
more water soluble components of released products. The oxygenates
in gasoline are some of the most soluble compounds followed by the
BTEX compounds. Understanding how these three weathering processes
effect the chemistry of released products and the chromatograms
is essential to accurately interpret the type or types of products
Example of Biodegradation
Example of Water Washing
Several techniques have been postulated for estimating the age
or time of release of petroleum products. Of these, the one developed
by Christiansen and Larsen (1993) and further substantiated
by Schmidt, Beckmann and Torkelson (1999) appears to
be the most useful for middle distillates such as diesel fuel.
Christensen and Larsen analyzed a set of samples from sites where
the date of the diesel fuel spill was known. They discovered that
the ratio of nC17 to Pristane had a high correlation with the
age of the spill. From their work a formula (-8.4 x nC17/Pristane
+ 19.8 +/-2) can be used as a way to estimate the age of a spill.
Schmidt, Beckmann and Torkelson expanded the number of known age
spills in the data base and further validated the original work
of Christiansen and Larsen.
Comparison to Nearby Samples
Comparison of samples collected and analyzed from the same site
can be useful for evaluating the lateral extent of individual
spills (plumes), the commingling of two or more plumes, and likely
direction of the source of a spill.
Routine Data Presentation
The results of the gas chromatography analyses are usually e-mailed
to clients in the form of an MS-Word document. There will be two
pages for each sample. One page has the chromatogram filling the
entire page. The second page has four widows and two columns of
data. One window shows the entire chromatogram and three smaller
windows show different segments of the chromatogram. The two columns
of data are the peak heights and peak areas for the peaks identified
on the chromatogram. There will also be a scan of the chain of
custody form that came with the samples.
Example of full-size
Example of Multi-panel
Any of the identified peaks can be reported as percentage of the
entire chromatogram. This is not true quantitative data since there
is no calibration of the instruments. The reported semiquantitative
data is probably plus or minus 10% of a true quantitative analysis,
ie if a true quantitative value is 10% the semiquantitative value
might be reported as low as 9% and as high as 11%.
Customized Data Presentation
Customized presentation of the analytical results are available
for an additional fee.
[Top of Page]