SPME Coupled with GC-

FID for the Detection of

n-Propyl Alcohol and Its
Use as a Geothermal
Tracer

Michael Mella1,2
1
Energy and Geoscience Institute - University of Utah,
2 Chemical Engineering Department – University of Utah
Senior Projects Lab I - 2006
Why n-propanol?

 Liquid phase only tracers and vapor

phase only tracers are in common use
 Two-phase tracers are needed to
better trace water
 n-Propanol has a similar partition
coefficient to water, similar two-phase
characteristics to water
Objectives

 Lab work - Develop an analytical

method to reduce the limit of
detection of n-propanol
 Field work - Validate method with a
field test
Lab Development

 Solid Phase MicroExtraction (SPME)

was used to help lower the limit of
detection over previous methods by 30
fold
 Gas Chromatography with a Flame
Ionization Detector used to analyze n-
propanol solutions
SPME basics

 A flexible fiber coated with 85µm thick

Carboxen/PDMS layer
 A needle that houses the fiber and an
injection assembly
GC analysis

 Needle injected into 300°C GC inlet

 Separation by HP-5 capillary column
 Detection by FID
 Analysis of signal using HP-CHEM
software
Analytical method results

 Limit of detection at 1 ppb

 Reduction by a factor of 30 from
previous methods
 Lower limit of detection means less n-
propanol needed for test
 Method can be extended to other
alcohols and aldehydes
Objectives

 Lab work - Develop an analytical

method to reduce the limit of
detection of n-propanol
 Field work - Validate method with
a field test
Field test

 Injector 34-9RD2 of Coso East Flank

tagged with 165 gallons n-propanol
 Samples taken from surrounding East
Flank producers
Field Work

 Alcohol returns
 Comparison with a liquid tracer test
Alcohol returns

 Raw results
 E(t) scaled results and recovery
 Liquid phase tracer results
Alcohol returns

 Raw results
 E(t) scaled results and recovery
 Liquid phase tracer results
E(t)
 E(t) residence-time distribution function
 E(t) is a way to normalize for mass of tracer
injected and flow rates
 E(t) required for future assessment of
return data, an example is the convolution
integral and tracer recovery
C (t )
E (t )  

 C (t ) dt
0
Tracer Recovery
 Use E(t) to calculate the amount of tracer
recovered in both the liquid phase and the
vapor phase.

t
%returned   E (t )dt
0
Alcohol returns

 Raw results
 E(t) scaled results and recovery
 Liquid phase tracer return
Liquid phase tracer return

 2 months prior 100 kg 1,3,5-NTS

injected into 34-9RD2
 Samples from the same area were
taken and analyzed by HPLC with a
fluorescence detector
Return comparisons

 Normalized n-propanol and 1,3,5-NTS

return curves were plotted together
with a common x-axis of days after
their respective injection date.
Return comparisons

 Tracer recovery of n-propanol = 3.5%

 Tracer recover of 1,3,5-NTS = 74.8%
Conclusions

 Similar arrival times for 1,3,5-NTS

and n-propanol in well 38C-9
 Appearance of n-propanol in 38D-9
but not 1,3,5-NTS
 38B-9 seems to have been “skipped”
by both tracers
 Less return of n-propanol than of
1,3,5-NTS
Conclusions

 Similar arrival times for 1,3,5-NTS and

n-propanol in well 38C-9
 Appearance of n-propanol in 38D-
9 but not 1,3,5-NTS
 38B-9 seems to have been “skipped”
by both tracers
 Less return of n-propanol than of
1,3,5-NTS
Conclusions

 Similar arrival times for 1,3,5-NTS and

n-propanol in well 38C-9
 Appearance of n-propanol in 38D-9
but not 1,3,5-NTS
 38B-9 seems to have been
“skipped” by both tracers
 Less return of n-propanol than of
1,3,5-NTS
Conclusions

 Similar arrival times for 1,3,5-NTS and

n-propanol in well 38C-9
 Appearance of n-propanol in 38D-9
but not 1,3,5-NTS
 38B-9 seems to have been “skipped”
by both tracers
 Less return of n-propanol than of
1,3,5-NTS
Conclusion

 Lab work - n-propanol is appropriate

as a geothermal tracer in smaller
volume by using SPME-GC-FID
 Lab work - Alcohols can be a powerful
tool in determining two-phase
pathways in reservoirs
Acknowledgements

This work was supported by grants from

the Department of Energy. Done with
the support of Coso Operating
Company, LLC; and the Geothermal
Program Office of the Naval Air
Weapons Station.
Acknowledgements

Peter Rose1, Nick Dahdah1, Michael

Adams1, Jess McCulloch2, Cliff Buck2,
and G. Michael Shook3
1 Energy and Geoscience Institute – University of Utah
2 Coso Operating Company – Catihness Energy LLC
3 Idaho National Laboratory
References
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Tracers,” World Geothermal Congress p. 3015­3019
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Dahdah, N. (2004), “Alcohols as Two­Phase Tracers,”  Proceedings, 
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Geothermal Reservoir Engineering
References
Mella,  M.J.,  Rose,  P.E.,  McCulloch,  J.,  Buck,  C.,  Adams,  M.C., 
Dahdah, N.F. (2006), “The Use of n­Propanol as a Tracer at the site 
of  the  Coso  Engineered  Geothermal  System,”  PROCEEDINGS, 
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Stanford University,SGP­TR­179  
Rose, P.E., Mella, M.J., Kasteler, C. (2003), “A New Tracer For Use in 
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Liquid­Dominated,  High­Temperature  Geothermal  Reservoirs,” 
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Questions?