SPE 77899
In-Situ Contamination Monitoring and GOR Measurement of Formation Fluid Samples
C. Dong, O.C. Mullins and P.S. Hegeman, Schlumberger; R. Teague, Unocal; A. Kurkjian and H. Elshahawi,
Schlumberger
Copyright 2002, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE Asia Pacific Oil and Gas Conference and
Exhibition held in Melbourne, Australia, 8–10 October 2002.
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Abstract
Formation fluid sampling early in the life of a well ensures
that vital information is available for timely input to field
planning decisions. Particularly in subsea wells, flow
assurance is a major concern, and formation fluid samples
from openhole logging help operators optimize investment in
both upstream and downstream facilities.
Oils have different color due to the amount of large,
complex aromatic compounds they contain. Since synthetic
and oil-base drilling muds contain simple aliphatic
compounds, they absorb little in the shorter wavelength color
channels. The Oil-Base Contamination Monitoring (OCM)
technique uses optical means to monitor the buildup of color
during sampling. The technique provides real-time analysis of
sample contamination, as well as prediction of how long it will
take to achieve an acceptably low level of contamination.
As reservoir fluid replaces filtrate in the flow line, the
optical density (OD) of the methane signal also increases, in
proportion to the oil’s methane content. Methane detection is
essential for condensates and for lightly colored crude oils.
For such fluids, the color buildup becomes difficult to detect;
however, the high methane content of these fluids makes
possible a reliable methane-based OCM algorithm.
Furthermore, the methane content can be used to determine
the gas/oil ratio (GOR) of the sample. When these methane-
based techniques are applied for darker oils, the color
absorption of the crude extends to the near infrared region and
covers the methane molecular vibration peak, resulting in a
higher methane signal optical magnitude. If uncorrected for,
this would result in errors in the methane-based contamination
prediction and GOR determination.
In this paper, we show how to measure GOR downhole
during sampling using the OD of the methane signal. We also
describe a decolorization algorithm to remove the color effect
from the methane optical channel. The algorithm is based on
the exponential decay of color absorption toward the high
wavelengths in the near infrared region. After decolorization,
the methane channel contains only methane molecular
vibration absorption, which is then used to derive an accurate
crude oil contamination value and GOR.
Introduction
When a formation fluid sample is taken from a well drilled
with Oil-Base Mud (OBM), the sample contamination by the
OBM filtrate is a critical factor for the accurate measurement
of the sample PVT properties. Usually when the
contamination is too high, the sample may become useless.
The in-situ sample OBM contamination can be predicted in
real time by Live Fluid Analyzer (LFA)1,2, a module of the
Modular Dynamics Tester3 MDT*, using the technique of
OBM Contamination Monitoring (OCM). This technique is
based on the change of color and methane concentration in the
flow line as the fluid cleans up. For very dark oil, the
contamination prediction from methane component becomes
unreliable because of the color effect. We developed a
decolorization technique to remove the color effect of heavy
oils and improve the real-time contamination monitoring
results.
Gas/Oil Ratio (GOR) is an important property of crude oil,
which has profound value in the design of the production
facilities. Conventionally, GOR is measured at a PVT lab by
flashing the crude oil into gaseous and liquid phases at
standard conditions (1 atm and 60oF). It may take many weeks
before the lab can provide this critical information. We
developed an in-situ GOR measurement technique, which uses
the optical properties of methane and oil components in crude
oil. With this technique, GOR can be measured downhole in
real time, when the sample is taken. Furthermore, GOR is
measured from live crude oil without phase separation. This
technique has many advantages over the conventional GOR
measurement. It keeps the sample intact and provides a
confirmation check for the lab PVT analysis. It also ensures
that GOR information is available at the wellsite. Downhole
*
Mark of Schlumberger
2 C. Dong, O.C. Mullins, P.S. Hegeman, R. Teague, A. Kurkjian, H. Elshahawi
GOR measurement also aids fingerprinting oils from different
layers and helps maintain the fluid in a single-phase during
sampling.
Color Absorption and Molecular Vibration
Absorption
The techniques of contamination monitoring, decolorization
and in-situ GOR measurement all rely on the optical
absorptions of crude oil in the Near Infrared (NIR) region.
Crude oils have two types of absorptions: color absorption and
molecular vibration absorption. Current sample contamination
assessment technique uses the color absorption and the
methane molecular vibration absorption. The downhole GOR
measurement uses the molecular vibration absorptions of
methane and oil.
Color Absorption. Color absorption is caused by electronic
excitations that convert light to heat. Oils have different color
due to their content of aromatic compounds. Aromatics, being
the heavy end of crude oil, yield significant light absorption
continuously from the visible to near infrared spectrum. Heavy
oils contain large amounts of aromatic compounds like
asphaltenes, and therefore have high absorption in the visible
wavelength region giving them a characteristic black color.
Light oils and gas condensates, on the other hand, have low
concentrations of aromatic compounds and low absorption in
the visible region, and usually are colorless or have a light
yellowish color as shown in Figure 1.
For most crude oils, the color absorption is wavelength
dependent and decays exponentially as the wavelength
increases4 as
β (4)
OD = α 0 Le λ (1)
where OD is the optical density, α0 and β are constants, L is
the path length and λ is the wavelength. Figure 1 demonstrates
this relation.
Molecular Vibration Absorption. In addition to color
absorption, crude oils also absorb light due to resonance of the
chemical bonds in the molecules. Whereas color absorption
occurs in a continuous wavelength, molecular vibration
absorption only occurs at certain wavelengths, which are
related to the molecule structure and the type of chemical
bond. As shown in Figure 1, oils have molecular vibration
absorption peaks near 1200 nm, 1400 nm and 1750 nm.
Molecular vibration absorption is a function of the component
density and does not change when the component phase
changes. For instance, with the same methane density, the
magnitudes of the molecular vibration absorptions of methane
are the same regardless of whether the methane is in a gas
phase or dissolved in crude oil.
The spectrum of crude oil is the sum of color absorption
and molecular vibration absorption as shown in Figure 1. Note
that black oils and tars have a very large absorption near 1750
nm due to their combined molecular vibration absorption and
color absorption in this region.
SPE 77899
Contamination Monitoring
When the reservoir fluid sample is taken by the MDT tool
from a well drilled with OBM, the fluid in the invaded zone,
which is typically a mixture of reservoir fluid and OBM
filtrate, flows into the LFA flow line first. As fluid in deeper
reservoir flows in, the fraction of the OBM filtrate in the flow
line decreases, and the fluid color as well as the methane
content both change. Mullins et al.1-3 developed the OCM
technique by measuring the optical density (OD) of both color
and methane channels in the LFA tool. Their study shows that
at a constant pumping rate, as the fraction of the reservoir
fluid increases, the buildup of the optical density follows
Equation 2
D (2)
OD = ODinf − 5
t 12
where ODinf is the optical density of the pure reservoir fluid,
which can be reached after infinite pumping time, D is a
constant and t is pumping time. ODinf and D can be calculated
by fitting the buildup curve with Equation 2.
Assuming the coloration of the crude oil is significantly
higher than that of the OBM filtrate, the contamination of the
fluid in the flow line at time t is given by
ODc _ inf − ODc (t )
Cc = (3)
ODc _ inf
where Cc is the volume fraction of the OBM filtrate
contamination calculated from color, ODc_inf is the optical
density of the color channel at infinite time and ODc(t) is the
color difference channel at time t. ODc(t) that is calculated by
ODc (t ) = ODcolor _ channel (t ) − ODbase _ channel (t )
The LFA tool has six color channels. ODcolor_channel is the
optical density of a selected color channel, and ODbase_channel is
the optical density of the base channel, which usually has no
absorption and is used as the baseline.
Because OBM filtrate usually contains no methane, but
crude oil, and especially gas condensate, contains significant
amounts of methane, the OBM filtrate contamination can be
monitored also by monitoring the change of methane content.
This is reflected by the methane molecular vibration
absorption with
ODm _ inf − ODm (t ) (5)
Cm =
ODm _ inf
where Cm is the volume fraction of OBM filtrate
contamination calculated from methane, ODm_inf is the optical
density of the LFA methane channel at infinite time and
ODm(t) is the methane difference channel at time t as
ODm = ODmethane _ channel − ODbase _ channel (6)
Figure 2 shows the buildup of the methane channel (red
curve) and color channel (green curve) as the sample is
cleaned up in an LFA sampling job. The base channel (light
SPE 77899 In-Situ Contamination Monitoring and GOR Measurement of Formation Fluid Samples
blue curve) is stable and close to zero and should not buildup
with time, because at the wavelength of this channel, most
crude oils have no absorption. By fitting the color and
methane difference channels with Equation 2, the OBM
contaminations from color and methane are calculated from
Equations 3 and 5 respectively.
Methane and color represent the light and heavy ends of
crude oil respectively, and contaminations from both methane
and color provide an internal consistency check on the data
quality. When these two measurements give similar values of
contamination, confidence can be placed on the results.
Furthermore, for light oils and gas condensates, there is very
little or no color contrast between the oil and the filtrate, and
the buildup of color is hard to detect. Therefore, color
monitoring will not provide a reliable contamination
prediction. In these cases, since condensate usually has a high
methane fraction, methane monitoring is the only reliable
measurement of contamination.
Color Effect and Decolorization
The OBM contamination monitoring technique works well for
most crude oils, but when the oil is very dark, color absorption
extends to the methane channel and the base channel, and as a
result, contamination prediction from methane becomes
incorrect. As shown in Figure 1, the entire spectrum of dark
oils (between black oil and tar) is shifted up because of the
heavy color absorption. The color absorption is wavelength
dependent, so subtracting the base channel from methane
channel cannot remove the color effect. As a result, the
methane difference channel (methane channel – base channel)
predicts an incorrect contamination.
Figure 3 shows the methane channel, base channel and
methane difference channel from an LFA sampling job of a
very dark oil. Because the oil is very dark, color absorption
extends to both the methane channel and the base channel.
Therefore, the methane channel contains both color absorption
and methane molecular vibration absorption, and the buildup
of the methane channel is the combination of both color and
methane effects. Because the color absorption extends to the
base channel too, as the fraction of the reservoir fluid (dark
oil) in the flow line increases, the base channel builds up with
time and is almost parallel to the methane channel as shown in
Figure 3. Compared with the base channel of the light oil in
Figure 2, the color effect in Figure 3 is significant. As a result
of the buildup of the base channel, the methane difference
channel (black curve in Figure 3) is very flat or even slightly
building down, which gives a nil contamination prediction. In
this case, the contamination from color is 20%, which is quite
different from the result of methane prediction.
The error is due to the color absorption on the base channel
and methane channel. To remove the color effect, the
correlation between color absorption and wavelength in
Equation 1 is used. Taking the natural logarithm of both sides
in Equation 1 yields
β the major component in the gaseous phase after crude oil is
ln(OD) = ln(α 0 L) + (7)
λ
3
Equation 7 suggests that ln(OD) has a linear relationship with
1/λ for crude oils as shown in Figure 4, which means we can
extrapolate the color absorption at other wavelengths from the
measured points. Because OBM filtrate is usually clear, we
assume Equation 7 is valid for a mixture of crude and filtrate.
The LFA has six color channels that have only color
absorption and no molecular vibration absorption. These color
channels are used to fit Equation 7 to determine the color
absorptions in the methane and base channels. Then, the color
absorption is subtracted from the methane and base channels,
and what is left in the methane channel is only the methane
molecular vibration absorption, and the base channel should
be close to zero and not build up with time.
This decolorization algorithm is applied to the dark oil in
Figure 3, and the result is shown in Figure 5. After
decolorization, the base channel (light blue curve) is very
close to zero and does not build up with time, indicating that
most of the absorption in the original base channel is due to
color. The methane channel after decolorization (red curve in
Figure 5) has a much lower optical density compared to before
decolorization (red curve in Figure 3), because all color
absorptions are removed and what is left is only the methane
molecular vibration absorption. The methane difference
channel (methane - base channel) after decolorization (black
curve in Figure 5) builds up with time, which is a significant
improvement compared to the builddown curve before
decolorization (black curve in Figure 3). The methane
difference channel is higher than before decolorization,
because there is more color absorption in the base channel
than in the methane channel. The contamination prediction
from the decolorized methane difference channel is 16%,
which is close to the prediction from color of 20%.
For dark oils, the decolorization algorithm effectively
removes the color effect and significantly improves the
methane contamination prediction. We also applied the
decolorization algorithm to light and medium oils. As
expected, the results show that the algorithm has almost no
effect on these oils, because color absorption does not affect
the methane and base channels.
In-Situ GOR Measurement
Theory. Gas/Oil Ratio (GOR) is defined as the volumetric
ratio of gas to liquid of crude oil at 1 atm and 60oF. It has a
large impact on the design of surface facilities and the
production process from the subsurface formation. The
conventional way to measure GOR in a PVT lab is to flash the
reservoir sample at 1 atm and 60oF and measure the volumes
of gas and liquid. This is termed “single-phase flash GOR.”
Using the optical properties of methane and oil
components in crude oil, we developed a technique of in-situ
downhole GOR measurement for live crude oil in real time.
Figure 65 shows the spectra of several live oils with different
GORs, of a dead oil and methane. The peak near 1660 nm is
due to vibrational absorption of methane molecules, which is
flashed at standard conditions. The peak near 1730 nm is due
4 C. Dong, O.C. Mullins, P.S. Hegeman, R. Teague, A. Kurkjian, H. Elshahawi
to the vibration absorption of the –CH2– group, which is the
major constituent of the molecular structure of most crude
oils. As GOR increases from dead oil (zero) to methane
(infinite), methane fraction increases and oil fraction
decreases, and as a result, the methane peak becomes higher
and the oil peak diminishes as shown in Figure 6.
Mullins’ study6 shows that the magnitude of the methane
peak is proportional to the methane density, and the magnitude
of the oil peak is proportional to the oil density. Therefore, the
ratio of the methane peak to oil peak can be used to calculate
the mass ratio of gas to liquid in crude oil, and furthermore,
the GOR can be calculated from the mass ratio. The LFA tool
has channels that cover the methane and oil peaks, and these
channels are used to calculate GOR of live crude oils.
Mullins7 analyzed the NIR spectra of binary mixtures of
methane and n-heptane to develop his GOR algorithm. In this
study, we followed a similar approach, but replaced the binary
mixture with live crude oils, and replaced the NIR spectra with
the signals from the LFA tool.
As shown in Figure 6, the methane and oil channels in the
LFA each have absorption contributions from both methane
and oil. A response matrix, B̂ , is formed to capture these
effects as
 bm _ m bm _ o 
(8)
B̂ =  
 bo _ m bo _ o 
where bm_m, bm_o are the response factors of the methane
channel to methane and dead oil, respectively, and bo_m, bo_o
are the response factors of the oil channel to methane and dead
oil, respectively. The response matrix is a critical factor in
GOR calculation; we measured the optical absorptions of
more than 30 live and dead oils and condensates to determine
and verify the LFA response matrix.
The mass fraction vector of methane and dead oil in crude
r
oil, m , is
r m  (9)
m =  m 
 mo 
where mm is the mass fraction of the methane and mo is the
mass fraction of dead oil. The signal vector from the LFA tool,
r
S , is
r s 
S =  m  (10)
 so 
where sm and so are the optical density responses of the
methane channel and oil channel respectively. The OD ratio of
the methane channel to oil channel is calculated by
sm (11)
OD Ratio =
so
r r
The signal vector S and the mass fraction vector m are
correlated as
r r
S = Bˆ m (12)
SPE 77899
Equation 12 provides a way to calculate the mass fractions of
methane and dead oil in a live crude oil from the optical
densities of the methane and oil channels.
When the live crude oil is flashed at 1atm and 60oF, the
gaseous phase contains methane (C1), other light gases (C2-
C5), non-hydrocarbon gases (CO2, H2S, N2) and the vapor of
the dead oil at its equilibrium vapor pressure. Assuming ideal
gas behavior at standard conditions, the mass ratio of the dead
oil vapor to methane is
mdead_oil_vapor pdead_oil_vapor wdead_oil_vapor (13)
=
mm pmethane wmethane
where mdead_oil_vapor is the mass fraction of the dead oil vapor
inside the gaseous phase, pdead_oil_vapor is the vapor pressure of
the dead oil vapor, pmethane is the partial pressure of methane,
wdead_oil_vapor is the average molecular weight of the dead oil
vapor and wmethane is the molecular weight of methane.
From our analysis of over 25 crude oils, we calculate an
average vapor pressure of the dead oil vapor to be 23.4 torr at
60oF and its average molecular weight to be 80.3 g/mol. The
molecular weight of methane is 16.04 g/mol. We assume a
typical gas is about 80% by volume of methane, so pmethane is
608 tor. Inserting these values into Equation 13 gives
mheptane_vapor = 0.193mm (14)
All gaseous components occupy the same volume, so we
can use either methane or dead oil vapor to calculate the
volume of the gaseous phase. GOR is the volume ratio of gas
to liquid at 1 atm and 60oF, and is calculated by
mm
RT
wmethane
p methane (15)
GOR =
(mo − 0.193mm )
ρ dead _ oil
where R is the universal gas constant, T is the temperature in
Kelvin, ρdead_oil is the average density of dead oil at 1 atm and
60oF. Inserting the values of wmethane (16.04 g/mol), R (8.31
J/mol/k), T (288.73 k), pmethane (608 torr) and ρdead_oil (0.862
g/cm3) into Equation 15 and converting units yield the
equation to calculate GOR from mass fraction
mm
GOR = 8930 scf/bbl (16)
mo − 0.193mm
Combining Equations 11, 12 and 16 gives the algorithm
for calculating GOR from OD ratio of methane channel to oil
channel, for live crude oils. Non-hydrocarbon components,
such as CO2 and H2S are not accounted for in this algorithm;
therefore, if the crude oil contains large amounts of these
impurities, this algorithm will underestimate the GOR.
Effect of Pressure and Temperature on OD Ratio. The real-
time GOR measurement is made at downhole conditions,
which vary considerably from well to well. If the OD ratio
SPE 77899 In-Situ Contamination Monitoring and GOR Measurement of Formation Fluid Samples 5

r
changes with pressure and/or temperature for the same GOR, m= mass fraction vector of methane and oil
it would be difficult to predict GOR from OD ratio alone. To OD = optical density
find the effect of pressure and temperature on OD ratio, the p= pressure, torr
spectra of four binary mixtures of methane and n-heptane, and R= universal gas constant, J/mol/k
a condensate, covering a wide GOR range, were analyzed. s= optical signal
r
The OD ratios of each sample measured at more than 13 S= optical signal vector
different pressures and temperatures are shown in Figure 7. t= pumping time, sec
The pressure ranges from 6000 psi to 20000 psi, and the T= temperature, k
temperature ranges from 20oC to 175oC. Figure 7 shows that w= molecular weight, g/mol
both pressure and temperature do not affect OD ratio α0 = defined by Eq. 1
significantly. OD ratio is a function of only GOR. Thus, the β= defined by Eq. 1
OD ratio measured at downhole conditions can be used to
λ= wavelength, nm
calculate GOR of live crude oil.
ρ= fluid density, g/cm3
Comparison with Field Data. We collected the LFA job data
Subscripts
and corresponding PVT lab reports from the Gulf of Mexico,
c = color
North Sea and other areas. The results are shown in Figure 8.
c_inf = color at infinite time
For the blue points, the OD ratios are measured with the LFA
inf = at infinite time
tool, and the GOR are from the PVT lab reports. The red line
m = methane
in Figure 8 is the GOR prediction from the OD ratio by the in-
m_inf = methane at infinite time
situ GOR measurement technique we have developed. There is
m_m = methane channel to methane
a very good agreement between the lab results and what GOR
m_o = methane channel to oil
model predicts. For most points in Figure 8, the error is less
o_m = oil channel to methane
than 10%. This comparison validates the technique of in-situ
o_o = oil channel to oil
GOR measurement in single-phase live crude oil.
o = oil
Conclusions
References
The optical absorption of crude oils is caused by both color
and molecular vibration absorptions. Sample contamination 1. Mullins, O. C. and Schroer, J.: “Real-Time Determination of
Filtrate Contamination During Openhole Wireline Sampling by
during formation testing can be monitored independently with Optical Spectroscopy”, paper SPE 63071 presented at the 2000
both the color channel and methane channel, and this provides SPE Annual Technical Conference and Exhibition, Dallas,
an internal consistency check. Based on the exponential decay Texas, October 1-4.
of color absorption with wavelength, a decolorization 2. Smits, A. R., Fincher, D. V., Nishida, K., Mullins, O. C.,
technique has been developed to remove the color effect on Schroeder, R. J. and Yamate, T.: “In-Situ Optical Fluid Analysis
the methane and base channels to improve the contamination as an Aid to Wireline Formation Sampling,” paper SPE 26496
prediction from methane. A real-time downhole GOR presented at the 1993 SPE Annual Technical Conference and
measurement of live crude oil has already been developed Exhibition, Houston, Texas, October 3-6.
based on the optical properties of live crude oils, with 3. Crombie, A., Halford, F., Hashem, M., McNeil, R., Thomas, E.
parameters determined from experiments and crude oil C., Melbourne, G. and Mullins, O. C.: “Innovations in Wireline
properties. The prediction of the GOR algorithm gives Fluid Sampling,” Oilfield Review, Autumn 1998.
excellent agreement with the PVT lab analysis for crude oils 4. Mullins, O. C., Sheu, E. Y.: Structures and Dynamics of
from many locations around the world. Asphaltenes, Plenum Press, New York and London.
5. Mullins, O. C. and Fujisawa, G., private communication.
Acknowledgements 6. Mullins, O. C., Joshi, N. B., Groenzin, H., Daigle, T., Crowell,
The authors gratefully acknowledge the assistance of our C., Joseph, M. T. and Jamaluddin, A.: “Linearity of Near-
colleagues at Oilphase, DBR, SKK, SDR and SPC. We thank Infrared Spectra of Alkanes,” Applied Spectroscopy 54, No. 4,
2000, 624-629.
Schlumberger for permission to present this paper.
7. Mullins, O. C., Daigle, T., Crowell, C., Groenzin, H. and Joshi,
N. B.: “Gas-Oil Ratio of Live Crude Oils Determined by Near-
Nomenclature Infrared Spectroscopy,” Applied Spectroscopy 55, No. 2, 2001,
b = optical channel response factor
197-201.
B̂ = response matrix of methane and oil channels
C = volume fraction of contamination
D = defined by Eq. 2
GOR = gas/oil ratio, scf/bbl
L = path length of light, mm
m = mass fraction
6 C. Dong, O.C. Mullins, P.S. Hegeman, R. Teague, A. Kurkjian, H. Elshahawi SPE 77899

Figure 1. Color absorption and molecular vibration absorptions of crude oils.

Figure 2. Color, methane and base channels of a light oil during a sampling job.
SPE 77899 In-Situ Contamination Monitoring and GOR Measurement of Formation Fluid Samples 7

Figure 3. Methane, base and difference channels of a dark oil before decolorization.

Figure 4. Linear relationship between ln(OD) and 1/λ for crude oils.
8 C. Dong, O.C. Mullins, P.S. Hegeman, R. Teague, A. Kurkjian, H. Elshahawi SPE 77899

Figure 5. Methane, base and difference channels of a dark oil after decolorization.

5
Figure 6. Spectra of live crude oils, methane and dead oil .
SPE 77899 In-Situ Contamination Monitoring and GOR Measurement of Formation Fluid Samples 9

Figure 7. OD ratios at different pressures and temperatures.

Figure 8. Comparison of GOR algorithm with field data.