Magnetic susceptibility of petroleum reservoir uids

Oleksandr P. Ivakhnenko, David K. Potter

*
Institute of Petroleum Engineering, Heriot-Watt University, Edinburgh EH14 4AS, UK
Abstract
A knowledge of the magnetic properties of petroleum reservoir uids may provide new techniques for improved reservoir char-
acterisation, petroleum exploration and production. However, magnetic information is currently scarce for the vast majority of res-
ervoir uids. For instance, there is little in the literature concerning basic magnetic susceptibility values of crude oils or formation
waters. We have therefore measured the mass magnetic susceptibility (v
m
) of several crude oils, rened oil fractions, and formation
waters from local and world-wide sites. All the uids measured were diamagnetic, however there were distinct dierences in mag-
nitude between the dierent uid types. In particular, v
m
for the crude oils was more negative than for the formation waters of the
same locality. The magnetic susceptibility of the oils appears to be related to their main physical and chemical properties. The results
correlated with the density, residue content, API (American Petroleum Institute) gravity, viscosity, sulphur content and metal con-
centration of the uids. Light fractions of crude oil were the most diamagnetic. The magnetic measurements potentially allow phys-
ical and chemical dierences between the uids to be rapidly characterised. The results suggest other possible applications, such as
passive in situ magnetic susceptibility sensors for uid monitoring (for example, the onset of water breakthrough, or the detection of
migrating nes) in reservoirs, which would provide an environmentally friendly alternative to radioactive tracers. The mass magnetic
susceptibilities of the uids in relation to typical reservoir minerals may also play a role in uidrock interactions, such as studies of
wettability. The v
m
of crude oil from the various world-wide oil provinces that were tested also showed some dierences, possibly
reecting broad physical and chemical features of the geological history of each province.
2004 Elsevier Ltd. All rights reserved.
Keywords: Magnetic susceptibility; Crude oil; Formation water; Petroleum reservoir
1. Introduction
Magnetic methods and techniques are prominent in
the area of geoscience. However, there is little widely
available data concerning the magnetic susceptibility of
the majority of natural reservoir uids. The most com-
plete studies are by Ergin et al. (1975), and Ergin and
Yarulin (1979), which are written in Russian and are
not well known to worldwide researchers. These studies
determined the mass magnetic susceptibility of crude oils
in some of the oil provinces of the former USSR. Ergin
and Yarulin (1979) showed that the mass magnetic sus-
ceptibility of the crude oils was diamagnetic (low and neg-
ative) and varied from 0.942 to 1.04210
8
m
3
kg
1
,
but mainly within the range 0.98 to 1.0210
8
m
3
kg
1
. They also analysed many of the components
of crude oil, which we have compiled and plotted in
Fig. 1, and showed that the most diamagnetic hydrocar-
bon compounds were the alkanes, cyclopentanes and cy-
clohexanes. These ranged in value from about 1.00 to
1.1310
8
m
3
kg
1
. In contrast, the oxygen and nitro-
gen compounds were signicantly less diamagnetic. The
Ergin and Yarulin (1979) study also found some correla-
tions between the mass susceptibility and certain other
physical and chemical properties of the oils. In general,
the authors found that the magnetic susceptibility of
the oils increased with depth, although there were excep-
tions. More signicantly, they found that the mass
1474-7065/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pce.2004.06.001
*
Corresponding author.
E-mail address: david.potter@pet.hw.ac.uk (D.K. Potter).
www.elsevier.com/locate/pce
Physics and Chemistry of the Earth 29 (2004) 899907
susceptibilities of the oil from individual oil provinces had
distinctly dierent values. There were also small varia-
tions in the values between dierent tectonic areas in
the same oil province, and even between dierent collec-
tors of the same oil deposit. On the basis of these results
the authors suggested the possibility of distinguishing oils
from dierent provinces and stratigraphic intervals by
comparing their average magnetic susceptibility values.
In our present paper we detail a systematic study of
the mass magnetic susceptibility of natural reservoir u-
ids. These included crude oils from various oil provinces
worldwide, and also rened oil fractions. In addition we
analysed the magnetic susceptibility of formation
waters, which represent the rst such measurements as
far as we are aware.
2. Experimental measurements
2.1. Description of uid samples
Three types of reservoir uids were involved in the
current study: crude oil from active petroleum reser-
voirs, rened oil fractions, and formation waters. A suite
of 22 samples of fresh crude oil were collected mainly
from sites in the North Sea and other representative
world oil provinces such as the Middle East, North
America, the Far East and Russia. The samples of crude
oil from the other world provinces were chosen with a
range of distinctive physical and chemical dierences.
The uids were kept in their sealed containers until a
few days before the measurements when they were
poured into glass sealed tubes. The rened petroleum
uids came from the Forties eld crude oil and con-
tained light to heavier fractions including gasoline, ker-
osene, light gas oil, heavy gas oil and vacuum gas oil.
The formation waters came from the Dunbar and
Forties elds in the North Sea oil province. This allowed
magnetic susceptibility results to be directly compared
with those for crude oil samples from the same oilelds.
The composition of the solutes in these two formation
waters is shown in Table 1. We also studied a sample
of sea water, which was pumped through the injection
wells into the reservoirs, and measured the magnetic sus-
ceptibility of distilled water for comparison.
All the uid samples were clean from mechanical and
other uid contamination. All the samples were previ-
ously well characterised by the supplying companies,
who assured us of the sample cleanliness. We are there-
fore condent that the results we observe are not due to
some artefact of the extraction infrastructure (pipelines
etc.).
-1.15
-1.10
-1.05
-1.00
-0.95
-0.90
-0.85
-0.80
-0.75
-0.70
-0.65
-0.60
-0.55
0 50 100 150 200 250 300 350 400 450
Crude Oil Compounds
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8

m
3
/
k
g
)
Alkanes
Cyclopentanes and cyclohexanes
Benzol and its homologue series
Naphtheno-aromatic
hydrocarbons
Polycyclic aromatic hydrocarbons
Monocarboxylic acids
Phenols
Naphthenic acids
Piradines
Quinolines
Thiols
Sulphides
Thiophenes and thiophanes
Hydrocarbons
Sulphur compounds
Nitrogen
compounds
Oxygen
compounds
Fig. 1. Mass magnetic susceptibility of crude oil compounds (based on the data of Ergin and Yarulin (1979)).
Table 1
Formation waters and sea water solute composition
Solute composition Concentration
Dunbar formation water (kgm
3
) Forties formation water (kgm
3
) Sea water (kgm
3
)
NaCl 34.13 79.5 24.41
CaCl
2
6H
2
O 7.74 10.93 2.34
MgCl
2
H
2
O 1.25 6.18 11.44
KCl 0.43 1.25 0.88
BaCl
2
0.43 0.48 0.00
SrCl
2
0.47 2.35 0.00
Na
2
SO
4
0.00 0.00 3.98
900 O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907
2.2. Experimental procedures
Since we expected that the uids would have diamag-
netic (low and negative) magnetic susceptibilities we
required very sensitive measuring equipment. We there-
fore initially measured the mass magnetic susceptibility
(v
m
) of the uids using a Sherwood Scientic mag-
netic susceptibility balance (MSB) Mark I. The MSB
Mark I or Evans magnetic balance is designed as a re-
verse traditional Gouy magnetic balance. The Evans
method uses the same conguration as the Gouy meth-
od except that instead of measuring the force with which
a magnet exerts on the sample, the equal and opposite
force which the sample exerts on moving permanent
magnets is measured. Two pairs of magnets are posi-
tioned at opposite ends of a beam making a balanced
system. When the sample is placed in the susceptibility
balance between one pair of magnets, the beam is no
longer in equilibrium and is deected, and the move-
ment is optically detected. A compensating force is ap-
plied by a coil between the other pair of magnets. The
current required to bring the beam back into equilib-
rium is proportional to the force exerted by the sample,
which in turn is proportional to the magnetic suscepti-
bility. Note that the measurements in this case depend
on a dc eld and not the more common ac susceptibility
bridge method.
The calibration of the MSB was made using distilled
water, produced in the presence of air. The presence of
dissolved atmospheric oxygen in the calibrating sample
and uid samples was ignored. A value of 0.9043
(10
8
m
3
kg
1
) for the mass magnetic susceptibility of
water at 20 C (Selwood, 1956) was used for the calibra-
tion. Repeat calibration measurements were regularly
made throughout the measurement period and were
within 0.35% of the published value for water. The val-
ues of v
m
for the studied uids were determined at room
temperature (normally about 18 C), and corrected for
the displaced air in the measuring tube.
In order to gain sensitive independent magnetic sus-
ceptibility measurements we analysed some samples
using a Magnetic Properties Measuring System (MPMS
2) SQUID magnetometer. The measurements again de-
pend on a dc eld. The crude oil samples were measured
in gelatine capsules, while the formation water was mea-
sured in glass capsules. The eect of the uid containers
was subtracted from the results. The measurements in
these cases were made at a temperature of 20 C. The
measurement time using the SQUID was signicantly
longer than for the MSB.
3. Results
3.1. Mass magnetic susceptibilities of crude oils and
formation waters
Fig. 2 details the measurements made on the Sher-
wood Scientic MSB Mark I, and shows that the mass
magnetic susceptibilities of all the natural reservoir u-
ids studied were diamagnetic. There is a distinct dier-
ence between the values for the crude oils and all the
water samples. The crude oils all have more negative
mass magnetic susceptibilities than the waters. This is
exemplied by the Dunbar and Forties results, where
there are clear dierences between the values for crude
oil and formation water from the same oileld. This
demonstrates that there is a real dierence between the
O
i
l

R
u
s
s
i
a
O
i
l

N
.

S
e
a

M
c
G
e
e

O
i
l

N
.

S
e
a

B
i
l
o
n
d
o
O
i
l

N
.

S
e
a

O
r
q
u
i
d
e
a

1
O
i
l

N
.

S
e
a
O
i
l

N
.

S
e
a

K
u
i
t
o
O
i
l

M
i
d
d
l
e

E
a
s
t
O
i
l

N
.

S
e
a

M
i
l
l
e
r
O
i
l

N
.

S
e
a

D
a
l
i
a

2
O
i
l

N
.

S
e
a

H
a
r
d
i
n
g

O
i
l

N
.

S
e
a

O
i
l

N
.

S
e
a

M
o
h
o
O
i
l

N
.

S
e
a

C
l
a
r
e

O
i
l

N
.

S
e
a

D
a
l
i
a

3
O
i
l

N
.

S
e
a
O
i
l

N
o
r
t
h

A
m
e
r
i
c
a
O
i
l

N
.

S
e
a

D
u
n
b
a
r
O
i
l

N
.

S
e
a

M
a
r
a
t
h
o
n

O
i
l

N
.

S
e
a

F
o
r
t
i
e
s
O
i
l

M
i
d
d
l
e

E
a
s
t
O
i
l

N
o
r
t
h

A
m
e
r
i
c
a
O
i
l

F
a
r

E
a
s
t
D
i
s
t
i
l
l
e
d

w
a
t
e
r

F
W

N
.

S
e
a

F
o
r
t
i
e
s


F
W

N
.

S
e
a

D
u
n
b
a
r

S
e
a

w
a
t
e
r

-1.06
-1.04
-1.02
-1.00
-0.98
-0.96
-0.94
-0.92
-0.90
-0.88
-0.86
-0.84
0 5 10 15 20 25
Formation Waters and Crude Oils
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0

-
8

m
3
/
k
g
)
Fig. 2. Mass magnetic susceptibility of formation waters (FW) and crude oils determined using a Sherwood MSB Mark I. The measurement errors
are of the order of 0.004 (10
8
m
3
kg
1
), close to the size of the symbols.
O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907 901
mass magnetic susceptibility of the crude oils and the
formation waters, which may have been less clear had
we only measured crude oil from one locality and com-
pared it with formation water from another locality. The
reproducibility of the readings was tested by subjecting
the samples to ve repeat measurements, and was found
to be very high, with the standard deviation being below
0.00410
8
m
3
kg
1
. Our values for crude oil are com-
parable to those determined by Ergin and Yarulin
(1979). Most of their results were within the range
0.98 to 1.0210
8
m
3
kg
1
, which is within the range
of the majority of our crude oil samples, and is distinct
from the formation waters measured here.
As an independent check on the dierences between
the formation waters and the crude oils we measured
the Dunbar samples in a Magnetic Properties Measuring
System (MPMS 2) SQUID magnetometer. Fig. 3 shows
the results of the mass magnetisation versus the applied
eld. The slope of the lines represents the mass magnetic
susceptibility. The results show that the susceptibility of
the Dunbar crude oil is lower than that of the Dunbar
formation water, consistent with the results shown in
Fig. 2 derived from the Sherwood MSB. The absolute
values of magnetic susceptibility are within about 4%
of the Sherwood MSB measurements for the crude oil
and under 1% for the formation water. These appear
to be satisfactory independent measurements consider-
ing the dierent operating principles of the two sets of
equipment.
Small dierences in the values for the dierent water
samples may be related to the solutes they contain. Since
the compositions are relatively straightforward, we the-
oretically calculated the mass magnetic susceptibilities.
The results are given in Table 2 and show that the the-
oretical values are very close to those determined exper-
imentally, the dierence between them being less than
1%.
Since the composition of the crude oils is much more
complex, and we do not have detailed compositional
information for many of the samples, we have not as
yet attempted to theoretically calculate the susceptibil-
ity. It seems clear from Fig. 2 that there are variations
between the dierent crude oil samples, and these may
be related to their physical and chemical properties as
detailed below.
3.2. Relation between mass magnetic susceptibility and
physical properties
The main purpose of the following analyses was to
determine whether magnetic susceptibility measure-
ments correlated with various physical properties of
the reservoir uids, and to establish whether magnetic
measurements might provide a rapid alternative means
of characterising dierent petroleum reservoir uids.
Fig. 4 shows a plot of density versus mass magnetic sus-
ceptibility for the crude oils, rened fractions, formation
waters, and other water samples. There is a trend of
higher density corresponding to higher mass magnetic
susceptibilities, with a clear dierence between the oils
and the formation waters. The same general trend is also
shown for the rened oil fractions, where the mass mag-
netic susceptibility increases from the lighter to the hea-
vier fractions (from gasoline to light gas oil, heavy gas
oil and vacuum gas oil). The exception is kerosene, the
fraction extracted after gasoline. The oxygen com-
pounds of crude oil, usually naphthenic acids, are highly
represented in the kerosene fraction. These compounds
have relatively higher (less negative) mass susceptibilities
than many of the other components of the oil (see Fig.
1), and this may contribute towards the higher value
of v
m
for kerosene. Light fractions of crude oil, such
as gasoline, are the most diamagnetic.
Fig. 5 shows the residue content above 342 C versus
mass magnetic susceptibility for the crude oils for which
we had some compositional data. The residue is what
remains after fractional distillation of the lighter hydro-
carbon components. It is evident that the higher the
residue content the higher is the mass magnetic suscep-
tibility. The samples with higher residue content are also
-80
-70
-60
-50
-40
-30
-20
-10
0
0 10 20 30 40 50 60 70 80 90
Magnetic Field (10
-3
A/m)
M
a
s
s

M
a
g
n
e
t
i
s
a
t
i
o
n

(
1
0

-
5
A
m
2
/
k
g
)
Crude oil (Dunbar)
Formation water (Dunbar)
Fig. 3. Mass magnetisation as a function of applied magnetic eld for
North Sea Dunbar crude oil and formation water using the Magnetic
Properties Measuring System (MPMS-2) SQUID magnetometer. The
slope of the lines gives the mass susceptibility.
Table 2
Experimentally measured and theoretically calculated mass magnetic
susceptibility of waters
Waters Mass magnetic susceptibility
(10
8
m
3
kg
1
)
Measured Calculated
Formation water (Forties) 0.873 0.878
Formation water (Dunbar) 0.886 0.893
Sea water 0.897 0.892
902 O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907
the samples with higher density, so the trend given in
Fig. 5 is consistent with the density versus susceptibility
results of Fig. 4.
The stock tank oil gravity versus mass magnetic sus-
ceptibility is given in Fig. 6 for the crude oil samples for
which we had data. Stock stank oil is oil as it exists at
atmospheric conditions in a stock tank (it tends to lack
much of the dissolved gas present at reservoir tempera-
tures and pressures). The gravity is expressed in API de-
grees as follows: API = [141.5/S
o
] 131.5, where S
o
is
the stock tank oil specic gravity, or relative density, to
water at 288 K, and API is an acronym for American
Oil Dunbar
Oil Forties
Kerosine
Heavy gas oil
Vacuum gas oil
Light gas oil
Gasoline
FW Forties
FW Dunbar
-1.08
-1.06
-1.04
-1.02
-1.00
-0.98
-0.96
-0.94
-0.92
-0.90
-0.88
-0.86
0 200 400 600 800 1000 1200
Density (kg/m
3
)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8
m
3
/
k
g
)
Crude oil
Oil fraction
Distilled water
Sea water
Formation water
Fig. 4. Density versus mass magnetic susceptibility of crude oils, rened oil fractions and formation waters.
R
2
= 0.75
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
-0.94
0 10 20 30 40 50 60 70 80 90
Residue Content above 342
o
C (wt %)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8

m
3
/
k
g
)


Fig. 5. Residue content above 342 C versus mass magnetic susceptibility of crude oil samples.
R
2
= 0.72
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
-0.94
0 5 10 15 20 25 30 35 40 45 50
Gravity (API degrees)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8
m
3
/
k
g
)


Fig. 6. Stock tank oil gravity versus mass magnetic susceptibility of crude oil samples.
O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907 903
Petroleum Institute. For a value of 10 API, S
o
is 1.0, the
specic gravity of water. Fig. 6 shows that there is a dis-
tinct trend of decreasing mass magnetic susceptibility
with increasing gravity, consistent with the expected trend
on the basis of the density versus susceptibility results.
Fig. 7 shows results for the viscosity at a temperature
of 40 C versus the mass magnetic susceptibility for
those crude oils for which we had data. There is a sug-
gestion that the higher the magnetic susceptibility, the
higher the viscosity. We have omitted the linear regre-
ssion line, where R
2
=0.73, since it is fairly meaningless
given that there appear to be two clusters, and the cor-
relation may be non-linear. The broad trend we observe
might be expected since the samples with higher viscos-
ity are also the ones with higher density, which gave
higher (less negative) values of magnetic susceptibility.
Whilst our data does not appear to be very well con-
strained, we include it because Ergin and Yarulin
(1979, Fig. 4.1, p. 159) also found a similar broad trend
of higher magnetic susceptibility with increasing visco-
sity. Their relationship was non-linear and slightly better
constrained.
3.3. Relation between mass magnetic susceptibility of
crude oils and concentration of sulphur and metals
The mass magnetic susceptibility of crude oils may
also reect their chemical composition, such as the sul-
phur content and the concentration of organometallic
compounds. Fig. 8 shows the sulphur content versus
mass magnetic susceptibility for the crude oils for which
we had compositional data. In general, a higher sulphur
content corresponds to a higher (less negative) mass sus-
ceptibility. There is a suggestion of possibly two trends:
one including the Russian and North Sea samples, and
the other containing the North American and Middle
East samples. The Russian and uppermost North Sea
sample have higher residue concentrations and higher
densities than the uppermost North American and Mid-
dle East samples. Higher sulphur content also generally
corresponds to higher residue content and density within
each of the two trending groups.
Fig. 9(a)(d) show results for the content of trace
amounts of vanadium, cadmium, nickel and iron versus
mass magnetic susceptibility. In each case there appears
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
-0.94
0 20 40 60 80 100 120 140 160
Viscosity at 40
o
C (cSt)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8

m
3
/
k
g
)


Fig. 7. Viscosity at 40 C versus mass magnetic susceptibility of crude oil samples.
North Sea
Far East
North America
Middle East
North America
Middle East
North Sea
North Sea
Russia
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
-0.94
0 0.5 1 1.5 2 2.5 3
Sulphur Content (%wt)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8

m
3
/
k
g
)
Fig. 8. Sulphur content versus mass magnetic susceptibility of crude oil samples.
904 O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907
to be a trend of higher mass magnetic susceptibility with
increasing metal content. This trend might ordinarily be
expected. However, the results should be treated with
some caution as we noticed that samples with higher
metal content also had higher density, which also corre-
sponds to higher mass susceptibility. The relative roles
of the metal content versus the intrinsic uid density
are presently unclear. It seems that crude oil samples
with higher density have higher residue content and that
these contain greater amounts of organometallic com-
pounds. If the metal content was due to elemental metal,
then trace amounts would have a signicant eect on the
susceptibility. For instance, just 10 ppm by weight of
ferromagnetic elemental iron would increase the mass
susceptibility of the sample by about 0.60.710
8
m
3
kg
1
, using values of mass susceptibility for iron
given by Potter and Stephenson (1988, Table 1). In real-
ity the metals are likely to be components in organome-
tallic compounds (which would have substantially lower
intrinsic values of magnetic susceptibility), and without
knowing the exact composition of these compounds
their precise inuence on the magnetic susceptibility of
the crude oils remains uncertain.
3.4. Dierences between oil provinces
Our preliminary data on the v
m
of the crude oils we
studied (from the Far East, North America, North
Sea, the Middle East and Russia) seems to show some
dierences between the various oil provinces (Fig. 10).
Whilst there is quite a large range between the various
North Sea samples, and a fair degree of overlap with
the North American and Middle East samples, the Rus-
sian sample and the Far East sample appear to be quite
distinct. This may reect specic features of the geolog-
ical and geochemical history of the oil provinces, and
might lend some support to the suggestion by Ergin
and Yarulin (1979) that crude oils from dierent prov-
inces might be distinguished on the basis of their mag-
netic susceptibility. Clearly, however, more samples
need to be measured in order to conrm any broad con-
sistent dierences between the various oil provinces.
R
2
= 0.78
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
-0.94
0 10 20 30 40 50 60 70 80
Vanadium Content (ppm wt)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8

m
3
/
k
g
)
R
2
= 0.63
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
-0.94
0 2 4 6 8 10 12 14 16
18
Cadmium Content (ppb wt)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8
m
3
/
k
g
)


R
2
= 0.69
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
-0.94
0 5 10 15 20 25 30 35
Nickel Content (ppm wt)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8
m
3
/
k
g
)


R
2
= 0.37
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
-0.94
0 2 4 6 8 10 12
Iron Content (ppm wt)
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8
m
3
/
k
g
)


(a) (b)
(c)
(d)
Fig. 9. Mass magnetic susceptibility of crude oils as a function of (a) vanadium content, (b) cadmium content, (c) nickel content, and (d) iron
content.
Russia
N. Sea
N. Sea
N. Sea
N. Sea
N. Sea
Middle East
N. Sea
N. Sea
Middle East
North America
Far East
N. Sea
N. Sea
N. Sea
N. Sea North America
N. Sea
-1.05
-1.04
-1.03
-1.02
-1.01
-1.00
-0.99
-0.98
-0.97
-0.96
-0.95
0 1 2 3 4 5 6
Location
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8
m
3
/
k
g
)
Fig. 10. Mass magnetic susceptibility in relation to specic oil
provinces.
O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907 905
4. Discussion of possible applications for petroleum
reservoirs
Magnetic susceptibility measurements might nd a
use in passive sensors in reservoirs for distinguishing be-
tween formation waters and crude oils. For example,
such a sensor could potentially help to monitor the onset
of water breakthrough. Current automated versions of
the MSB system are capable of being used as a detector
in conjunction with a ow cell, and it ought to be possi-
ble to further miniaturize such a system and employ it
downhole. Such sensors would provide an environmen-
tally friendly alternative to radioactive tracers. Although
viscosity meters might also distinguish between forma-
tion waters and crude oils, magnetic sensors would
have a further advantage in being able to also rapidly
detect small concentrations of ferrimagnetic or antiferri-
magnetic minerals, or migrating nes from important
paramagnetic clays such as illite or chlorite (small con-
centrations of which can dramatically aect uid perme-
ability). The magnetic susceptibility sensors might thus
also be used to monitor formation damage, or any
anomalous eects arising from the hydrocarbon extrac-
tion infrastructure.
It is also worth noting the values of the mass suscep-
tibility of crude oils and formation waters in relation to
some typical petroleum reservoir minerals, such as the
diamagnetic matrix minerals and the paramagnetic per-
meability controlling clays. The dierences are shown in
Fig. 11. The mass susceptibilities of the natural reservoir
uids are more negative than the majority of the dia-
magnetic matrix reservoir minerals such as quartz, feld-
spar, and calcite. However, the values are signicantly
less diamagnetic than the clay kaolinite. Magnetic prop-
erties may possibly play some role in rockuid interac-
tions. The relative magnetic forces between quartz and
formation water and between quartz and crude oil, in
the Earths eld, might be a factor in determining the
wettability (water wet or oil wet) of the reservoir rock.
For reservoir rocks containing signicant amounts of
paramagnetic clays, such as illite, the relative magnetic
roles of formation water and crude oil could be reversed
(compared to the quartz case) according to Fig. 11. This
might be a factor in inuencing the changes in wettabil-
ity that one often observes between clean sandstones
(quartz rich with little clay) and muddy sandstones (con-
taining higher concentrations of paramagnetic clays).
Recent work has shown links between nuclear magnetic
resonance (NMR) and wettability (Guan et al., 2002),
and so a link between magnetic susceptibility and wetta-
bility may also be a possibility.
5. Conclusions
The following conclusions can be drawn from the
present study:
There were distinct dierences between the mass
magnetic susceptibilities (v
m
) of crude oils and forma-
tion waters. All the samples studied were diamag-
netic, but the values for the crude oils were more
negative. Two independent pieces of sensitive equip-
ment conrmed the dierences between samples of
formation water and crude oil from the same oileld,
and each measurement system yielded very similar
results.
The values of v
m
for the crude oils, rened oil frac-
tions and formation waters correlated with their den-
sities. The values for crude oil also correlated with
other physical properties, namely residue content,
stock tank oil gravity, and viscosity. The results sug-
gest that the magnetic measurements could poten-
tially be used to rapidly characterise the physical
dierences between various petroleum reservoir
uids.
D
o
l
o
m
i
t
e
L
e
p
i
d
o
c
r
o
c
i
t
e
C
a
l
c
i
t
e
V
e
r
m
i
c
u
l
i
t
e
C
h
a
m
o
s
i
t
e
N
o
n
t
r
o
n
i
t
e
K
a
o
l
i
n
i
t
e
I
l
m
e
n
i
t
e

M
a
g
n
e
s
i
t
e
C
r
u
d
e

o
i
l
F
o
r
m
a
t
i
o
n
w
a
t
e
r
H
a
l
i
t
e

Q
u
a
r
t
z
M
o
n
t
m
o
r
i
l
l
o
n
i
t
e
G
l
a
u
c
o
n
i
t
e
M
u
s
c
o
v
i
t
e
I
l
l
i
t
e
S
i
d
e
r
i
t
e
G
y
p
s
u
m
F
e
l
d
s
p
a
r
A
n
h
y
d
r
i
t
e
C
h
l
o
r
i
t
e

B
V
S

C
h
l
o
r
i
t
e

C
F
S

-30
-20
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
Minerals and Fluids
M
a
s
s

M
a
g
n
e
t
i
c

S
u
s
c
e
p
t
i
b
i
l
i
t
y

(
1
0
-
8

m
3
/
k
g
)
Diamagnetic Paramagnetic
Fig. 11. A comparison of the mass magnetic susceptibility of typical reservoir diamagnetic and paramagnetic minerals in relation to average crude oil
and formation water values from the present study. The values for the minerals were taken from Hunt et al. (1995), Borradaile et al. (1990), and
Thompson and Oldeld (1986).
906 O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907
The values of v
m
for the crude oils also showed correla-
tions with trace amounts of chemical components,
namely the contents of sulphur, vanadium, cadmium,
nickel, andiron. The results, however, shouldbe treated
with some caution, since the samples with higher con-
tents of these elements also generally have higher den-
sity, which also correlates with v
m
. It appears that
crude oils with higher density have higher residue con-
tent, and also contain higher concentrations of the
above components. The relative contributions of intrin-
sic uid density and these trace components to the total
magnetic susceptibility signal is presently unclear.
The values of v
m
for the formation waters was related
to their solute composition. The experimental mea-
surements were within 1% of the theoretically calcu-
lated values based on the water compositions.
There is some suggestion from the results that crude
oils from dierent world oil provinces might be
broadly distinguished on the basis of their magnetic
susceptibility. However, there are signicant ranges
and overlaps between the results for some provinces,
and more samples need to be measured before consis-
tent dierences can be conrmed.
Acknowledgments
We are grateful to B. Woods and J. Gordon of BP for
providing us with some of the crude oils and rened oil
fractions, and also for associated data on those samples.
We thank the oileld scale group, and especially Nor-
man Lang, of the Institute of Petroleum Engineering
at Heriot-Watt for providing us with crude oil and for-
mation water samples and data. We thank Dr. A. Powell
(Heriot-Watt University) for the use of the Sherwood
MSB Mark I, and Prof. A. Harrison (Edinburgh Uni-
versity) for useful discussions and the use of the MPMS
2 SQUID magnetometer. We are grateful to reviewers
Brooks Ellwood and Bill Morris, and guest editor Edu-
ard Petrovsky, for their constructive comments, which
helped to improve the manuscript.
References
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O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907 907