Magnetic susceptibility of petroleum reservoir fluids may provide new techniques for improved reservoir characterisation, exploration and production. Magnetic information is currently scarce for the vast majority of reservoir fluids. V m of crude oils from various world-wide oil provinces also showed some differences, possibly reflecting broad physical and chemical features of the geological history of each province.
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Magnetic susceptibility of petroleum reservoir fluids.pdf
Magnetic susceptibility of petroleum reservoir fluids may provide new techniques for improved reservoir characterisation, exploration and production. Magnetic information is currently scarce for the vast majority of reservoir fluids. V m of crude oils from various world-wide oil provinces also showed some differences, possibly reflecting broad physical and chemical features of the geological history of each province.
Magnetic susceptibility of petroleum reservoir fluids may provide new techniques for improved reservoir characterisation, exploration and production. Magnetic information is currently scarce for the vast majority of reservoir fluids. V m of crude oils from various world-wide oil provinces also showed some differences, possibly reflecting broad physical and chemical features of the geological history of each province.
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
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-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 Borradaile, G.J., MacKenzie, A., Jensen, E., 1990. Silicate versus trace mineral susceptibility in metamorphic rocks. Journal of Geophys- ical ResearchSolid Earth 95, 84478451. Ergin, Y.V., Kostrova, L.I., Subaev, I.Kh., Yarulin, K.S., 1975. Magnetic Properties of Oils (in Russian). Depositor of VINITI, N3265-75. Ergin, Y.V., Yarulin, K.S., 1979. Magnetic Properties of Oils (in Russian). Nauka Publishers, Moscow p. 200. Guan, H., Brougham, D., Sorbie, K.S., Packer, K.J., 2002. Wettability eects in a sandstone reservoir and outcrop cores from NMR relaxation time distributions. Journal of Petroleum Science and Engineering 34, 3352. Hunt, C.P., Moskowitz, B.M., Banerjee, S.K., 1995. Magnetic properties of rocks and minerals. In: Ahrens, T.J. (Ed.), Rock Physics and Phase Relations: a Handbook of Physical Con- stants. American Geophysical Union Reference Shelf 3, pp. 189 204. Potter, D.K., Stephenson, A., 1988. Gyroremanent magnetization in magnetic tape and in iron and iron alloy particles. IEEE Trans- actions on Magnetics MAG-24, 18051807. Selwood, P.W., 1956. Magnetochemistry, 2nd edition. Interscience Publishers, New York p. 435. Thompson, R., Oldeld, F., 1986. Environmental Magnetism. Allen and Unwin, London p. 277. O.P. Ivakhnenko, D.K. Potter / Physics and Chemistry of the Earth 29 (2004) 899907 907