Journal of Petroleum Science and Engineering 29 2001.

8595
www.elsevier.nlrlocaterjpetscieng

The kinetics of carbonate scalingapplication for the prediction

of downhole carbonate scaling
Yuping Zhang a,) , Harry Shaw b, Rod Farquhar a , Richard Dawe c
a

Read Well Serices Ltd., Offshore Technology Park 1, Claymore Aenue, Aberdeen AB23 8GW, UK
b
Centre for Petroleum Studies, T.H. Huxley School, Imperial College, London SW7 2BP, UK
Department of Petroleum Engineering, Uniersity of West Indies, St. Augustine, Trinidad and Tobago
Received 10 January 2000; accepted 31 October 2000

Abstract
Reliable prediction of calcium carbonate, CaCO 3 , scaling for estimating scale production oilfield production wells and
surface facilities requires both thermodynamic models to indicate the tendency for scaling from solution and kinetic models
to predict the rate of scaling and thus the time required to cause blockage. The application of such models could contribute
to field scale management and in the development of more effective treatments of carbonate scale during oilfield production.
The performance of a kinetic model for calcium carbonate scaling rate based on the measurements of individual calcite
crystal growth rates is tested against scale deposition in tube blocking experiments using synthetic formation brines under
pressure and temperature levels. The profile of the scale formed on the internal surface of the tube during the experiments
was measured and compared with the predicted results from the kinetic model. The application of the kinetic model to the
prediction of carbonate scaling in a North Sea well has also been tested. The results from the model are in good agreement
with the actual scale profile recorded in the tubing by a downhole multi-finger caliper MFC. tool. q 2001 Elsevier Science
B.V. All rights reserved.
Keywords: Scale prediction; Scaling kinetics; Carbonate scale; Crystal growth; Nucleation

1. Introduction
Chemical scale formation associated with the production of formation and injection waters can result
in oilfield production problems which are frequently
expensive to remedy. Calcium carbonate, CaCO 3 , is
one of the most common scale components found in
oilfield production wells and surface facilities. Car-

Corresponding author.
E-mail address: yuping.zhang@read.scotnet.co.uk Y. Zhang..

bonate scale formation can impair production by

blockage of tubing and flowlines, fouling of equipment and concealment of corrosion. In order to
manage a potential scale problem, it is important to
know where and how much CaCO 3 scale will be
deposited during oil and water production. Effective
prediction of scaling requires a reliable thermodynamic model for the prediction of the scaling tendency and a kinetic model for the prediction of
scaling rate. Normally, the field operator does not
have control over all the variables that determine
scale deposition, particularly the water composition,

0920-4105r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 4 1 0 5 0 0 . 0 0 0 9 5 - 4

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

86

but the application of these models could help identify some production parameters that could be controlled. This could then minimise the scale deposition as well as facilitate the design of more effective
treatment of carbonate scale during oilfield production.
The scale tendencies of the solutions used in our
experiments were calculated by a thermodynamic
modelSolmineq 88 Kharaka et al., 1988.. The
kinetic model has been developed from measurements of the growth rate of individual calcite crystals
in a dynamic flowing system Zhang, 1997; Zhang
and Dawe, 1998.. The rate equation and rate constant obtained from our previous experiments are:
RL s kp S

0.5

y 1.

log k p s 0.126 IS .

built-up along the length of the tube predicted by the

kinetic model has been compared with the measured
scale thickness in the tubes produced by the experiments. The kinetic model has also been used to
analyse carbonate scaling in a North Sea well and
the performance of the model compared against the
actual scale profile measured by a downhole MultiFinger Caliper MFC. survey Desbrandes, 1985..
Finally, the general application of the kinetic model
to the management of scale downhole is also discussed.

2. Experimental

1.

0.5

Tube blocking experiments were conducted in a

dynamic flowing system to model the actual scaling
process. Two different solution systems were used
for the experiments: the first is a simple NaCl
CaCO 3 H 2 O system, and the second is a synthetic
formation water which simulates a typical oilfield
formation water. Table 1 gives the water compositions used for the tube blocking experiments and the
calculated saturation indices at ambient conditions.
To maintain a constant pH, CO 2 saturated solutions
at ambient conditions were used in most of our
experiments. The composition and pH of the solutions were monitored throughout the experiments
and no change was recorded during two days standing time for each batch of solution. The saturation
indices of the solutions at room temperature around
208C. and experimental conditions were calculated
using Solmineq 88. Large errors in the calculation of
the saturation states of calcium carbonate solutions at
high pHs ) 7. from Solmineq 88 have been noticed
previously Zhang, 1997.. Corrections have been

y 2400r T q 273 . y 2.11

2.
where R L and k p are the crystal surface linear
growth rate and rate constant in metre per second
mrs., respectively, IS is the ionic strength in mole
per kg molrkg. water, T is temperature in centigrade and S is the saturation ratio; for CaCO 3 , S can
be expressed as:
S s aCa 2q aCO 32yrK sp

3.

where a i is the activity of the ith item for a given

solution and K sp is the solubility product of the
scale forming mineral. The saturation index SI.,
equal to log S, is also commonly used to express
scaling tendency. To validate the kinetic model for
CaCO 3 scaling rate prediction under oilfield downhole conditions, tube blocking experiments have been
conducted under controlled saturation states and temperature and pressure conditions. The scale profile

Table 1
The chemical compositions molrkg. of the brines used in tube blocking, their calcite saturation indexes and pH at the ambient conditions
No.

Naq

Kq

Ca2q

Mg 2q

Cly

HCOy
3

SO42y

pH 20

SI 20

1
2
3
4
5
6

1.00
1.03
1.04
1.28
1.28
1.29

0
0
0
0.05
0.05
0.05

0.00305
0.01720
0.01851
0.02482
0.02412
0.02708

0
0
0
0.011
0.012
0.013

1.00
1.03
1.04
1.37
1.37
1.38

0.00613
0.03442
0.03628
0.03276
0.03288
0.03615

0
0
0
0.0011
0.0011
0.0011

7.98
6.07
6.10
6.01
6.00
6.05

0.39
0.07
0.15
0.10
0.10
0.23

pH 20 and SI 20 are the brine pH and SI at 208C and 1 bar pressure.

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

made by changing the two complex constants K CaCO 3

and K NaCO y3 . according to the experimental data
obtained from previous experiments Zhang, 1997..
A schematic representation of the tube blocking
experiment apparatus is presented in Fig. 1. A solution containing both calcium and carbonate ions was
pumped through a stainless steel tube placed in a
water bath heated to the required experimental temperature. The tube length was about 1 m and internal
diameter was 3.04 except for experiment No. 3 in
which the tube internal diameter was 2.28 mm. The
pumping rate for all the tests was fixed at 90 mlrh.
A back pressure regulator was installed at the end of
the test tube to set a required system pressure. The
temperature profile inside the tube was measured
while the solution was being pumped by using a
temperature sensor inserted into the tube. At 708C
and a flow rate of 90 mlrh, the pumped solution
reached the water bath temperature within 3 cm.
Water samples were collected at the tube outlet at
regular time intervals to monitor the Ca2q ion concentration and alkalinity. As the carbonate scale
formed in the tube, there were pressure drops over
the test tubes. When the pressure drop increased
above 1 bar, the pump was stopped and the experiment ceased. The blocked tube was washed with a
CaCO 3 saturated solution to remove soluble salts
and then cut into small pieces to inspect the scale
profile. The thickness of the carbonate scale within
each cross-section of tube was measured under a
microscope. Some scale deposits were also examined
using scanning electronic microscopy SEM. and
X-ray diffraction XRD. techniques to determine the
scale morphologies and mineralogies.

87

3. The calculations of CaCO 3 scale profile along a

tube
According to Eqs. 1. 3., CaCO 3 scaling rate is
a function of its saturation index. When scale is
deposited inside a tube, the concentration of scaleforming ions decreases, resulting in a change in
saturation index as well as scale thickness downstream. The amount of scale deposited inside the
tube is a function of the crystal growth rate, the total
crystal surface area and solution flow rate. If it is
assumed that the total surface area for scaling is
equal to the tube internal surface area and the tube
length of L m. is uniformly sliced into n sections,
the scale thickness in one section, d x in meter, can
be obtained from:

dx s RL . x t

4.

where x gives the positions of the tube, x s 1, 2,

3 . . . n, R L . x is the scale growth rate in x section
and t is the total scale forming time in second. The
amount of ions precipitated from one kg of water
within one section length of the tube can be calculated from:

PPT. x s

Vs . x rs
Vw

543p r 2 y r y d x .

nMQ w t

rs L

5.
PPT. x is the total precipitation within the x section
in molrl, Vs . x is the total scale volume formed in x
section when a Vw volume of solution flowing
through the tube, rs is the density of the scale
kgrm3 ., M is the molecular weight of the scale

Fig. 1. A schematic representation of the tube block experimental system.

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

88

component kgrmol., r is the radius of the tube m.

and Q w is the water production rate in barrels per
day. The scale forming ions at the end of the x
section can be then calculated from:

CCa2q . xq1. s CCa2q . x y PPT. x

6.

Alk xq1. s Alk x y 2 PPT . x

7.

where Ci refers to the concentration of ith item, Alk

is the alkalinity of the water system. For oilfield
produced water, the alkalinity is roughly equal to the
concentration of HCO 3y if there is no organic acid
presence in the water system. The CO 32 y concentration can be calculated from solution pH and alkalinity. The saturation index at the following section
x q 1. can be then obtained from the Ca2q and
CO 32y concentrations.
An oilfield production system is more complicated than the system used in our experiments, normally including water, oil and gas. The water pH
varies with the amount of CO 2 dissolved in the water
phase, which is influenced by the partitioning of CO 2
between the water, oil and gas phases. An estimate
of downhole pH can be made from the water chemistry and the CO 2 partial pressure in the gas phase.
The CO 2 partial pressure can be obtained from:
PCO 2 s Pfg XCO 2

8.

where PCO 2 is the CO 2 partial pressure, P is the

total pressure inside the tubing, fg is the CO 2 gas
fugacity coefficient and XCO 2 is the mole fraction of
CO 2 in the gas phase. Both fg and XCO 2 are functions of pressure and temperature. According to Oddo

and Tomson 1994., fg and XCO 2 under oilfield

downhole conditions can be calculated from:

fg s exp P 4.12 = 10y4 y

2.05
T q 273

//

9.

and:
o
XCO 2 s XCO
2

1.0 q

4 pfg Q w q 2 Qo . = 10y4
Qg T q 273 .

/
10 .

o
XCO
2

where
is the mole fractions of CO 2 in gas
phase at standard conditions, respectively, Qo is oil
production rate barrels per day., Qg is the total gas
production rate million standard cubic feet per day.,
and P is the pressure in bar. NB the constants have
been changed as the units of P and T used here are
different in the Oddo and Tomson, 1994 paper..

4. Results and discussions

Table 2 lists the calculated solution pH values and
saturation indices under the test temperatures and
pressures. The measured tube blocking time and
Ca2q concentration at the outlet of the tubes for all
six tests are given in Table 2. If Eqs. 1. and 2.
were used to calculate blocking times for all the tube
blocking experiments, only experiment No. 1 gives
good agreement with the measured blocking time.
For the other five tests, the calculated blocking times
are about three times longer than the measured values. As we can see, the significant difference be-

Table 2
Prediction of CaCO 3 scaling rate using our kinetic model
No.

T 8C.

P bar.

pH TP

SI TP

1
2
3
4
5
6

90
90
70
90
90
70

10
10
10
100
15
15

7.47
5.96
5.98
5.87
5.88
5.92

0.68
0.64
0.52
0.58
0.62
0.58

Block time day.

Ca2q . out

k p mrs = 10 9 .

6.0
2.1
5.0
3.5
3.3
8.2

6.0
1.9
5.9
3.4
3.0
9.0

0.0026
0.0121
0.0141
0.0207
0.0190
0.0230

0.0025
0.0114
0.0141
0.0193
0.0184
0.0224

2.5
8.6
3.5
5.8
5.7
2.2

pH PT and SI PT are the pH and SI at the experimental pressure and temperature. Ca2q . out : Ca2q concentration at the out let,
Ccalculated, Mmeasured.

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

tween experiment No. 1 and the others is the solution

pH, suggesting that the CaCO 3 scaling rate is strongly
influenced by solution pH. For constant saturation
index, the lower the solution pH, the higher the
calcite growth rate. The rate constant given in Eq.
2. was obtained from test solutions with relatively
high pH approximately 8. Dawe and Zhang, 1997..
The influence of pH on calcite growth rate has also
been reported in other studies Dreybrodt et al.,
1997; Przybylinski, 1985; Zhang and Dawe, 1998;
Zhang and Grattoni, 1998.. Therefore, the influence
of pH on calcite growth rates has now been included
in the rate constant equation:
log k p s 0.126 IS .

0.5

y 2400r T q 273 .

y 0.34pH q 0.444.

11 .

For the synthetic formation brine solution containing Mg 2q, the inhibition effect of Mg 2q on calcite
growth rate also needs to be considered. For MgrCa
molar ratios between 0.1 and 0.5, the growth rate is
reduced by 40% as found in previous studies Dawe
and Zhang, 1997.. The rate constant for the solutions
containing low concentration of Mg 2q should be
calculated from:
log k p s 0.126 IS .

0.5

y 2400r T q 273 .

y 0.34pH q 0.222.

12 .

The tube blocking time for each experiment, calculated using Eqs. 11. and 12., are listed in Table
2. It seems that although many other ions were

present in the complex water systems, the calcite

growth rate can be well described by considering
only the inhibition from Mg 2q.
Variations in the analysed Ca2q concentrations
with time at the outlet of the tube for test No. 6,
together with the calculated Ca2q concentrations at
the outlet and at the equilibrium state are shown in
Fig. 2. As we can see, the Ca2q concentrations at the
outlet gradually decreased with time. At the end of
the experiment, the measured outlet Ca2q concentration was very close to the calculated value.
Most natural scaling processes starts by heterogeneous nucleation with many isolated and unconnected crystals formed on the metal surface Nancollas and Sawada, 1980; Sohnel
and Garside, 1992..

To simulate the natural scaling process, the saturation indexes of all the solutions used in our experiments are designed to be below the levels at which
homogeneous nucleation1 under the test conditions
may occur. Therefore, the reduction of scale forming
ions through the tube can be considered as due to the
formation of scale. As the surface area of the scale
crystals is initially smaller than the total tube internal
surface area, the concentration of scale forming ions
at the outlet of the tube will be higher than the
calculated values at the initial stage of scale forming.
As the size of the nuclei increase with time, the
Ca2q concentration will gradually decrease until the
whole surface of the tube is covered with crystals. A
constant Ca2q concentration at the tube outlet can be
achieved or the Ca2q concentration slightly increases
as a result of the tube inner diameter decreasing.
The SEM photomicrographs Fig. 3. of carbonate
scales show that the inner surface of the tube near
the inlet Fig. 3a. has been covered by scale, whereas
the surface near the outlet Fig. 3b. has not been
completely covered. This may be the reason why our
measured Ca2q concentration did not reach the stable stage for this test.
The scale developed along the tube for test No. 6
is shown in Fig. 4. As we can see, the highest
scaling rate is located at the inlet of the tube where

Fig. 2. The measured Ca2q concentrations at the outlet of the

tube.

89

The critical saturation indexes for homogeneous nucleation,

SI c , can be calculated from the critical free energy required to
form a solid phase in a solution, for calcite SI c s 0.75 at 908C
Mullin, 1993..

90

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

the temperature reaches the water bath temperature.

The scale profile along the tube for test No. 6 has
also been calculated and compared with the measured scale profile Fig. 5.. The predicted scale
profile matches the measured values very well at the
upstream end of the tube, but are lower than the
measured values near the outlet of the tube. This

may be because before the tube surface is completely

covered with crystals, the saturation index at the end
of the tube is higher than the calculated value, which
provided a higher scaling rate than the calculated
values.
The XRD analysis shows that almost all the precipitated scale is calcite when simple water systems

Fig. 3. The CaCO 3 scales and the morphologies SEM photomicrographs.. a. across length of the picture represents 2.3 mm. the scale
formed near the inlet of the tube, calcite is the main mineral of the scale; b. across length 1.7 mm. the scale formed near the outlet of the
tube, both calcite rhombohedron. and aragonite hexagon. are found.

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

91

Fig. 3 continued ..

were used in the experiments, but in the experiments

using synthetic formation water initial MgrCa ratio
0.5., the precipitated scale is composed of 90%
calcite and 10% aragonite. The SEM photomicrographs of scale from these experiments show evidence of the characteristic morphologies of aragonite
Fig. 3b.. Calcite is the most common form of the
three CaCO 3 mineral polymorphs calcite, aragonite
and vaterite. observed in downhole carbonate scales

although other carbonate minerals have also been

reported Nancollas and Sawada, 1980.. The mineralogy of the precipitates depends mainly on the
saturation index, temperature and the presence of
inhibitors e.g. Mg 2q .. Many studies have shown
that Mg 2q inhibits the growth rate of calcite but not
aragonite Akin and Lagerwerff, 1965; Morse and
Mackenzie, 1990; Mucci, 1987; Paquette et al.,
1996.. In general, the higher the MgrCa ratio, tem-

92

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

Fig. 4. The photographs of the scale formed at different positions along the tube exp. No. 6..

perature and saturation index, the higher the percentage of aragonite precipitated Zhang, 1997.. The
saturation index under downhole conditions is nor-

mally much lower than that used in our experiment

demonstrated later. and the MgrCa ratios of most
formation waters are below 0.5 Warren and Smal-

Fig. 5. The measured scale profile along a metal tube compared with the calculated scale profile No. 6..

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

ley, 1994.. From such solutions with a low saturation

index and low MgrCa ratios, it is more likely for
calcite to form Zhang and Dawe, 1998.. Therefore,
our kinetic model obtained from the growth rate of
calcite can be generally used for the prediction of
CaCO 3 scaling rates.

5. Application for the prediction of oilfield downhole scaling

Analysis of the scale profile logged in a well from
a North Sea field with a recognised carbonate scale
problem has been used to evaluate the potential field
application of the kinetic model. A MFC tool was
used to generate a profile of the internal geometry of
a production tubing string in which scale build-up
was suspected. The MFC tool is run downhole on
wireline and a number of sensor arms arranged
around the circumference of the tool measure changes
in the radial dimensions of the internal profile. In
this case, 40 sensors in 5.5 in. tubing results in a
high density image from sensors spaced only 0.38 in.
apart. These types of tools have proved to be very

93

useful for monitoring scale deposition downhole. In

this well, a MFC survey conducted 11 months previously did not indicate any presence of scale since
inhibitor squeezes had been conducted regularly to
control the scaling. However, in the intervening period, the operator became aware that the inhibitor
concentration had fallen far below the required level,
which is presumably the main cause for the scale
deposition. The information provided by the MFC
tool combined with advanced data processing and
interpretation software, not only provides a reliable
image of the actual scale profile downhole, but also
facilitates the determination of scale volumes. In this
gas lifted well, the scale found at gas entry points is
shown in Fig. 6 and similar profiles were found to
have developed in the well at each gas entry point.
Generally, the greatest scale thickness appeared at
the gas entry point and gradually declined to almost
zero. The scale formed in this way is most likely to
be composed of carbonate minerals whose precipitation is strongly influenced by pressure change. As
the pressure decreases, dissolved CO 2 in the water
phase will escape and raise the pH and subsequently
increase the saturation index. The turbulent flow at

Fig. 6. The calcium carbonate scale profile in an oil production well detected by an MFC logging tool with 40 sensor arms and calculated
from the tubing mean internal diameter ID. and minimum ID.

94

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

the gas entry points can increase the speed of CO 2

coming out of solution. This may be one reason why
higher scaling rates occurred at gas entry points. It is
also possible that the CO 2 content in the lift gas was
lower than the original produced gas, thus when the
lift gas entered the tubing and mixed with the produced gas, the pCO 2 reduced sharply and caused the
saturation index to rise.
To model the scale profile for this field scaling
case, the temperature and pressure profiles were
calculated from the reported downhole and wellhead
data assuming linear changes with well depth. The
reported CO 2 content in the produced gas at the
wellhead was reported to vary from 4.3% to 7.3%
which corresponds to SI s 0.28 to 0.08. These saturation index values are much lower than the SI
values used in our tube blocking experiments. As
discussed earlier, with lower SI and lower MgrCa
ratios, the mineralogy of the scale can be expected to
be calcite. Our kinetic model has been used to
calculate the CaCO 3 scaling rate at downhole temperatures and pressures to fit the detected scale
profile from the MFC survey by modifying slightly
the input XCO 2 . The simulated scale profile is shown
in Fig. 7, which shows very good agreement with the
actual logged profile. To form CaCO 3 scale at a rate

of less than 8 mm in 11 months, the saturation index

required should be below 0.15 with XCO 2 6.0%,
which is consistent with the range of the values
measured at the wellhead. It is also possible that the
scale formed in this well was at a much higher rate
over a shorter period when the lower XCO 2 lift gas
was being supplied. If the XCO 2 in the lift gas had
been the same as in the produced gas, the amount of
scale would have been much smaller. The opportunity for the operator to adjust such production parameters will vary from case to case, however, the
example considered here shows that the kinetic model
could contribute to the identification of some possible parameters which the operator could control. For
example, by an appropriate change in the lift gas
composition, significant scale problems could possibly be avoided or at least reduced. The cost of
controlling the lift gas composition may prove to be
less in the long run than the costs of lost oil production and well workovers.
More work will be required to compare the prediction from the kinetic model with actual scale
profiles recorded downhole by MFC tools in other
wells to confirm the reliability of the model. However, the initial results presented here are promising
and suggests that the model could also be used to

Fig. 7. Calcium carbonate scale profile calculated using kinetic model and compared with the detected scale profile.

Y. Zhang et al.r Journal of Petroleum Science and Engineering 29 (2001) 8595

optimise downhole monitoring by increasing the

confidence in targeting wells vulnerable to scaling.
6. Conclusions
1. The most probable mineral in downhole calcium carbonate scales under oilfield reservoir
conditions is calcite.
2. A kinetic model derived from the growth rate
of calcite can be generally used for the prediction of downhole CaCO 3 scaling rates.
3. As far as formation brines are concerned, the
calcite growth rate can be well described by
considering only the inhibition by Mg 2q.
4. The scale profile predicted by the kinetic model
agrees well with a measured downhole carbonate scale profile.
5. The application of the kinetic model could
contribute to the management of downhole carbonate scaling problems.

Acknowledgements
The authors are grateful to Bryan Clarke, Carlos
Grattoni and Sean Mulshaw of Imperial College for
technical assistance, Garry Williams and Keith
Young of Read Well Services for their help in
preparing the paper. The laboratory work was financially supported by the EU Joule III QC-Scale project.
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