NACE Paper No.

MECCOCT18-12374

Corrosion and Scaling Prediction Using Different Indices for Formation Water Samples
Nasir Ullattumpoyil, Abdulaziz Rueshed
nasirchemistry@yahoo.com
Southern Area Oil Operation Technical Support Department
Southern Area Laboratories Division. Saudi Aramco, Abqaiq-31311
Kingdom of Saudi Arabia

ABSTRACT

The significance and importance of water to the Oil and Gas industry cannot be overstated.
Unanticipated water production, particularly if it contains unwanted impurities, can significantly
impact hydrocarbon production. The degree of risk posed by deposition of mineral scales to the
injection and production wells during different operations has been much studied. Additionally
presence of different microbes such as SRB and GAB also pose threat to water system by
forming fouling and corrosion. Geochemical and microbial analysis is one of the basic tool,
which can predict the formation of scales and corrosion. The scale formation and corrosivity is
qualitatively predicted using various indices. The Langelier Saturation Index (LSI) is an indicator
of water scaling potential. Ryznar Stability Index (RSI) can predict the corrosion and scaling in
water samples with different hardness. In the current study water samples were collected from
different wellheads and tested for geochemical and microbial parameters. Geochemical test
indicated scaling potential in most of the samples and some corrosion products such as iron in
few samples. Different indices calculated based on geochemical data indicated scaling potential
in most of the samples. At the same time higher concentration of SRBs in few samples indicated
corrosion threat to the system as well. The study concluded the importance of different scale
inhibition mechanism and corrosion control in Oil and Gas industry.

Key words: corrosion, scaling, formation water, oil and gas

INTRODUCTION

Within the oil and gas industry, water is produced as a by-product of the production of oil and
gas. The presence of water can result in many production challenges, including the formation of
mineral scales, increased corrosion of metallic equipment, gas well loading, emulsions, and
bacterial activity. While water, to the oil and gas industry, is viewed as a by-product of
production, it can yield vital information on the reservoir characteristics, corrosiveness within a
well, the tendency for the deposition of mineral scales, and influences many other factors
pertaining to oil and gas production. Without water, many of the production challenges
experienced within the oil and gas industry would be substantially minimized. An accurate water
analysis can indicate the tendency for many of these production problems. A water analysis is
one of the basic analytical tests performed within the oil and gas industry; however, its accuracy
and interpretation are often left to chance.

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Scale and corrosion can be a major cause of equipment failure and other problems in oil and
gas industry. Corrosion and scaling processes are complex and interactive. It is most often an
issue with wells that produce a great deal of water. If the formation water is saturated or
supersaturated with respect to calcite, mineral scaling may occur along with moderate
corrosion. Localized corrosion processes, such as that related to bacterial sulphate reduction,
can cause severe damage to steel. Corrosion is the destruction of a metal by chemical or
electrochemical action of the surrounding environment. It is well known that iron and ordinary
unalloyed steels corrode easily into rust. The most common case of corrosion is wet corrosion.
The corrosive processes are very complex and take place in widely differing conditions1. A
water saturated with calcium carbonate tends to precipitate a scale which may protect against
corrosion. The degree of calcite saturation is a useful index in corrosion and scaling studies.
Water of a high carbon dioxide concentration may be more destructive than conventional criteria
indicate. There is reason to suspect significant localized damage at least to iron and steel when
the carbon dioxide concentration exceeds 20 mg/l, regardless of the index value.

Although a number of indices have been developed, none has demonstrated the ability to
accurately quantify and predict the corrosively or scaling of water. They can only give a
probable indication. Experience has shown that if conditions encourage the formation of a
protective calcium carbonate film, then corrosion will generally be minimized 2. The most
common methods used for calculating the stability of water are Langelier saturation index (LSI)
and Ryznar stability index (RSI). LSI and RSI are designed to be predictive tools for calcium
carbonate scale and they are not suitable for estimating calcium phosphate, calcium sulfate,
silica or magnesium silicate scales3. Millete et al.4 showed that almost 70% of the representative
utilities to have moderately to highly aggressive waters, where 16% - 18% had highly
aggressive waters and indicating aggressive to very aggressive waters as well as a comparison
between the two indices showed good agreement in the results. Pisigan and Singly5 reported
the influence of some water quality parameters in particular the LSI on the corrosion of
galvanized steel using a dynamic circulating water system. Change in water quality parameter
were monitored, hardness and alkalinity exhibited a continuous decline. Pisigan and Singly6
dictated from their experimental work that increasing the buffer capacity at a constant water
alkalinity of 100 mg/L as CaCO3 in the pH range 6 - 9 decreased the corrosion rate of mild steel.
However an increase in the buffer capacity at various pH by raising the alkalinity did not lower
the corrosion rate because of the effects of higher ionic strength and conductivity. Also higher
chloride content increased the corrosion rate in some waters of high buffer capacities. Steve et
al.7 evaluated the relationship between copper plumbing corrosion and variations in delivered
water quality in several communities in the Pacific Northwest. Significant relationships were
found for copper corrosion rate dependence on pH and free chlorine residual. The regression
equation coefficient indicated that the corrosion rate changes with chlorine residual,
approximately 25.6 μm/year per mg/L chlorine

Formation water samples were collected using surface sampling procedure and analysed for
different geochemical parameters. The current paper describes the variation of water
composition in different wells with emphasis for scaling/corrosion tendency and the values of
formation water analysis throughout the reservoir life. The paper also examines the potential of
corrosion/scaling whereby emphasizing the importance of different scale inhibition mechanism
and corrosion control in Oil and Gas industry
 NACE Paper No.
MECCOCT18-12374

EXPERIMENTAL PROCEDURE

The objective of sampling is to collect a portion of material small enough in volume to be

transported conveniently and yet large enough for analytical purposes while still accurately
representing the material being sampled. Before sample collection began, field personnel took
steps to ensure that the samples collected are representative of the system being investigated.

Surface sampling of the produced fluids from oil wells is performed periodically according to the
frequency guidelines. Surface water samples are usually collected from the wellheads or
separators, this is the water that comes with oil; water separated from the oil is used for the
analysis. When the well is flowing for some time the wellhead sample may be considered as a
representative sample from the desired formation and it is used for the analysis.

There are many publications available that recommend sampling, labeling and analytical testing
procedure. The most common of these are the National Association of Corrosion Engineers
(NACE), American Petroleum Institute (API), and American Society for Testing and Materials
(ASTM). The collected formation water samples were preserved and transported to laboratory
as per the standard procedure. Water analysis consists of determination of physical and
chemical properties. Conductivity is performed on a filtered and undiluted sample using
conductivity meter by noting the temperature. Specific gravity is determined by densitometer on
a filtered and undiluted sample. Most of the chemical composition of the water are identified by
inductively coupled plasma (ICP). Chloride is determined by potentiometric titration, sulfate is
determined by turbidimetry.

Calculations of the Water Stability Indices

Langelier Saturation Index

Work by professor W. F. Langelier, published in 1936 deals with the conditions at which water is
in equilibrium with calcium carbonate. An equation developed by Langelier makes it possible to
predict the tendency of calcium carbonate either to precipitate or to dissolve under varying
conditions. Langelier Saturation Index (LSI) is an equilibrium model derived from the theoretical
concept of saturation and provides an indicator of the degree of saturation of water with respect
to calcium carbonate and can be calculate from

LSI = pHa − pHs (1)

Where:

pHa: the measured water pH.

pHs: the pH at which water with a given calcium content and alkalinity is in equilibrium
with calcium carbonate.

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The equation expresses the relationship of pH, calcium, total alkalinity, dissolved solids, and
temperature as they are related to the solubility of calcium carbonate in waters with pH of 6.5 to
9.5. This is known as the pHs:

pHs = (9.3+ A+ B) − (C + D) (2)

Where:

A= [Log10(TDS)-1]/10 (3)

B= -13.12*Log10(˚C+273)+34.55 (4)

C= Log10(Ca2+ as CaCO3)-0.4 (5)

D= Log10[Alkalinity as CaCO3] (6)

Ryznar Stability Index (RSI)

The Ryznar index is an empirical method for predicting scaling tendencies of water based on
study of operating results with water at various saturation indices. The Stability Index developed
by John Ryzner in 1944 used the Langelier Index (LSI) as a component in a new formula to
improve the accuracy in predicting the scaling or corrosion tendencies of water

The Ryznar index (RSI) takes the form:

(RSI) = 2(pHs) − pH = pHs − LSI (7)

The criteria used to give an indication of the stability indices are summarized in Table 1.

Puckorius Scaling Index (PSI)

The Puckorius scaling index is calculated in a manner similar to the Ryznar stability index. The
Puckorius scaling index provides another tool for evaluating the calcium carbonate scale
potential for a water and is included in the Water Cycle indices of calcium carbonate scale
potential. LSI, RSI, and PSI are designed to be predictive tools for calcium carbonate scale only.
They are not suitable for estimating calcium phosphate, calcium sulfate, silica or magnesium
silicate scale. The PSI can be calculated as follows:

PSI=2pHs-pHeq (8)

Where

pHeq=1.465log (M alk) +4.54 (9)

Table 1

Summary of water stability indices

 NACE Paper No.
MECCOCT18-12374

Index Value Water Condition

Water is supersaturated with respect to calcium carbonate (CaCO3) and
LSI>0
scale forming and CaCO3 precipitation may occur
Water is considered to be neutral. Neither scale-forming nor scale
LSI=0 removing. Saturated, CaCO3 is in equilibrium. Borderline scale
potential.
Water is under saturated with respect to calcium carbonate. Under
saturated water has a tendency to remove existing calcium carbonate
LSI<0
protective coatings in pipelines and equipment. No potential to scale,
the water will dissolve CaCO3.
Supersaturated, tend to precipitate CaCO3. The scale tendency
RSI,PSI≤6
increase as the index decrease
Saturated, CaCO3 is in equilibrium. The calcium carbonate formation
6<RSI,PSI<7
probably does not lead to a protective corrosion inhibitor film
Under saturated, tend to dissolved CaCO3. Mild steel corrosion
RSI,PSI≥7
becomes an increasing problem

RESULTS AND DISCUSSION

We have selected four wells named Well A, Well B, Well C and Well D for the current study. The
collected water samples were analyzed for different geochemical parameters by following the
standard procedures. The results are tabulated in Table 2.

Table 2

Geochemical analysis results for the respective wells

Parameter Well A Well B Well C Well D

pH 7.62 6.98 6.75 6.93
Conductivity, S/cm 6540 32700 34900 14900
Sp.Gravity 1.0034 1.0163 1.0182 1.0073
Ca, mg/L 351 1370 5260 692
Mg, mg/L 128 440 108 111
Na, mg/L 890 5600 2400 2400
K, mg/L 35 221 121 132
Sr, mg/L 9 35 12 13
Dissolved Fe, mg/L 0.54 0.61 1.55 10.8
Cl, mg/L 1790 12300 13200 4700
Sulfate, mg/L 771 935 950 994
T. Alkalinity, mg/L 170 153 182 194
LSI 1.15 0.98 1.41 0.77
RSI 5.31 5.01 3.92 5.38
PSI 5.00 4.12 2.70 4.29

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One of the most important properties of water is its pH. The pH is a measure of the acidity or
alkalinity of a water. It is extremely important in a water analysis for several reasons. The
solubility of calcium carbonate (CaCO3) and iron compounds is highly dependent on the pH of
the water. Generally, oil-field waters have a pH ranging from 5.0 – 8.0. If a water’s pH is below
7.0, it is said to be acidic, and corrosion rates can increase. If a water’s pH is above 7.0, it is
said to be alkaline in nature, and calcium carbonate and iron compounds are less soluble.

With increasing amounts of acid gases (hydrogen sulfide and carbon dioxide) the pH of the
water will decrease. Understanding their effect on pH will help us to understand and predict their
impact on the corrosivity of the water.

The constituents affecting the pH are very unstable upon a pressure release (ie, H2S, CO2,
HCO3), therefore, the pH of water will rapidly change when removed from a pressurized system.
It is imperative that the pH be measured immediately upon sampling. For the present study all
the pH values are between 6.0 and 8.0.

Major Cations

Calcium (Ca)

The calcium ion is a major constituent of oilfield brines and can range in concentration up to
30,000 mg/L, although it is generally much lower. This ion is of major importance due to its
ability to combine with bicarbonate, carbonate or sulfate ions and precipitate mineral scales,
adherent and/or suspended.

Magnesium (Mg)

The magnesium ion concentration is generally much lower than the calcium ion concentration.
The primary importance of the magnesium ion is also its ability to form scales with the
carbonate ions; however, these magnesium scales are 50 times more soluble in water than the
CaCO3. Most other magnesium salts, such as MgSO4 are quite soluble in water and cause few
problems in the oil-field environment.

Sodium (Na)

Most sodium salts are soluble in water; therefore, sodium is a major constituent of oil-field and
drinking waters. Generally, sodium does not result in any specific problems. The exception
would be the precipitation of sodium chloride (NaCl) from extremely salty brines.

Iron (Fe)

Natural iron content in most oil-field waters varies. Many times, its presence signifies active
corrosion. Iron counts are often utilized in “sweet” systems to monitor and semi-quantify
corrosion rates. In “sour” systems, the iron will be present as a form of iron sulfide and is often
responsible for plugging issues downhole or within surface equipment. Iron sulfide is almost
always an indicator of corrosion, bacterial activity, or incompatible mixtures of water. The
present study shows higher dissolved iron concentration in Well 4 indicating higher corrosion
rates.
 NACE Paper No.
MECCOCT18-12374

Strontium (Sr)

Strontium is important because of its ability to combine with sulfate ion and precipitate insoluble
strontium sulfate. The formation of strontium sulfate will result in serious plugging problems.
Although more soluble than the barium sulfate, it is very likely to co-precipitate with the barium
sulfate.

Major Anions

Chloride (Cl)

The chloride is almost always the major anion produced in oil-field brines. It is also a major
constituent of fresh waters. Although salt deposition in high saline brines can be a problem,
usually the concern with chlorides is that with increasing chlorides comes increasing
conductivity and thus, increased corrosion. Furthermore, chlorides are utilized to assist in
determining the identity of a producing formation. The chloride levels can assist in monitoring
wells for casing or packer leaks as well as flood-water break-through in water flood applications.

Carbonates and Bicarbonates (CO3 and HCO3)

These ions are important because they are the natural buffer for the water. These ions will
influence the pH of a water, and the pH of the water will define which ion, or if both ions, are
present in a water sample. Bicarbonates are present in waters with pH’s ranging from 4.5-8.2.
Above 8.2, carbonates can also be present. These ions can combine with cations to form
insoluble mineral scales. Most carbonate scales are soluble in hydrochloric acid.

Sulfate (SO4)

The sulfate ion is important because of its ability to react with calcium, barium and/or strontium
to form acid insoluble scales. This also serves as a nutrient for sulfate reducing bacteria
(SRB’s).

Water Stability Indices

The water analysis can also indicate whether corrosion is likely to occur, based on several
factors. The acid gas content such as CO2 and H2S determines the dominate type of corrosion
and greatly influences the corrosion rate of a system. As the levels of dissolved CO 2 and H2S
increase in the water, the pH of the produced fluids will continue to decline. This creates a
corrosive environment. Dissolved carbon dioxide acid gas or dissolved hydrogen sulfide gas
present in the water, when combined with the low pH and high chloride content, would indicate
the water is potentially corrosive in nature. Similarly high Iron and Manganese levels can be
indicative of active corrosion occurring downhole or in surface equipment. From the current
study the Well D have higher alkalinity with high sulfate concentration, which can cause higher
corrosion which is confirmed by indicating high dissolved iron and manganese in this sample.
The same sample was analyzed for SRB’s indicating higher population.

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At present we know that the extent of mineral scaling from water is not wholly dependent upon
the water itself, or it’s dissolved ion content. The mechanism of mineral scales formation is
dependent upon the degree of supersaturation of the water with respect to a particular mineral,
the rate of temperature change and changes in the pressure as well as the pH of the water.
Thus, where water is used, one can expect a variety of potential deposition problems. Mineral
scales are defined as a mineral deposition that results from an oversaturation of a given
compound within a solution under a certain set of conditions. Scales can result in plugging
problems within the producing formation, within the downhole equipment, and/or within the
surface piping/equipment. Additionally, under-deposit corrosion can occur beneath scale
depositions, resulting in high corrosion rates and pre-mature failure of production equipment.
For the current study all the water samples shows positive value for LSI which indicates that the
water is supersaturated with respect to calcium carbonate (CaCO3) and scale forming and
CaCO3 precipitation may occur. Similarly for RSI and PSI, the value is below six which confirms
the scaling potential for all the samples.

CONCLUSIONS

A water analysis can be an extremely informative piece of analytical information. The water
analysis can assist in identifying the production zone, contamination to the production zone, the
tendency for corrosion and/or scale deposition, plays an integral role in production chemical
selection, and can aid in the design and development of secondary and tertiary recovery
systems for the oil and gas industry. The scale formation and corrosivity is qualitatively
predicted using various indices. The Langelier Saturation Index (LSI) is an indicator of water
scaling potential. Ryznar Stability Index (RSI) can predict the corrosion and scaling in water
samples with different hardness. In the current study water samples were collected from
different wellheads and tested for geochemical and microbial parameters. Geochemical test
indicated scaling potential in most of the samples and some corrosion products such as iron and
manganese in a sample. Different indices calculated based on geochemical data indicated
scaling potential in most of the samples. At the same time higher concentration of SRBs in few
samples indicated corrosion threat to the system as well. Using the water analysis to
understand the potential for corrosion and relating this information to actual failure records
within a field or area, the engineer can design an appropriate corrosion mitigation program. This
program can consist of engineering solutions to remove the corrosive species, selection of
corrosion resistant alloys, the application of protective coatings, or the application of corrosion
inhibitors. The study concluded the importance of different scale inhibition mechanism and
corrosion control in Oil and Gas industry.

ACKNOWLEDGEMENTS

The authors wish to express their gratitude to the Southern Area Oil Operation Technical
Support Department Management for their assistance to carry out the present work.

REFERENCES

1. Y. Hayashi, Fundamentals of corrosion. No. 29 textbook of the IGTCGE, (1988): Kyushu,

Japan.
2. J.R. Rossum, D.T. Merrill, “An Evaluation of the Calcium Carbonate Saturation Indexes”,
Journal of American Water Works Association 75(1983): pp. 95-100.
3. MWH, Water Treatment Principles and Design, (2005): 2nd Edition, John Wiley & Sons, Inc.,
Hoboken.
 NACE Paper No.
MECCOCT18-12374

4. J.R. Millette, A.F. Hammonds, M.F. Pansing, E.C. Hansen, P.J. Clark, Aggressive Water:
Assessing the Extent of the Problem. American Water Works Association, 72(1980): pp.
262-266.
5. R.A. Pisigan Jr., J.E. Singley, Effects of Quality Parameters on the Corrosion of Galvanized
Steel. American Water Works Association, 77(1985): pp. 76-82.
6. R.A. Pisigan Jr., J.E. Singley, Influence of Buffer Capacity, Chlorine Residual and Flow Rate
on Corrosion of Mild Steel and Copper. American Water Works Association, 79(1987): pp.
62-70.
7. S.H. Reiber, J.F. Ferguson, M.M. Benjamin, Corrosion Monitoring and Control in the Pacific
Northwest. American Water Works Association, 79(1987): pp. 71-74.