MGS 3233
PETROLEUM GEOLOGY
EXPERIMENT 1 - 4
Introduction
Pore spaces in sedimentary basins are mostly filled with water. Formation water and
connate water are terms that are often used interchangeably. Bjorlykke (2010) defined formation
water as “water that is analyzed from exploration wells or produced during oil production”. SLB
defines formation water as water that “naturally occurs within pores of rock” and “might not be
present when the rock originally formed”. Akinade (2013) stated that formation water is “the
water which was found to be present in oil reservoirs with the crude oil without any fluid
injection”. Meanwhile, connate water, also known as fossil water, is defined as the water that
was trapped in the pores of a rock during its formation (Energy Glossary, n.d.). Selley (2022)
defined connate water as “interstitial water existing in the reservoir rock prior to disturbance by
drilling” and “waters which have been buried in a closed hydraulic system and have not formed
part of the hydraulic cycle for a long time”.
Evaluation of formation water is important for various stages of hydrocarbon generation,
transportation, and storage (Feng, 2016). There have been numerous studies conducted on
formation water, mainly focusing on its origin, mechanism of concentration and desalination as
well as the origin of the ionic content (Wang et al., 2022).
Extensive research has been done to understand the origin of formation water. Study by
Knauth & Beeunas (1986) found that seawater evaporation can lead to the production of
formation water. Bjorlykke (2010) in Petroleum Geoscience: From Sedimentary Environments to
Rock Physics defined subsurface water as the water that fills the pore spaces in sedimentary
basins. He also stated that several sources of subsurface waters, including (1) burial of
seawater with sediments; (2) flow of groundwater (meteoric water/rainwater) from land to
offshore; (3) release of water through dehydration of minerals, like from gypsum or clay minerals
like smectite; and (4) introduction of water (juvenile water) from igneous activity.
Connate water, along with meteoric water, juvenile water and mixed water, is among
several types of subsurface waters (Selley & Sonnenberg, 2022). Meteoric water is present in
the subsurface due to rainwater infiltration, has oxidizing salinity and often low pH value due to
high acidity that resulted from dissolved humic, carbonic and nitrous acid from the atmosphere.
Juvenile water is considered to be of magmatic origin. Case (1956) defined connate water as
“interstitial water existing in the reservoir rock prior to disturbance by drilling, and White (1957)
referred to connate water as “waters which have been buried in a closed hydraulic system and
have not formed part of the hydraulic cycle for a long time”. Water buried in sedimentary layers
used to be generally referred to as connate water and mistaken for the original seawater,
however, nowadays it has been found that meteoric water is far more dominant in the
sedimentary basins.
Besides, numerous research has also been done to identify the origin of salinity in
subsurface waters, including underground evaporation of seawater, as suggested by
Rittenhouse (1967), evaporite dissolution and shale membrane infiltration, as stated by Graf
(1982).
Meteoric water aquifers are found to be widespread, as evidenced from drilling activities
on continental shelves on the east coast of the USA and offshore Africa. Some meteoric water
aquifers were also discovered beneath the seabed some 100km from the coast. In the northern
North Sea, via isotopic analysis it has been found that formation water obtained from shallow
reservoirs partly originates from meteoric water (Bjorlykke, 2010).
Composition of formation water
Total solid concentration in formation waters has been widely explained by many
authors. Firstly, the amount of total solid concentration in formation water can differ across
geographical regions. Case (1956) revealed that the value for subsurface waters (ie.
connate/meteoric/juvenile waters) can range from 0 ppm for fresh meteoric water up to 642,798
ppm for brine in Saline dolomite of Michigan. The high value for dissolved minerals is due to the
dissolution of evaporites in the area.
Concentration of dissolved minerals can also differ vertically or horizontally. Vertical
changes in dissolved solid concentration can occur as the depth increases, especially for sand
(Selley & Sonnenberg, 2022). The increase of salinity with depth is less significant in shales. It
is estimated that the salinity in sand is three times greater than that in shales when these two
sedimentary rocks are found interbedded. Horizontal changes of salinity can be found to
increase from basin margin towards the center. High salinity at the basin center can be
interpreted to result from stagnant regions unaffected by meteoric water flow, thus increasing
the probability for oil and gas accumulations. Selley & Sonnenberg (2022) stated that for most
connate water, the dissolved solid content is mostly below 350,000 ppm.
Roughly, dissolved material in seawater amounts to 35,000 ppm, while meteoric water
has <10,000 ppm (Bjorlykke, 2010). Also, the bicarbonate concentration in seawater is much
higher than that of meteoric water. Besides, increased depth can also lead to increase in
dissolved solid concentration, especially when the basins have evaporite beds, where typical
concentrations of dissolved matter can range between 100,000 - 300,000 ppm. Increase in
temperature can also lead to higher solid concentration, because of the reduced kinetic
obstacles. Another significant difference between seawater and meteoric water is that seawater
has a higher amount of dissolved bicarbonate (HCO3-) (Bjorlykke, 2010).
Variations in the composition of formation water is attributed to the effects of flow
processes and water-rock interactions that took place during the period of sedimentation and
burial (Wang et al., 2022). Studies conducted by Billings et al. (1969) and Hitchon et al. (1971)
revealed that diagenesis and cation exchange on clay surface can influence alterations in
formation water.
Common physical parameters of formation water include density, viscosity, and
compressibility, all of which are normally discovered using charts as there is only little alterations
due to the influence of pressure and temperature to the formation water as compared to crude
oil (Renpu, 2011). Salt content in formation water include K+, Na+, Ca2+, Mg2+, Cl-, SO42-,
Co32-, and HCO3-. While analyzing the salt content, a unit of total salinity is usually
represented by a unit mg/liter.
The order of the ion content in formation water is depicted as shown below:
Table 1 The compositions of various ion and atoms found in formation water (Renpu, 2011)
Ion Composition (mg/liter)
K+, Na+, Cl- 10^3 -10^5
Ca2+, Mg2+, So42-, CO32-, HCO3- 10^3-10^4
K+, Na+, Sr2+ 10^1-10^3
Al3+, B, Fe2+, Li+ 10^0-10^2
Cr, Cu, Mn, Ni, Sn, Ti, Zr 10^-3 (most field water)
Be, Co, Ga, Ge, Pb, V, W, Zn 10^-3
In general, the bicarbonate system governs the pH value of formation water. This in turn
can influence the solubility of carbonate and ionic compounds. High pH value is associated with
increased scaling, while low pH value is related to decreased sealing as well as higher
corrosiveness (Renpu, 2011). Normal range for pH value of formation water in most regions is
between 4 to 9. However, this number can be elevated as it is stored in a laboratory because of
the transformation of HCO3- to CO32- (Renpu, 2011).
Combining cationic and anionic concentration of formation water allows us to discover
total salinity, which is crucial to identify the degree of corrosiveness that it can bring to the
casing in regards to the well completion process, a step through which a well is prepared for
production following drilling. Failure to identify the high salinity of formation water can lead to
tube damage as the salt precipitation can occur within the tube during production and cause
blockage (Renpu, 2011).
Analysis of formation water is highly substantial in well completion engineering. This is
true as the analysis of chemical composition in formation water helps scientists to track the
origin of the water and calculate potential water production rate. Formation water property data
also facilitates the analysis for reservoir sensitivity and the degree of working fluid damage
(Renpu, 2011). Besides, calculation of the resistivity of formation water (Rw) helps to determine
the oil and gas saturations as well as the reservoirs. Formation water analysis also helps
engineers to make decisions in regards to well completion by identifying type, tendency of scale
and compatibility with drilling and completion, as well as fluid perforation, fractures and
acidization (Renpu, 2011).
Besides well completion, formation water has significant application in enhanced oil
recovery (EOR), a process that allows oil to be forcefully mobilized into production well by
applying fluid injection or heat onto the hydrocarbon formation (Jamekhorshid & Azin, 2023).
Other industrial applications of formation water, including for dynamic reservoir modeling,
calculating reserves and cost of completion, facilitating estimation of operating expenditures,
aiding the comprehension of reservoir connectivity (Akinade, 2013).
Bjorlykke (2010) highlighted several uses of subsurface waters, including to identify their origin
and study the fluid flow pattern by studying the water composition; to understand the
permeability transcending barriers like shale layers and faults through salinity and isotopic
study; to understand the rock units from which the water flow through; to assess the density of
the water column through water composition to gather information for the interpretation and
calibration of fluid pressure data from wells; and to calibrate well logs through information in
water composition and resistivity.
Salinity
Measurement of salt concentration or salinity is important as part of evaluation method
on formation water as well as an exploration tool when plotted regionally (Selley & Sonnenberg,
2022). Salinity, defined as total dissolved solids, is commonly quantified in parts per million
(ppm), but sometimes also expressed in milligrams per liter (mg/L):
mg/L = ppm/density
Amount of 70 g/L salt concentration and above would indicate a high salinity, as stated by
Xinquan (2013), and at 300 g/L, the salinity is considered very high and can cause
corrosiveness and severe deterioration to casing during well completion (Renpu, 2011).
Total dissolved solids
Total dissolved solids (TDS) differ from salinity in that TDS comprise of the mass of anhydrous
residue remain in sample vessel after evaporation and subsequent over drying at a defined
temperature, whereas salinity can be defined as the measure of mass of dissolved salts in a
given mass of solution (McCleskey et al., 2023).
Resistivity value of saltwater and freshwater
It has been found that the resistivity value for freshwater and saltwater differ greatly between
each other. In a study by Hodlur et ak (2006), range resistivity of fresh water is between 5.5 - 16
ohm-m while for saltwater the range is 1.9 to 3.16 ohm-m.
Objectives
1. To determine the concentration of salt from well logging.
2. To determine the concentration of hydroxide, carbonate, bicarbonate in formation water
from well logging.
3. To determine the concentration of chloride and sodium in formation water.
4. To determine the resistivity of the formation water.
Method
Experiment 1
Apparatus: weighing balance, conical flask, cork cover, Bunsen burner, oven Formation water
Procedure:
1. An empty 150ml conical flask was weighed with a cork stopper and the weight is
recorded.
2. 75 ml of formation water was poured into the flask and the weight was taken.
3. The flask with the contents was heated until a white precipitate started to appear.
4. The Bunsen burner was turned off and the flask was stored in a 105°C oven and left
overnight.
5. After it was completely dry, the flask was placed in a drying jar for 15 minutes, then the
new weight was taken.
6. The salt concentration in the formation water was calculated (units in mg/l).
Experiment 2
Apparatus: measuring cylinder, conical flask, beaker, retort stand, filter paper and funnel,
formation water, phenolphthalein, sulphuric acid (0.1 N), methyl orange indicator
Procedure:
1. 100 ml of formation water was poured into a beaker, then 3 or 4 drops of phenolphthalein
indicator were added, the red color indicated the presence of carbonate.
2. This solution was titrated with decinormal (0.1N) sulfuric acid until the color disappeared. The
amount of acid used corresponded to 'p' in the table below.
3. The solution was mixed with 2 drops of methyl orange indicator, and the titration continued
until it was reddish purple (neutral). The amount of acid used for both titrations corresponded to
'T' in the table.
Experiment 3
Apparatus: Conical flask, beaker, measuring cylinder, filter paper and funnel, retort stand,
pipette, formation water, silver nitrate, potassium chromate
Procedure:
1. 10 ml of formation water was titrated with 0.1 N silver nitrate using 0.1 N potassium chromate
as an indicator.
2. The titration was carried out until a reddish color indicated the presence of silver nitrate
3. 10 ml of silver nitrate was equivalent to 35.435 mg of chloride. Since 10 ml of solution was
used for titration, the number of millimeters of 0.1 N silver nitrate used will be multiplied by
354.53 to give the chloride concentration (CL) in mg/L.
Experiment 4
Experiment 4 aims to find out the sodium concentration through calculation, and it is shown in
Result section (Experiment 4)
Result
Experiment 1
Empty conical flask weight + cork cover, W0 86.2868 g
Conical flask weight with formation water + 157.566 g
cork cover, W1
Conical flask weight + cork cover after 89.0165 g
heated, W2
Salt weight in formation water, W W2 - W0 = (89.0165 - 86.2868) g = (2.7297)
g = 2729.7 mg
Concentration of salt in formation water Salt weight information water/Volume of
formation water
= (2729.7 mg / 75 ml) x 1000 mg/L
= 36396 mg/L
Experiment 2
Titration result: P = 0.3 ml and T = 7.3 ml
T/2 = 3.65 ml, hence P = <T/2
Carbonate concentration in formation water = 2P x molecular weight g/ml
= 2 x 0.3/1000 x 60 x 1000 mg/L
= 36 mg/L
Concentration of bicarbonate in formation water = (T - 2P) x molecular weight g/ml
= (7.3 - 2 x 0.3) x 61 g/ml
= 6.7/1000 x 61 x 1000 mg/L
= 408.7 mg/L
Experiment 3
Concentration of Cl information water
= 10 ml 0.1N silver nitrate x 354.53 mg/L
= 49.4 x 354.53 mg/L
= 17513.7820 mg/L
Reaction value for Cl
= 17513.7820 x 1/35.453
= 494 me/L
Experiment 4
Concentration of Natrium in formation water
= (a - b) x Na molecular weight
= (584.9590 - 132.1470) x 22.997 mg/L
= 10413.3176 mg/L
Ion Concentration Coefficient Reaction value Value total
(mg/L) reaction (me/L)
(mg/me)
Cl- 17513.7820 1/35.453 494
S02-4 4340 2/96.061 90.359
HCO-3 36.611 1/61.018 0.66
Total a = 584.959
Ca2+ 981.00 2/40.078 48.954
Mg2+ 1011.00 2/24.305 83.193
Total b = 132.147
Finding total solid concentration in formation water
Element Concentration (mg/L) Multiplier
Ca 981.00 0.8
SO4 4340 0.4
Na 10413.32 1
Cl 17513.78 1
Total solid concentration = (Ca x multiplier) + (SO4 x multiplier) + (Na x multiplier) + (Cl x
multiplier
= (981.00 x 0.8) + (4340 x 0.4) + (10413.32 x 1) + (17513.78 x 1)
= 30447.9 ppm
So it was found that the estimated resistivity for this formation water is 0.24 ohm-m.
Discussion
1. Interpretation on the value of salt concentration in formation water
Measurement of salt concentration or salinity is important as part of evaluation method
on formation water as well as an exploration tool when plotted regionally (Selley & Sonnenberg,
2022). Salinity, defined as total dissolved solids, is commonly quantified in parts per million
(ppm), but sometimes also expressed in milligrams per liter (mg/L):
mg/L = ppm/density
Based on our experiment, the salt concentration in the formation water is 36.396 g/L.
This level of salt concentration in formation water indicates low salinity, referring to Xinquan
(2013).
2. Interpretation on the value of each of the elements in total solid concentration
Total solid concentration calculated from the experiment is 30447.9 ppm.
I. Cl-
Bjorlykke (2010) stated in general, formation water is saline, and Cl- is the most
dominant anion, while the rest of the cations are mostly Mg2+ and Ca2+. This is true as we also
found Cl- from our formation water to have the highest value at 17,513.7820 mg/L. The high Cl-
content can be attributed to the fact that Cl- is not affected by any diagenetic processes
(Bjorlykke, 2010), unlike other ions like SO2-4 and Mg2+.
II. SO2-4
The formation water has 4,340 mg/L of sulfate content. The sulfate ion content in
formation water varies across different origins. For seawater origin, the sulfate ion is significantly
lower compared to meteoric water because as the seawater gets buried a few meters below the
seabed, all the sulfate content will be taken up by sulfate-reducing bacteria. Hence, it is very
common for connate water to contain very low sulfate (Bjorlykke, 2010). Our formation water
has very high sulfate content, as compared with freshwater sulfate analyzed by Zak et al (2021)
& Wu (2018).
III. Ca2+
The amount of Ca2+ in the formation water is 981 mg/L. This is low calcium ion content
according to Xinquan (2013). Low calcium ions are less likely to cause scale of calcium
carbonate, CaCO3 or calcium sulfate, CaSO4 in the tubing of production well.
IV. Mg2+
The formation water has 1011 mg/L of magnesium ion Mg2+. The magnesium ion
content is much higher compared to magnesium content obtained from formation water in
Forties, Miller and Prudhoe Bay oil fields. Mg2+ contained in marine seawater can potentially
react with clay minerals, as it can be absorbed from the marine porewater and form carbonate
minerals such as dolomite (Bjorlykke, 2010). It has been said that in general, freshwater has
lower magnesium ion content compared to calcium ion (Taipei Ministry of Environment, n.d.) due
to abundance of calcium in the Earth’s crust.
Bicarbonate content in this formation water is in moderate amounts, at 487 mg/L,
compared to what has been reported by Wu (2018). Various oil field locations like Forties, Miller
and Prudhoe Bay have bicarbonate content in formation water at 360 mg/L, 2090 mg/L, and
1978 mg/L respectively.
However, in reality, the determination of formation water does not rely solely on the result
of formation water analysis, but also on evaluation on mineralogy and isotopes. Determination
of the origin of formation water can be a complex process as it may not only involve analysis of
formation water, but also mineralogical evaluation of related core samples, as what have been
conducted by Birkle et al. (2009) through which they found connection between seawater
evaporation, infiltration of seawater and meteoric water into reservoir, and extensive
dolomitization of carbonate that constitute large part of evolution of the formation water in
Jujo-Tecominoacan oil reservoir in the Gulf of Mexico. Meanwhile, Stueber & Walter (1990)
incorporated isotope study in finding formation water origin and its chemical evolution from
Illinois basin.
3. Interpretation of the resistivity value of the formation water
The resistivity value of the formation water is 0.24 ohm-m. In general, formation water has low
resistivity hence it is a good electric conductor. Resistivity varies significantly with temperature,
but does not change much with increasing pressure (Glover, n.d.). Formation water with 0.24
ohm-m has a high possibility to originate from the marine environment.
4. Origin of the formation water
This formation is found to have low salinity and very high sulfate, low carbonate, which is not
common in formation water of seawater origin, but the amount of total solid concentration and
high magnesium, low calcium, and low resistivity suggest otherwise. Hence, it is more
appropriate to assume that this formation water is of seawater origin.
Conclusion
In conclusion, the objectives stated earlier in this report have been achieved through a series of
experiment, calculations. The concentration of salt is 36,396 g/L, the total solid concentration is
30447.9 ppm, comprising many dissolved ions including sodium (10,413.32 mg/L), chloride
(17,513.78 mg/L), sulfate (4340 mg/L), calcium (981 mg/L) and magnesium (1011 mg/L). With
the given chemical content of the formation water and comparison with current literatures, it has
been concluded that the formation water is of seawater origin. The analysis of formation water is
crucial for understanding the fluid flow pattern, permeability and density. To obtain more
accurate results on the origin of the formation water, it is suggested to gather more data on pH,
Eh and resistivity.
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