Chemical Analysis

Engineering Encyclopedia
Saudi Aramco DeskTop Standards
CHEMICAL ANALYSIS
Note: The source of the technical material in this volume is the Professional
Engineering Development Program (PEDP) of Engineering Services.
Warning: The material contained in this document was developed for Saudi
Aramco and is intended for the exclusive use of Saudi Aramco’s employees.
Any material contained in this document which is not already in the public
domain may not be copied, reproduced, sold, given, or disclosed to third
parties, or otherwise used in whole, or in part, without the written permission
of the Vice President, Engineering Services, Saudi Aramco.
Chapter : Corrosion For additional information on this subject, contact

File Reference: COE-102.06 PEDD Coordinator on 874-6556
Engineering Encyclopedia Corrosion Monitoring
Chemical Analysis
Content Page
INTRODUCTION ........................................................................................................... 4
SAMPLING .................................................................................................................... 5
Access to the System ......................................................................................... 6
TYPES OF CHEMICAL ANALYSIS............................................................................... 8
Water Analysis.................................................................................................... 9
pH ..................................................................................................................... 10
Deposit Analysis ............................................................................................... 14
Residual Chemical............................................................................................ 16
Gas Analysis..................................................................................................... 16
Oxygen Analysis ............................................................................................... 19
Iron Count ......................................................................................................... 23
Analysis.................................................................................................. 27
Interpretation.......................................................................................... 28
Case Study A ......................................................................................... 32
Case Study B – Qurayyah Seawater Injection System .......................... 32
Bacterial Activity ............................................................................................... 35
Microscopic Techniques......................................................................... 36
Culture Techniques................................................................................ 37
ATP ........................................................................................................ 44
Radiotracer Techniques ......................................................................... 45
Case Study A – Qurayyah Seawater Injection System ........................ 45
Case Study B – Sour Oil Field .............................................................. 50
Case Study C – Water Injection System ............................................... 51
WORK AIDS................................................................................................................ 53
Reference Tables ............................................................................................. 53
Saudi Aramco DeskTop Standards i

Chemical Analysis
Sampling And Measurement ............................................................................ 54

Temperature, Humidity, And Atmospheric Pressure Correction ....................... 55
Interferences..................................................................................................... 55
Hazardous Properties Of Hydrogen Sulfide...................................................... 55
Chemical Reaction In Detector Tubes .............................................................. 55
Field Method For Determination Of Iron (Ferrous)
In Sweet Oil-Field Waters ................................................................................. 56
Apparatus............................................................................................... 56
Solutions ................................................................................................ 56
Procedure .............................................................................................. 56
Calculation ............................................................................................. 57
REFERENCE .............................................................................................................. 60
List Of Articles................................................................................................... 60
Api Recommended Practices ........................................................................... 60
GLOSSARY................................................................................................................. 61
List of Figures
FIGURE 1. pH Values of Common Processes and Products..................................... 12

FIGURE 2. Produced Gas CO2 Content .................................................................... 19
FIGURE 3. Oxygen Analysis – Colorimetric Kit .......................................................... 20

FIGURE 4. Dissolved Oxygen Meter Probe ............................................................... 21
FIGURE 5. Double-ended Sampler and Receiver –
Typical Location in the Bottom of a Flowline ........................................................ 26
FIGURE 6. Iron-Loss Nomograph .............................................................................. 30
FIGURE 7. Iron Activity with Pertinent Operating Information .................................... 31
FIGURE 8. Qurayyah Seawater Treatment and Injection System.............................. 33
Saudi Aramco DeskTop Standards ii

Chemical Analysis
FIGURE 9. Iron Count at Various Locations

in the Qurayyah Seawater Injection System, 1981-89 ......................................... 34
FIGURE 10. Techniques Used to Detect Microorganisms
(Sessile and Planktonics) ..................................................................................... 35
FIGURE 11. Extinction Dilution Technique................................................................. 38
FIGURE 12. Robbins Device Biofilm Sampler............................................................ 41
FIGURE 13. Biological Sample Probe Assembly ....................................................... 42
FIGURE 14. Biofilm Sampling Spool in Place ............................................................ 43
FIGURE 15. Seawater SRB (Planktonic) Monthly Average – UWSS......................... 47
FIGURE 16. Seawater SRB (Sessile) Monthly Average – UWSS.............................. 48
FIGURE 17. Seawater SRB (Planktonic) Monthly Average – Qurayyah .................... 49
Hydrogen Sulfide Length-Of-Stain Detector Tubes ..................................................... 53
Gas Detector ............................................................................................................... 54
Iron-Loss Nomograph.................................................................................................. 58
Extinction Dilution Technique ...................................................................................... 59
List of Tables
TABLE 1. Hydrogen Ion Concentration in Moles/Liter at 25 C .................................. 10

TABLE 2. Acid Solutions for Deposit Testing ............................................................. 15
TABLE 3. Amount of H2S to Reach NACE Limit (0.05 psia)...................................... 17
TABLE 4. Effect of Partial Pressure of CO2 on Corrosion ......................................... 17
TABLE 5. Extinction Dilution Test Results.................................................................. 50

TABLE 6. Detection of Planktonic and Sessile SRB
Using API and Specific Field Water Medium........................................................ 52
Saudi Aramco DeskTop Standards iii

Chemical Analysis
INTRODUCTION
Chemical analysis is an essential part of a corrosion monitoring

program. Many chemical tests are available to detect corrosion.
Other tests trace or measure the processes associated with
corrosion. Chemical analysis measures the concentrations of
the ions involved in the corrosion reactions. Repeated analysis
at the same point helps to identify the types of changes taking
place in the system as a function of time. Analysis at different
points in the system measures the interaction between the fluid
composition and the surface of the system.
The condition of an oil field production system is constantly

changing and is dependent on several factors.
• Most oil field systems are based on once-through flow.

As the flow passes through the system, its physical
properties and chemical composition are changed by
pressure and temperature variations, phase separation,
and chemical/electrochemical reaction with the exposed
metal surfaces.
• Deposits in the system that build up in stagnant or low

flow rate parts of the system may be removed partly or
completely by periodic cleaning. These deposits may
even change in character with time. With low flow rates,
deposits can build up and create different environments
where localized corrosion can occur. Even anaerobic
sulfate-reducing bacteria can thrive under these deposits
while most of the system is an aerobic environment.
• Few oil field sources supply fluid of constant composition.

For example, water supply wells can produce water of
changing salinity that will affect its corrosivity.
Saudi Aramco DeskTop Standards 4

Chemical Analysis
SAMPLING
The critical part of any chemical analysis testing is obtaining a

meaningful sample. The sample must be protected from
contamination or natural alteration from the time it is collected in
the plant or in the field until the analysis is actually made.
Freshness and minimal contact with atmospheric oxygen is
most critical for iron count and pH.
The sample must be representative of the material of interest or

the analysis will lead to false conclusions. The importance of
good sampling can not be overemphasized. For routine water
samples, clean plastic bottles with tightly fitting plastic caps are
recommended. Pint or quart (500 ml or 1-liter) bottles are
commonly used. The bottles – not the caps – should be
carefully labeled to identify the sample. The caps could be
switched accidentally.
Never use a metal container or a metal cap. The water will

corrode them and become contaminated with corrosion
products.
If a sampling valve is available, connect a piece of plastic tubing

to the end of the valve. Once the valve is opened, allow the
water to run for at least 1 minute. Observe the color of the
water. If the color is changing, wait until the color becomes
constant. There is probably debris in the valve or in the bottom
of the line. This debris needs to be flushed out before the
sample is taken.
Once the color of the water is constant, rinse the bottle at least
three times. Place the end of the plastic hose in the bottom of
the bottle and allow the water to overflow the bottle. Slowly pull
the hose out then quickly cap the bottle to minimize oxygen
contamination and the escape of dissolved gases.

Chemical Analysis
Access to the System
Usually hot tapping and welding of access points not in the

original design weakens the system and may lead to failure at
the welds. Thus, it is preferable for all sampling points to be
included in the design stage. Guidelines for the location of
sampling/monitoring points in oil field production systems
include:
• Water source wells
• Upstream and downstream of filters
• In flowline downstream of well head, located far

enough from the well to avoid turbulence
• Gas lift wells
• Install from side of line if water level permits.
• If this is not possible, install from bottom of line.
• Avoid dry exposure at top or sand erosion at the

bottom of the line.
• Water injection stations
Access points should be located between pieces of

equipment and vessels – such as boots, surge tanks,
pumps, and headers – to aid in locating problems such as
oxygen entry. Access points should also be installed at
the main inlets and outlets to the station.
• Water injection wells
Access points should be located in straight sections – but

not the meter run – of the system and preferably between
two valves to allow shutdown if needed.

Chemical Analysis
• Oil wells
• In flowline near well head with the sampling done

from the bottom of the line
• Not too close to the well head or a valve so as to

avoid turbulence
• Oil flow stations
• Bottom of incoming pipelines or headers
• Drain line of three-phase separators upstream of

water drain/dump valves
• Tank bottoms/surge tank bottoms
• Drain lines of desalters/heater treaters upstream of

water drain/dump valves
• Gas outlets from two-phase separators to

flare/compressors
• Gas main to compressors (vertically down from near

bottom or from bottom)
• Tank bottom
• Close to bottom of tank, typically 0.5 meters from

floor
• Not in downcomer inside tank or any other static

environment where oil might collect

Chemical Analysis
TYPES OF CHEMICAL ANALYSIS
Several chemical analysis methods are available for assessing

corrosive environments and monitoring changes.
• Water analysis – To determine the variations in ion

concentration of water
• pH – To monitor and adjust the degree of acidity for use in

corrosion control in glycol systems, drilling fluids, and
plant applications
• Deposit analysis – To determine the composition of

corrosion products in order to identify types of corrosion
problems or to detect changes in the system
• Residual chemical – In certain cases, to determine the

amount of corrosion inhibitor present, chlorine dosages
for microorganism control, or sulfite dosages for oxygen
scavenging
• Gas analysis – In most cases, to determine concentration

of acid gases such as CO2 and H2S
• Oxygen analysis – To determine the content of dissolved

oxygen in water and oxygen in gases
• Iron count – In most cases, to monitor inhibition programs

in sweet gas or oil wells
• Bacterial activity – To determine the activity of various

types of bacteria, especially sulfate reducers

Chemical Analysis
Water Analysis
Periodic analyses of water samples can indicate changes in

corrosivity of systems. They are often the initial step in solving
corrosion, scale, or pollution problems. The importance of
water analysis is very evident. Water treatment is based on the
results of the analysis. Casing leaks in producing wells can be
detected using the results of water analyses. Compatibilities of
waters for injection in secondary recovery can also be predicted
from water analysis data.
The chemical and physical properties of a water are greatly

influenced by the types and concentration of dissolved
substances in it. Routine water analyses in the petroleum
industry include measurement of pH, specific gravity, specific
resistivity, and determinations of the concentration of carbonate,
bicarbonate, sulfate, chloride, iron, calcium, magnesium,
sodium, and total dissolved solids. Generally, the corrosivity of
water containing dissolved salts increases with increasing salt
concentration until a maximum rate is reached, and then the
corrosivity decreases. If a water analysis indicates a corrosive
water, then measures for preventing corrosion can be included
in the initial design. It is more effective and less costly to know
a water is corrosive and design for the corrosivity than to modify
the system after it has been constructed.
On-site analysis of certain ions is desirable. Reactions can

occur in samples to change the equilibrium of some ions.
Bicarbonate (HCO3-) can convert to carbonate (CO3-2) when
dissolved CO2 comes out of solution. Iron can oxidize to
Fe2O3 unless the sample is preserved with acid. Therefore,
on-site analysis is sometimes needed.
On-site analysis of various ions in water can be accomplished

by using colorimetric kits or digital titration. Colorimetric kits
produce a color showing the presence and concentration of the
specific ion. In titration, the amount of reagent needed to
reach a certain visual standard is related to the concentration of
the specific ion.

Chemical Analysis
pH
pH is a measure of a solution’s acidity. A pH of 7.0 is neutral

and is neither acid nor base. A pH greater than 7.0 means that
the solution is alkaline. The highest pH possible is 14.0. A pH
less than 7.0 means that the solution is acidic. The lowest pH
possible is 0.0. pH is an important factor when considering
scaling tendencies of water. pH values greater than 7.0 support
scaling tendencies while pH values below 7.0 do not support
scaling tendencies but will render the water more corrosive with
materials such as steel. Some materials might corrode more
readily in alkaline rather than acidic conditions, and the
engineer must know the limitations of materials during pH
swings.
TABLE 1. Hydrogen Ion Concentration

in Moles/Liter at 25 C
pH H+ OH-
0 (100) 1 0.00000000000001 (10-14)
1 (10-1) 0.1 0.0000000000001 (10-13)
2 (10-2) 0.01 0.000000000001 (10-12)
3 (10-3) 0.001 0.00000000001 (10-11)
4 (10-4) 0.0001 0.0000000001 (10-10)
5 (10-5) 0.00001 0.000000001 (10-9)
6 (10-6) 0.000001 0.00000001 (10-8)
7 (10-7) 0.0000001 0.0000001 (10-7)
8 (10-8) 0.00000001 0.000001 (10-6)
9 (10-9) 0.000000001 0.00001 (10-5)
10 (10-10) 0.0000000001 0.0001 (10-4)
11 (10-11) 0.00000000001 0.001 (10-3)
12 (10-12) 0.000000000001 0.01 (10-2)
13 (10-13) 0.0000000000001 0.1 (10-1)
14 (10-14) 0.00000000000001 1 (100)

Chemical Analysis
The formal definition of pH is the negative logarithm of the

hydrogen ion activity.
pH = -log [H+]
The pH value of a substance is directly related to the ratio of the

hydrogen ion [H+] and the hydroxyl ion [OH-] concentrations.
Since pH is a logarithmic function, a change of one pH unit
represents a ten-fold change in hydrogen ion concentration.
Table 1 shows the concentration of both the hydrogen ion and
the hydroxyl ion at different pH values.
Figure 1 provides pH values for some common processes and

products.

Chemical Analysis
FIGURE 1. pH Values of Common Processes and Products

Chemical Analysis
The pH value is best determined in situ or immediately upon

taking the sample. The pH values of aged samples are usually
worthless. Laboratory pH values for field water samples are
usually not equal to the pH in the system. Since pH is a
function of ions and dissolved gases, it can change with time.
Oxidation of iron followed by precipitation of ferric hydroxide can
act to raise the pH. Loss of dissolved gases like CO2 and H2S
will also increase the pH. Therefore, pH should be measured
on-site to be meaningful.
A rough indication of pH can be obtained using pH papers or

indicators that change color as the pH level varies. These
papers are inexpensive and easy to use but have limited
accuracy. Indicating pH papers are available in various ranges.
They can be difficult to interpret correctly in colored or murky
samples.
More accurate measurements are obtained with a pH meter.

This type of meter will show immediate changes in process
conditions. This meter consists of three parts: a pH measuring
electrode, a reference electrode, and a high-input impedance
meter. The pH electrode can be thought of as a battery with a
voltage that varies with the pH of the measured solution. This
electrode is a hydrogen-ion sensitive glass bulb with a millivolt
output that varies with the changes in the relative hydrogen ion
concentration inside and outside the bulb. The reference
electrode is not affected by the variance of the hydrogen ion
activity. Essentially, the pH meter is a high impedance amplifier
that accurately measures minute electrode voltages and
displays the results in pH units.
The pH meters are subject to fouling and can be costly. The

extent of corrosion occurring in the process equipment cannot
be determined by this equipment. pH meters require a high
level of maintenance. They need to be calibrated periodically at
several specific pH values. Buffers are used to calibrate pH
meters. Buffers are solutions that have constant pH values and
the ability to resist changes in that pH level. Buffers are
available with a wide range of pH values.

Chemical Analysis
Glycols as received from a supplier should have a pH of 7.0 -

7.5. During usage, the pH may change from the original value
due to the accumulation of acids or bases absorbed from the
process streams. A decrease in pH is viewed as an indication
of glycol degradation. The pH of these glycols can be
determined with pH paper or a pH meter. The sample should
be diluted with an equal amount of distilled water prior to
testing.
Deposit Analysis
The chemical analysis of samples of corrosion product and

deposits in a system can be an important part of a monitoring
program. Samples may be taken directly from piping or vessels
or from coupons exposed to the system. For instance, samples
can be obtained when a scraper is run through a pipeline.
Knowledge of the composition of such deposits helps to
determine the type of problem and to detect changes in the
system.
Proper sample collection and handling are extremely important.

Full details on the dates, conditions, and locations of the
samples are very helpful in interpreting this data. NACE
recommended practice RP-01-73, “Collection and Identification
of Corrosion Products”, gives excellent guidelines.
Samples of corrosion products can change chemically after they

have been removed from a system. For example, when iron
sulfide comes in contact with air, it oxidizes to iron oxide. A
sample that was black from iron sulfide when collected may turn
brown from ferric iron oxide by the time it reaches the
laboratory. Thus the color of the sample when it was collected
is very important information.
Laboratory analysis for chemical composition should always be

performed on these samples. However, there are some simple
field tests that can be used to obtain immediate information.
Recipes for two test acids are given in Table 2.

Chemical Analysis
TABLE 2. Acid Solutions for Deposit Testing

Solution 1
Water 400 ml
Isopropyl alcohol 150 ml
Concentrated HCl acid (clear,
* 450 ml
pure acid required)
*Add acid last, slowly with stirring. If available, add 5 to
10 ml of a liquid detergent or wetting agent to final solution.
Solution 2
To 100 ml of Solution 1, add approximately 5 g (about
1 level teaspoon) of sodium arsenite (Na2HAsO3) powder
and stir to dissolve.
CAUTION: Protect eyes and skin when preparing acid
solution. Do not inhale or ingest the sodium arsenite
powder. Wash skin thoroughly with soap and water if
contacted by sodium arsenite.
Acid solution 1 can be used for testing the general nature of

heavy deposits scraped from corroded metal surfaces. Place a
small piece (1 cm3) of the corrosion product in a glass cup and
drop approximately 25 ml of solution 1 on it. Record the
observations. If the sample fizzes and gives off a rotten egg
smell (H2S), then iron sulfide is present. If the sample fizzes
and fails to emit any H2S odor, then the deposit is probably a
carbonate. A laboratory analysis is then needed to confirm this
composition.
Rust or iron oxide is usually reddish brown and dissolves slowly

in solution 1 acid without fizzing. Millscale (Fe3O4) also
dissolves slowly in this acid or not at all. When dry, millscale
can be attracted by a magnet.
Acid solution 2 is specifically used for detecting iron sulfide

directly on metal surfaces. This solution is used when
inspecting equipment that has failed brittlely, as in sulfide stress
corrosion cracking. In these situations, a thin, black deposit is
usually present on the equipment. The test for iron sulfide
consists of dropping a few drops of acid solution 2 directly on
the metal near the fracture. Appearance of a yellow precipitate
in the acid indicates that iron sulfide is present in the corrosion
product.

Chemical Analysis
Residual Chemical
The measurement of residual oil field chemicals can be very

helpful in troubleshooting a treating program. Chemicals such
as sulfite for oxygen scavenging or chlorine for bacterial control
in fresh waters have their residuals checked to optimize treating
programs. Both field colorimetric kits and online monitors are
available to check these residuals.
Sulfite concentrations in boilers and process waters must be

routinely monitored to avoid overtreatment. While sulfite
removes oxygen, an excess of sulfite can lower the pH and
make the water corrosive to steel.
Other useful information is the inhibitor concentration in a fluid.

It helps determine when to retreat. Laboratory procedures
include atomic absorption or fourier infrared spectroscopy used
to determine inhibitor concentrations. One very simple field test
to determine the presence of inhibitor in a system is the copper
ion displacement (CID) test. In this test, a coupon is dipped in
or exposed to the inhibited fluids and then immersed in a
saturated copper sulfate solution. Where an inhibitor is present
on the coupon, no copper will deposit. Copper will deposit on
those areas not filmed by the inhibitor. Therefore, this
examination can lead to a qualitative measure of the inhibitor
presence.
Gas Analysis
Gas analysis is an excellent tool when evaluating the corrosivity

of a system. Both carbon dioxide and hydrogen sulfide in the
presence of water can be corrosive. In gas wells or gas
handling, determination of the carbon dioxide and hydrogen
sulfide is fairly routine when they are present in large quantities.
Trace quantities of hydrogen sulfide are harder to detect but
can be of extreme importance. For instance, traces of
hydrogen sulfide can cause cracking of high-strength steels.
Table 3 shows the amount of H2S needed for various pressures
to reach the NACE limit (0.05 psia) for sulfide stress corrosion
cracking. If the H2S partial pressure is 0.05 psia or greater,
then sulfide stress corrosion cracking resistant materials are
needed.

Chemical Analysis
TABLE 3. Amount of H2S to Reach NACE Limit (0.05 psia)

psia Mol Fraction ppm percent
250 0.0002 200 0.02
500 0.0001 100 0.01
1,000 0.00005 50 0.005
2,000 0.000025 25 0.0025
5,000 0.00001 10 0.001
10,000 0.000005 5 0.0005
20,000 0.0000025 2.5 0.00025
The corrosivity of carbon dioxide is a function of pressure and is

based on the partial pressure of CO2 as shown in Table 4.
TABLE 4. Effect of Partial Pressure

of CO2 on Corrosion
0 - 7 psi Mild corrosion
7 - 30 psi Moderate corrosion
> 30 psi Severe corrosion
Partial pressure is the mole percentage of gas multiplied by the

total pressure.
In many flowing gas wells, corrosion occurs where water

condenses and carbon dioxide combines with it to form
carbonic acid. Some fields experience a rise in the percentage
of CO2 over time as shown in Figure 2.
Hydrogen sulfide can either occur naturally or be the by-product

of sulfate-reducing bacteria. In some waterfloods, the injection
of sulfate-reducing bacteria into originally “sweet” (no H2S)
reservoirs can turn the reservoirs “sour” (H2S)

Chemical Analysis
Produced gas analysis can be routinely performed in the

laboratory with chromatography. Periodic analyses can
determine the changes in CO2 content. Analysis for H2S must
be conducted on-site, however. H2S often reacts with steel
sample containers and may not be detectable if a long delay
exists between sampling and analysis. For field measurement,
“length-of-stain” detector tubes can be used to determine the
amount of CO2 or H2S. Each of these detector tubes contains
a reagent that is specifically sensitive to a particular vapor or
gas. The reagents are contained on a 5 grain silica gel,
activated alumina, or other absorbing medium inside a sealed
glass tube. In this technique, a specific detector tube has both
of its ends snapped off with one end inserted into a volumetric
pump and the other end inserted into the gas to be analyzed.
While the pump handle is pulled out, a measured volume of the

gas is pulled inside the tube where it comes in contact with the
reagent. The reagent instantly changes color. The more
reagent that changes color, the higher the concentration of the
specific gas. Thus, the gas concentration is shown by the
length of stain. These “length-of-stain” tubes are inexpensive
and easy to use. However, their accuracy is operator
dependent. Additional information is given in the Work Aids.

Chemical Analysis
FIGURE 2. Produced Gas CO2 Content
Oxygen Analysis
Oxygen dissolved in water is probably the most troublesome

corrosive agent. Oxygen concentrations as low as 0.05 ppm
can cause serious problems in water injection systems. Oxygen
can enter systems through loose packing, ineffective pump
seals, open tanks, or inadequate inert gas blankets.
Oxygen in the presence of water can greatly increase the

corrosivity of other gases such as carbon dioxide and hydrogen
sulfide. Industry experience indicates that a solution containing
carbon dioxide and oxygen is 10 to 40 percent more corrosive
than the sum of the corrosion caused by each of the individual
gases.

Chemical Analysis
There are several methods used to measure dissolved oxygen

in water: colorimetric kits and membrane probe oxygen meters.
Colorimetric kits quickly measure dissolved oxygen in water to
the parts-per-billion (ppb) level. Typically these kits consist of
glass tubes containing a highly sensitive colorimetric reagent,
Rhodazine D. When the tip of the tube is snapped, a sample of
water is pulled inside the tube to mix with the reagent and
produce a color change as shown in Figure 3. Results are
quantified by visual comparison with standards.
FIGURE 3. Oxygen Analysis – Colorimetric Kit
The membrane probe oxygen meter is designed to measure

oxygen content in both liquid and gaseous mixtures. It is
capable of measuring oxygen levels below 10 ppb. The cell
used with the meter is essentially an electrolytic cell consisting
of a gold cathode and a silver anode immersed in an electrolyte.
Figure 4 shows an exploded view of one of these probes.
Typically, a thin permeable Teflon membrane is used to isolate
the interior of the cell from the environment but allows the
passage of O2 into the cell. When a voltage is applied across
the cell, oxygen that has passed through the membrane reacts
at the cathode, causing a current to flow. The resulting current

Chemical Analysis
then gives a direct measure of the oxygen diffusion rate that is

related to oxygen concentration. The amount of current that
flows is proportional to the partial pressure of oxygen in the
environment to which the membrane is exposed.
FIGURE 4. Dissolved Oxygen Meter Probe

Chemical Analysis
The membrane passes oxygen at a rate proportional to the

pressure difference across it. Since oxygen is rapidly
consumed at the cathode, it can be assumed that the oxygen
pressure under the membrane is zero. Hence, the force
causing the oxygen to diffuse through the membrane is
proportional to the absolute pressure of oxygen outside the
membrane. If the oxygen pressure increases, more oxygen
diffuses through the membrane, and more current flows through
the sensor. A lower pressure results in less current.
During routine use, gases other than oxygen may diffuse

through the membrane and reduce at the cathode. Some
gases, especially H2S, react with the electrodes and may
“poison” the cell. This poisoning is usually indicated as a
tarnish on the gold cathode and can be overcome by periodic
wiping of the gold surface with a clean, lint-free cloth.
CAUTION: Do not clean the cathode with abrasives.
Temperature of the probe is also important since the

permeability of the membrane increases about 4 percent for
every degree C of temperature increase. Therefore, the meter
needs to be temperature compensated.
Membranes should never be touched. Any contamination on

the membrane surface will alter its permeability to oxygen and
could lead to a premature rupture. The membranes should be
tight and without wrinkles. Air bubbles should also be excluded
from the electrolyte. Air bubbles are a constant source of
oxygen and will interfere with the probe’s operation.
For accurate oxygen measurement, always use an airtight flow

cell for housing the probe. The fluid to be sampled can be
simply routed to the flow cell by plastic tubing. This tubing will
prevent the fluid from picking up oxygen prior to seeing the
probe. Preferably, the flow cell should be made of transparent
plastic in order to allow easy inspection of the probe membrane
during measurement. In this case, any deposits or gas bubbles
on the membrane that might interfere with the readings can be
noted.

Chemical Analysis
Iron Count
One of the easiest, quickest, and least expensive techniques for

predicting corrosion and evaluating inhibition is determination of
the iron content of the system fluid, also known as iron count.
From samples taken at regular intervals, plots of iron counts
versus time are constructed. Any significant increase in iron is
interpreted as an increase in corrosion within the system. This
technique is particularly useful in monitoring the effectiveness of
inhibition programs where the reduction in iron content from
pretreatment levels indicates the success of the control.
Iron counts are the most widely used method for monitoring
downhole corrosion rates in gas and gas condensate wells that
produce little or no H2S. In these wells, carbon dioxide is the
primary corrosive agent. In addition, organic acids are
frequently present. They tend to keep iron in solution for at
least a few minutes prior to oxidation after a water sample is
taken from the wellhead or flowline.
Iron analyses in sour systems are not as representative as

those in sweet systems. Chunks of iron sulfide peel off
periodically, causing a distortion in the iron count. Iron-loss
data is most useful in systems experiencing general corrosion
attack rather than pitting/localized attack.
The iron count may range from 5 ppm up to several hundred

ppm where large concentrations of iron are present in formation
water. Some sand formations containing clays, such as
chlorites, produce water with a natural iron content. This
background iron concentration is usually constant in relation to
the volume of formation water in the total produced water at the
wellhead. Therefore, treatment with a corrosion inhibitor would
not normally reduce the iron content in the produced fluids
below the level of formation iron.
There are three basic steps to an iron count study.
• Sampling
• Analysis
• Interpretation

Chemical Analysis
Samples should be taken from representative flowing fluids and

not from stagnant systems. When collecting samples for iron
count, the following factors must be considered:
• The sample valve and upstream nipples should be

flushed out completely prior to sampling. This flushing is
necessary to ensure that fresh fluid, not stagnant, is being
sampled.
• The sample jar must be clean and free of iron.
• Since iron will absorb on the sample jar wall, the water
sample should be acidified with several drops of
concentrated hydrochloric acid (HCl, pH 1 to 2) to hold
iron in solution.
• Aeration of the sample should be minimized and the

sample jar sealed before transporting to the laboratory.
Cleanliness is very important because it is very easy to

contaminate an iron count sample. A piece of iron oxide about
the size of a pinhead dissolved in a pint of fluid is equivalent to
about 10 ppm of iron. The water sample can easily turn either
red or black as it is collected. If red or rust colored, the sample
has reacted with air to form iron oxide. If black, iron sulfide has
probably formed. To prevent either iron oxide or iron sulfide
from forming, diluted hydrochloric acid should be placed in the
sample jar before the water sample is caught.
The sample point usually consists of a tee or nipple and valve

welded on a pipeline or vessel. This fitting may not be used
exclusively for sampling but may have been originally installed
to monitor pressure or other parameters in the system.
The container used to catch the sample can be a glass or

plastic bottle if the system pressure permits a safe collection.
After purging the sample line and while obtaining the desired
sample, it is important that the valve on the line not be adjusted
to either increase or decrease the flow. Any adjustments that
disrupt the flow rate may dislodge iron precipitates and cause
them to flow into the sample container.

Chemical Analysis
The time needed to obtain a sample must be extended if

sufficient water is not readily obtained. While sampling in some
systems may be done in a few minutes, other systems (for
example, gas well flowlines with intermittent slugs of water) may
require 12 to 24 hours. A corrosion resistant sample receiver
with a pressure rating consistent with the maximum system
pressure should be installed in a bottom sample fitting in a line
as shown in Figure 5. The receiver should be separated from
the system by an insulating flange to prevent galvanic attack
between dissimilar materials. The sample receiver can be
removed from the line after closing both the access fitting and
the top receiver valve. The pressure must be slowly bled when
removing the sample receiver from the access fitting.
CAUTION: If the system is sour, follow safety precautions

involving H2S handling.

Chemical Analysis
FIGURE 5. Double-ended Sampler and Receiver –

Typical Location in the Bottom of a Flowline

Chemical Analysis
Analysis
Iron counts are normally run on aqueous samples. Analysis of

hydrocarbon samples for iron content is possible. One
suggested technique for “iron in oil” determination is given in the
Work Aid section. This analysis for iron in hydrocarbons
requires that the iron be extracted into an acid-water phase.
One procedure used in this analysis consists of boiling the
hydrocarbon with HCl to achieve the extraction. Acid must be
added to the sample container to hold the dissolved iron in
solution if analysis cannot be performed on-site. Reagent grade
hydrochloric acid (HCl) should be used. Ten drops of 10% HCl
is recommended for a 100-ml sample.
If a sample is found to be completely emulsified with no free

water, the following methods may be used to separate free
water.
• The sample may be heated to break the emulsion.
• A portion of the sample may be separated by centrifuging

to obtain sufficient water.
• A small quantity of iron-free demulsifier may be added to

a sample followed by heat, agitation, and centrifugation to
aid water separation.
There are several methods for iron analysis in aqueous

samples. The most often used is the orthophenanthroline
colorimetric method. Portable kits similar to the ones shown in
Figure 3 can be used in the field both easily and quickly. A
sample of the water to be tested is placed in the kit’s snap cup.
Then the kit’s glass ampoule is placed in the cup with its
tapered tip down and snapped. These ampoules contain color-
forming reagents under vacuum. When the tip is snapped, the
vacuum pulls some of the sample water into the ampoule. The
sample and reagent are then mixed by tilting the ampoule back
and forth. Color comparators are then used to quantify the iron
content. The test ampoule is placed between pairs of standards
and compared until an appropriate color match is found.

Chemical Analysis
Other methods used to measure iron content (usually laboratory

analysis) include the atomic absorption spectrophotometric
method and both dichromate and ethylenediaminetetraacetic
acid (EDTA) titration. These methods, especially the last two,
are subject to interferences from detergents, inhibitors, and
hydrogen sulfide that may be present in the produced fluids.
The titration methods as well as several other methods are
given in API 45: Recommended Practice for Analysis of Oil-
Field Waters.
The section of this practice pertaining to iron (Paragraph 3.6)

has been included in the Word Aid section.
Interpretation
Iron counts can be considered a good corrosion monitoring

method only when viewed with a number of iron counts
gathered from the same sample point in the same manner and
analyzed by the same analytical method. Variations in flow rate
in a given system can lead to fluctuations in iron counts.
Therefore, the use of iron counts is only relevant to corrosion if
the flow rate in a system is constant. In gas wells where only
small quantities of water are produced, it is usually satisfactory
to use the iron count. If the flow rate varies, it is necessary to
convert the iron count to iron loss (pounds of iron removed/day).
Also note that 10 ppm of iron measured in a sample of water

from a well producing 1,000 bbls/day represents the same rate
of iron removal as 100 ppm of iron from a 100 bbls/day well.
Iron counts obtained from wells producing in excess of
500 bbls./day must be viewed with caution because in such
wells severe localized corrosion can begin with a resulting
change of iron count of less than 1 ppm.

Chemical Analysis
In systems where large quantities of fluids are produced, the

volume of produced fluid should be taken into consideration.
Fluid volume usually increases over a period of time due to
increases in produced water or changes in well conditions.
Figure 6 shows a nomograph used to simplify the conversion
of iron count and fluid volume data into iron-loss data. To
obtain an iron loss of a sample, draw a straight line from the
sample's iron content to the production rate in barrels of water
per day. The intersection of this line with the iron-loss
nomograph line will give the number of pounds of iron removed
per day from the system. If, for example, a water sample has
5 ppm and its water production rate is 1,000 barrels per day,
then 1.8 pounds of iron per day will be removed from the
system, as shown in Figure 6. This information can then be
used either to detect changes in corrosion rates or monitor
inhibitor programs. Since a single iron count cannot indicate
any information concerning a system, it is necessary to
accumulate the iron count data over a period of time. This data
can be displayed in graphs to signal changes or trends. A
typical example of the presentation of iron activity is shown in
Figure 7.

Chemical Analysis
FIGURE 6. Iron-Loss Nomograph

Chemical Analysis
FIGURE 7. Iron Activity with Pertinent Operating Information
When evaluating iron results, there are many factors that should
be considered. For instance, at the start of inhibitor application,
the detergent effect of the inhibitor will tend to clean up
corroded surfaces in both sweet and sour crude wells. This
results in a temporary increase of iron, which is carried out of
the well by the produced fluid. It is not unusual for iron sulfides
to fall off the rods and tubing in such large quantities within a
week of inhibitor application that plugging of the bottomhole
pumps results. Usually, a well will clean up within one month of
inhibitor application to the extent that significant drops in iron
concentration will be observed.

Chemical Analysis
Case Study A
A well was batch treated for 1 month with an oil soluble inhibitor
“A”. The well experienced an average iron loss of 0.32 pounds
per day. For the next 4 months, this same well was treated with
inhibitor “B”. Its iron loss dropped to an average of 0.20 pounds
per day. During the next 4 months, the well was treated with a
third inhibitor “C”. The iron loss rose to an average of
0.53 pounds per day. These trends in iron content illustrate that
inhibitor “B” was the best choice of these three inhibitors for this
system.
Case Study B – Qurayyah Seawater Injection System
The world’s largest seawater flood system was commissioned

by Saudi Aramco in 1978 for pressure maintenance of the
Ghawar oil field. Water treatment is done at the Qurayyah
seawater treatment plant (SWTP). At the SWTP, water from
the Arabian Gulf is filtered, stripped of oxygen, and treated with
bactericide. This water is then pumped to the water injection
pump stations (WIPS) via the Udhailiyah Water Supply Station
(UWSS). From the WIPS the water is distributed to the
injection wells. The distance between the SWTP and the
injection wells can be as much as 150 kilometers. The
residence time of the water in these pipelines can range from a
minimum of 16 hours to a maximum of 48 hours. Figure 8 is a
sketch of the system.
Two major problems for this system are controlling corrosion

and minimizing solids generation (corrosion products or
biomass). Water samples are routinely drawn from various
points of the system. The increase in iron as the water flows
through the system is indicative of corrosion taking place and
correlates well with coupon corrosion rates taken at the same
locations. Figure 9 shows the iron count at the Qurayyah
SWTP, UWSS, WIPS, and injection wells over almost a 10-year
period. Note that the iron count reached a maximum during
1983-84 but has decreased in more recent years.

Chemical Analysis
FIGURE 8. Qurayyah Seawater Treatment and Injection System

Chemical Analysis
FIGURE 9. Iron Count at Various Locations

in the Qurayyah Seawater Injection System, 1981-89

Chemical Analysis
Bacterial Activity
In testing for bacterial contamination, sampling locations is

extremely important. Since these organisms tend to grow in
stagnant areas, it is very important to test areas such as tank
bottoms and low areas in lines. Bacteria can live in groups or
colonies attached to solid surfaces or suspended in water.
Bacteria attached to a surface are called sessile bacteria while
bacteria suspended in water are called planktonic bacteria. It
has been reported that in a typical system, there are 1,000 to
10,000 times as many bacteria attached to a surface as there
are floating in the water. It should be noted that the presence of
bacteria does not necessarily mean trouble. However, if the
bacterial counts show an increase with time or across a system,
there might be bacterial corrosion occurring.
Various techniques are available for the detection and counting

of bacteria colonies in the oil field. Several of these techniques
are shown in Figure 10.
FIGURE 10. Techniques Used to Detect Microorganisms (Sessile and Planktonics)

Chemical Analysis
Microscopic Techniques
The microscopic techniques include light (brightfield),

epifluorescent, and scanning electron microscopy. These
techniques are some of the easiest, fastest, and most precise
techniques available for the identification and counting of
bacteria. Typical microscopy (brightfield) is extremely useful to
trained microbiologists. The advantages of this type microscopy
are that it is inexpensive to operate, somewhat quantitative, and
the fact that both live and dead cells are observed. The major
difficulty with this type of microscopy arises from attempting to
distinguish bacteria from the surrounding nonmicrobial
materials. Certain stains have been used to distinguish
bacteria, but in many cases, these stains also react with the
other debris.
Another technique, called epifluorescence microscopy, results

from staining the bacteria with dyes that are fluorescent and
react specifically with molecules found only in bacteria. This
technique is fairly precise and quantitative. Examples of some
of these dyes are fluorescein isothiocyanate (FITC), which
reacts with proteins in the bacterial cells, and acridine orange
(AO), which reacts with nucleic acids in the bacterial cells. This
technique then allows the use of common brightfield microscopy
and the counting of bacteria rather than the surrounding debris.
When FITC is used, the bacteria can be seen as green against
a black background. However, this technique still does not
distinguish between living and dead bacteria and doesn’t help in
establishing the identity of the bacteria.
Both transmission and scanning electron microscopy have been

used to study bacterial corrosion. This technique is especially
useful when trying to determine if bacteria caused the corrosion.
In many cases, bacterial corrosion is verified when the attack
appears as a small entry point leading to a larger subsurface
cavity. Unfortunately, this technique requires that the test
samples be removed from the field site, the tests are done by
only well-trained personnel, and these tests are expensive to
perform.

Chemical Analysis
Culture Techniques
Culture techniques are probably the most widely used. The

sample is either diluted into a liquid medium, known as a
culture medium, or spread in an agar medium. Both media are
designed to grow bacteria. Specific bacteria, such as aerobic
and anaerobic, require specific media for growth. Since the
media have to be formulated for specific types of bacteria, it is
possible to identify bacteria by simply noting the media in which
growth occurred.
API RP-38 describes a serial dilution technique used to

determine the relative presence of bacteria in water. This
technique gives the range of bacteria present in colonies/ml
dependent on the number of medium bottles with positive
results. This technique has also been used with other media. It
is usually desirable to make up the test media by using a
sodium chloride solution that matches the total dissolved solids
(TDS) of the water of interest. Saudi Aramco typically uses the
appropriate field water as a base with the addition of nutrients
for the specific bacteria to be studied. For sulfate reducing
bacteria (SRB) media, the addition of a large amount of iron
(typically a nail) is also needed to turn the medium black in the
presence of H2S. This change of color from a clear medium to
black indicates the presence of SRBs. For general aerobic
bacteria, growth is indicated when the media turns cloudy.
Some cultures may contain phenol red, an acid-base indicator.
In those cultures, a color change from red to yellow indicates
aerobic bacteria growth.
This technique is also known as the extinction dilution technique

and is illustrated in Figure 11. The procedure for this technique
is the following:
1. Line up a series of serum bottles containing 9 ml of sterile

growth medium.
2. Inject 1 ml of the water sample into the first bottle and

shake well.
3. Withdraw 1 ml of solution from the first bottle with a

disposable sterile syringe and inject it into the second
bottle. Shake the bottle well. Throw the syringe away.

Chemical Analysis
4. Withdraw 1 ml of solution from the second bottle with a

new sterile syringe and inject it into the third bottle.
Shake the bottle well and throw the syringe away.
NOTE: Each bottle contains 9 ml of growth medium.
FIGURE 11. Extinction Dilution Technique
This procedure can be repeated for as many bottles as desired.

The goal is to dilute the sample to the point that the final 1 ml of
solution that is injected into the last bottle has no bacteria in it.
After inoculation, the bottles are incubated at a temperature

within 9 ∞F (5 ∞C) of the recorded temperature at sampling.
Again either changes in color or the occurrence of a cloudy
medium will indicate the presence and growth of bacteria.
Usually 3 days are required for the growth of aerobic bacteria,
while 2 weeks to a month may be required for sulfate-reducing
bacteria growth. The final reading for aerobic bacteria should
be taken after 7 days and for sulfate-reducing bacteria after
28 days.

Chemical Analysis
Interpretation of the results is best explained by referring to

Figure 11. If the bottles 1, 2, 3, and 4 become cloudy or turn
black while the remaining bottles remain unchanged, depending
on which bacteria is being studied, then there are 1,000 to
10,000 bacteria per milliliter in the original 1-ml water sample.
NOTE: If the first bottle of the SRB media turns black within
2 hours after injection, it is not the result of bacterial
growth in the bottle. Usually this condition signifies
that a high level of H2S in the water sample reacted
with the steel nail to form iron sulfide. If this occurs,
then continue observation on the other bottles.
In addition, if the first bottle of the aerobic bacteria

media turns milky within 1 hour of injection, this is not
due to bacteria, but the result of the natural turbidity
of the water.
Usually the absolute number of bacteria is less important than

the trends in growth. If the number of bacteria increases with
time at a given point or if it increases as the water moves
through the system, then bacterial growth is occurring. For
aerobic bacteria, counts of less than 10,000 bacteria per
milliliter are not considered significant. A count of 100,000 per
milliliter usually indicates a strong possibility of plugging. For
sulfate-reducing bacteria, the presence of one bacterium could
represent a problem. These bacteria are typically sessile and
will not be readily detected in a serial dilution technique. This
type of bacteria should be monitored closely and treatment
started if the sulfate-reducing bacteria counts or H2S levels
increase.
Serial (extinction) dilution technique is simple and convenient

for field use. It does not require sophisticated equipment, can
be performed in a reasonable amount of time, and requires
minimal training of personnel. Unfortunately, this technique
permits the estimation of planktonic bacteria only. A technique,
“Field Determination of Approximate Bacteria Populations in
Water” (modified from API RP-38), can be found in the Work
Aid section.

Chemical Analysis
There are several types of samples taken to determine the

amount of sessile bacteria.
• Surface sample swabbed off a coupon
• Water and solid samples obtained during scraping of

pipelines
• Samples obtained during facility shutdowns or other times

when the equipment is opened
The solids removed will be a combination of corrosion products

and biomass that will provide information on bacterial activities
on the metal surface. Bacteria are cultured in a substrate of
agar and the necessary nutrients. The culture media on plates
are inoculated with the water being tested. Visible colonies
develop as spots on the agar. By counting the number of
colony spots, the number of organisms per milliliter of original
water can be estimated.
One device to obtain sessile bacteria is through the use of the

Robbins device, a section of 1-inch diameter pipe with a series
of sampling ports located symmetrically around the pipe. Small,
sterile, steel coupons or studs are placed in these sampling
ports such that the face of the studs are flush with the pipe wall.
A sidestream from the system under test is then flowed through
the device. After a given exposure period, the studs are
removed and the number of bacteria on each stud is evaluated.
Figure 12 illustrates a Robbins device biofilm sampler. Another
design of a retrievable biological sample probe assembly is
shown in Figure 13. A schematic in Figure 14 shows a biofilm
sampling spool in place.

Chemical Analysis
FIGURE 12. Robbins Device Biofilm Sampler

Removable test surfaces (T) have 0.5 cm2 exposed to circulating fluid.
All dimensions are in centimeters.

Chemical Analysis
FIGURE 13. Biological Sample Probe Assembly

Chemical Analysis
FIGURE 14. Biofilm Sampling Spool in Place

Chemical Analysis
There are three methods commonly used to evaluate the

number of bacteria on these studs.
• Each stud is placed in a plastic test tube containing a

special solution and glass beads. Bacteria are then
dislodged by vigorous hand shaking of the tube for a few
minutes. The resulting solution is then evaluated by the
serial dilution method.
• Biofilms are scraped from the studs with a sterile blade.

The scrapings, the stud, and the blade are then placed in
a special solution and exposed to an ultrasonic cleaning
device. The resulting solution is then evaluated by the
serial dilution method.
• The bacterial population on the stud may be determined

by epifluorescence microscopy.
ATP
An additional technique for monitoring bacterial activity is the

use of bioluminescence, commonly called adenosine
triphosphate or the ATP method. This technique rapidly
determines the quantity of living organisms present in a water
and can be particularly helpful in the evaluation of bactericides.
This technique proceeds as follows:
1. ATP is found in the cells of all living organisms.
2. A chemical is added to the water sample, causing the cell

walls of the bacteria to burst and release their cellular
contents, including ATP.
3. An enzyme luciferase is then added to the solution. The

emitted light is measured with a photometer. The amount
of ATP per cell is proportional to the amount of light
released.
With this procedure, water is first filtered through a membrane

to remove the bacteria and other organisms. The ATP must
then be extracted. Typically the membrane filter is dropped into
a boiling water solution of 0.05 molar tris hydroxy nitromethane
buffer solution. The enzyme luciferase is then added to this
buffer solution. The emitted light is measured with a
photometer.

Chemical Analysis
A disadvantage of this technique is that the test is not specific

for a particular type of bacteria. Whether the bacteria are
aerobic slime or anaerobic sulfate reducing cannot be
determined with this method.
Radiotracer Techniques
Radiotracer techniques have been used to aid in determining

whether bacteria are alive. One of these techniques involves
feeding C14 to a bacterial culture and later separating the
separate cells from the unused glucose. Additional processing
would then determine how much of the C14 ended up in cell
material. By use of this technique, the relative amount of
bacteria can be determined.
Disadvantages of this technique include:
• License required to use radioactive materials
• Difficulty of transporting radioactive materials on public

transportation
• Difficulty and expense of disposal after use
• Expense of equipment
• Trained personnel needed
Case Study A –
Qurayyah Seawater
Injection System
The world’s largest seawater flood system was commissioned

by Saudi Aramco in 1978 for pressure maintenance of the
Ghawar oil field. Water treatment is done at the Qurayyah
seawater treatment plant (SWTP). At the SWTP, water from
the Arabian Gulf is filtered, stripped of oxygen, and treated with
bactericide. This water is then pumped to the water injection
pump stations (WIPS) via the Udhailiyah Water Supply Station
(UWSS). From the WIPS the water is distributed to the
injection wells. The distance between the SWTP and the
injection wells can be as much as 150 kilometers. The
residence time of the water in these pipelines can range from a
minimum of 16 hours to a maximum of 48 hours. Figure 8 is a
sketch of the system.

Chemical Analysis
Two major problems for this system are controlling corrosion

and minimizing solids generation (corrosion products or
biomass). Water samples are routinely drawn from various
points of the system.
There are five general steps used to maintain this system.
• Maintain an effective bactericide program.
• Adjust pH to below the scaling range.
• Maintain an oxygen-free system.
• Avoid stagnant and low velocity zones.
• Scrape the cross-country pipelines between the SWTP

and the WIPS.
It is essential to monitor the performance of this system in order

to detect potential problems and take effective action. In
addition, the costs of treatment can be minimized by monitoring
the effectiveness of the bactericide. Coupons exposed to
system conditions via access fitting and in side streams have
been used. Saudi Aramco uses these coupons for evaluation
of both sessile sulfate reducing bacteria and general aerobic
coupons as indicators of the performance of bactericides and
determining time-concentration requirements. These coupons
are placed in vials of deoxygenated, sterile system water and
sonicated to remove the solids. The resulting mixture is then
tested for both types of bacteria by the serial dilution technique.
Figure 15 shows the planktonic bacteria count of SRBs at the
UWSS from 1981-1990 while Figure 16 shows the sessile count
of SRBs at the UWSS for the same period. Note that the
bacterial count axis is not the same scale for both figures.
Figure 17 shows the planktonic count of SRBs at the Qurayyah
SWTP located upstream.

Chemical Analysis
FIGURE 15. Seawater SRB (Planktonic) Monthly Average – UWSS

Chemical Analysis
FIGURE 16. Seawater SRB (Sessile) Monthly Average – UWSS

Chemical Analysis
FIGURE 17. Seawater SRB (Planktonic) Monthly Average – Qurayyah

Chemical Analysis
Case Study B –
Sour Oil Field
An oil field has an average H2S and CO2 content of 0.1 and
4.3 mol percent respectively. Bottomhole temperature is about
230 ∞F (110 ∞C) while pressure is approximately 2,500 psig.
Since acidic sour water corrosion was anticipated, a downhole
chemical injection valve was installed in each of the wells as
part of the completion design. However, it was discovered that
a corrosion inhibition program was not sufficient to control
bacterial corrosion.
A leak occurred at a low spot in the line after less than six
months of operation. The corrosion rate for this failure was
estimated to be greater than 500 mpy. Production waters were
then tested per the API extinction dilution method. As shown in
Table 5, all of the sample points gave positive identification of
SRB.
TABLE 5. Extinction Dilution Test Results

Location Colonies/ml
First stage separator inlet 100 - 101
First stage separator water outlet 101 - 102
Test separator inlet 101 - 102
Test separator outlet 101 - 102
Second stage separator water outlet 101 - 102
Skimmer water outlet 102 - 103
Low pressure blowcase water 103 - 104
The production wells were determined to be the source of

bacteria. The formation was probably contaminated during
drilling. Biocides were then used to solve this problem. To
monitor this program, the API extinction dilution technique,
corrosion coupons, and ultrasonic thickness measurements with
occasional visual inspections were used.
After the first biocide had been used, coupons were retrieved to
study its effect. These coupons were heavily and deeply pitted,
containing pits within pits. A different biocide was then used
and coupons from this period showed only slight uniform attack.
For about 5 months, biocide treatment was halted. As a result,
pitting attack reappeared on the corrosion coupons.1
1“Sulfate Reducing Bacteria in Oil and Gas Production”, K. C. Lunden and T. M. Stastny, Corrosion 85, Paper 296

Chemical Analysis
Case Study C –
Water Injection System
In one field, approximately 35,000 barrels of produced water

and 7,000 to 8,000 barrels of supply water are handled per day.
This produced water is commingled at a central battery and
injected into 18 system wells. Production is by gas lift.
Many corrosion failures occurred in the producing wells over the

years with the main cause being oxygen in the gas-lift gas. A
vapor recovery unit in the gas gathering system, which was a
major source of oxygen, was removed from service. While the
downhole corrosion rate dropped significantly, severe corrosion
continued in the water injection system. Deposits from the
water injection system indicated the presence of oil-wet iron
sulfide, and an increase in the amount of dissolved H2S was
noted. An anaerobic environment created by the elimination of
oxygen stimulated the growth of SRB. Corrosion related
failures in the water injection system increased and severe
buildup occurred in the injection lines, reducing the internal
diameter of the surface injection lines by 50 percent.
Despite these problems, SRB cultures of planktonic bacteria

indicated negligible numbers. On the other hand, examination
of coupon and pipe wall deposits by epifluorescent microscopy
indicated the presence of sessile SRB in abundance. This
discrepancy led to using cultures made from the specific field
water. The field water was sterilized and used for making both
aerobic and anaerobic media after supplementing with
appropriate nutrients. These prepared medium bottles were
then injected with field water.2
2“Solving Problems Associated with Biocorrosion in Oil Production Operations”, R. Prasad et al, Corrosion 89,
Paper 184

Chemical Analysis
As shown in Table 6, at least 1,000 cells/ml of planktonic SRB

were detected by the specific field water medium, whereas the
API method detected none.
TABLE 6. Detection of Planktonic and Sessile SRB

Using API and Specific Field Water Medium
API Medium Field Water Medium
Bacteria Aerobic SRB Aerobic SRB
Planktonic 0 - 10 0 ε 10 3 ε 103
Sessile 0 - 10 0 ε 102 ε 102

Chemical Analysis
WORK AIDS
REFERENCE TABLES
AMOUNT OF H2S TO REACH NACE LIMIT (0.05 psia)

psia Mol Fraction ppm percent
250 0.0002 200 0.02
500 0.0001 100 0.01
1,000 0.00005 50 0.005
2,000 0.000025 25 0.0025
5,000 0.00001 10 0.001
10,000 0.000005 5 0.0005
20,000 0.0000025 2.5 0.00025
EFFECT OF PARTIAL PRESSURE

OF CO2 ON CORROSION
0 - 7 psi Mild corrosion
7 - 30 psi Moderate corrosion
> 30 psi Severe corrosion
HYDROGEN SULFIDE LENGTH-OF-STAIN DETECTOR TUBES
Performance
Measuring range 1.25 to 150 ppm
Sampling time 3 to 12 minutes (1 to 4
pump strokes)
Color change White to dark brown
Sensing limit 0.3 ppm
(The minimum
detectable concentration
although not precise)

Chemical Analysis
SAMPLING AND MEASUREMENT
Gas Detector
1. Break tips of a fresh detector tube by bending each tube

end in the tube tip breaker. Insert the tube end, marked
with a red dot, securely into pump inlet as shown in the
above figure.
2. Align the guide marks (red dots) on shaft and back plate
of the pump. Pull the handle one full stroke then turn it
90∞ to the locked position. Wait 3 minutes.
3. Remove the detector tube from the pump inlet when the
sampling is completed. Position interface between the
reagent and end plugs on the line O and X of the
concentration chart. Read the concentration (C) at the
top of the length of the stain.
4. When concentrations are outside the scale range, use

multiple (2 to 4) pump strokes to determine these lower or
higher concentrations. Use the following formula to
determine true concentration.
1
True concentration = Measured value ∞ Number of strokes
NOTE: When the top of the stained layer is not perpendicular

to the length of the tube, read the concentration at the
center between the longest and shortest points of the
stained layer. The total stain length should be read
regardless of color variations.

Chemical Analysis
TEMPERATURE, HUMIDITY, AND ATMOSPHERIC PRESSURE CORRECTION
• No temperature correction is necessary between 0 ∞C (32

∞F) to 40 ∞C (104 ∞F).
• Relative humidity less than 80% (30 ∞C, 86 ∞F) requires

no correction.
• Use the following formula to correct measurements for

atmospheric pressure.
760 mm Hg
Corrected concentration = Measured value ∞ Air pressure (mm Hg)
INTERFERENCES
• Presence of more than 12 ppm of sulfur dioxide and more

then 550 ppm of mercaptans causes a higher reading.
• Presence of more than 2 ppm of nitrogen dioxide causes

a lower reading.
HAZARDOUS PROPERTIES OF HYDROGEN SULFIDE
• TLV*: 10 ppm
• Explosive range in air: 4.3% to 45%
CHEMICAL REACTION IN DETECTOR TUBES
H2S + Pb(CH3COO)2 ––––> PbS + 2CH3COOH
NOTE: Before testing, the pump should be checked for

proper performance. Leakage of air and varying flow
rates will affect the accuracy of readings.
* Threshold Limit Value established by the American Conference of Governmental Industrial Hygienists, 1978.

Chemical Analysis
FIELD METHOD FOR DETERMINATION OF

IRON (FERROUS) IN SWEET OIL-FIELD WATERS
Direct determination of dissolved iron in water can be made at

the wellhead or separator.
Apparatus
• 100-ml graduated cylinder
• 250-ml Erlenmeyer flask
• 5-ml graduated pipette
Solutions
• 0.01 normal potassium dichromate
• Indicator and acid mixture
The indicator solution is made up by dissolving 0.15 grams of

sodium diphenylamine-p-sulfonate in a quantity of water and
then diluting to 60 ml with distilled water. The acid solution is
made up by mixing 150 ml of sulfuric acid (sp. gr. 1.84) and 150
ml of phosphoric acid (sp. gr. 1.7) and then diluting to 1 liter with
distilled water.
Procedure
The collection of a fresh sample is critical. If collected from the

separator, the separator should first be drained of all water, and
then a fresh sample of water collected. The determination of
iron can either be made immediately upon obtaining the sample
or within a 16-hour period, if the acid mixture is added as soon
as the sample is taken.
To 100 ml of water measured in the 100 ml-cylinder, add

approximately 1 ml of the indicator solution and 15 ml of the
acid solution. Titrate the water with the potassium dichromate,
adding it dropwise from the pipette, gently swirling the flask
through the test. The end point is reached when a permanent
purple color is obtained.

Chemical Analysis
Calculation
The number of milliliters of 0.01 normal* potassium dichromate

added, multiplied by 5.6, is the iron (ferrous or soluble) content
in parts per million (ppm).
If the iron content of the sample is zero, no purple color or end

point is reached.
Another method suitable for field analysis for determination of

iron may be found in the appendix of the NGAA book,
Condensate Well Corrosion.
*If the iron content is high (above 25 ppm), 1/10 normal potassium dichromate may be used. The factor 5.6 then
becomes 56.

Chemical Analysis
Iron-Loss Nomograph

Chemical Analysis
NOTE: Each bottle contains 9 ml of growth medium.
Extinction Dilution Technique

Chemical Analysis
REFERENCE
LIST OF ARTICLES
• R. G. Rydell and W. H. Rodewald, “Iron in Oil Technique

as a Corrosion Control Criterion”
• Robert E. Tatnall, “Fundamentals of Bacteria Induced

Corrosion”
• E. Y. Chen and R. B. Chen, “Monitoring Microbial

Corrosion in Large Oilfield Water Systems”
• E. J. Dewar, “Control of Microbiologically-Induced

Corrosion and Solids Accumulation in a Seawater Flood
System”
API RECOMMENDED PRACTICES
• Analysis of Oil-Field Waters (Iron Determination Section,

API RP-45)
• Field Determination of Approximate Bacteria Population

in Water (Modified from API RP-38)

Chemical Analysis
GLOSSARY
aerobic A condition in which bacteria will grow in or on the

surface of a simple solid medium exposed to air
agar A plant extract with properties similar to gelatin
ampoule A sealed glass vessel for holding solutions that must be

kept absolutely free from contact with air
anaerobic A condition in which bacteria will not grow in or on the

surface of a simple solid medium freely exposed to air
bacteria Unicellular microscopic organisms found in soil, water,

air, foods, and the skin
buffer Solution that has constant pH values and the ability to

resist changes in that pH level. Buffers are used to
calibrate pH meters.
colorimetric Related to a technique for determining the intensity of

colors
ion An electrically charged particle that allows electricity to

pass through solutions
iron count Concentration of iron in solution that is usually

considered a measure of the corrosion rate
medium Specific environment used to grow bacteria
nomograph Table of data where two know parameters are connected

by a straight edge to determine an unknown parameter
partial pressure Mole percentage of gas multiplied by the total pressure
pH Measure of a solution’s acidity; - log [H+]
planktonic Floating in the water
Robbins device A section of pipe with a series of sampling ports located

symmetrically around the pipe. Steel coupons are placed
in these sampling ports and allowed to build up biofilms

Chemical Analysis
sessile Fixed or attached to a surface
titration Testing where the amount of reagent needed to reach a

certain visual standard is related to the concentration of a
specific ion

Chemical Analysis

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Engineering Encyclopedia

Saudi Aramco DeskTop Standards

Chapter : Corrosion For additional information on this subject, contact

Saudi Aramco DeskTop Standards i

Sampling And Measurement ............................................................................ 54

FIGURE 1. pH Values of Common Processes and Products..................................... 12

FIGURE 3. Oxygen Analysis – Colorimetric Kit .......................................................... 20

Saudi Aramco DeskTop Standards ii

FIGURE 9. Iron Count at Various Locations

TABLE 1. Hydrogen Ion Concentration in Moles/Liter at 25 C .................................. 10

TABLE 4. Effect of Partial Pressure of CO2 on Corrosion ......................................... 17

TABLE 5. Extinction Dilution Test Results.................................................................. 50

Saudi Aramco DeskTop Standards iii

Chemical analysis is an essential part of a corrosion monitoring

The condition of an oil field production system is constantly

• Most oil field systems are based on once-through flow.

• Deposits in the system that build up in stagnant or low

• Few oil field sources supply fluid of constant composition.

Saudi Aramco DeskTop Standards 4

The critical part of any chemical analysis testing is obtaining a

The sample must be representative of the material of interest or

Never use a metal container or a metal cap. The water will

If a sampling valve is available, connect a piece of plastic tubing

Saudi Aramco DeskTop Standards 5

Access to the System

Usually hot tapping and welding of access points not in the

• Water source wells

• Upstream and downstream of filters

• In flowline downstream of well head, located far

• Gas lift wells

• Install from side of line if water level permits.

• If this is not possible, install from bottom of line.

• Avoid dry exposure at top or sand erosion at the

• Water injection stations

Access points should be located between pieces of

• Water injection wells

Access points should be located in straight sections – but

Saudi Aramco DeskTop Standards 6

• In flowline near well head with the sampling done

• Not too close to the well head or a valve so as to

• Oil flow stations

• Bottom of incoming pipelines or headers

• Drain line of three-phase separators upstream of

• Tank bottoms/surge tank bottoms

• Drain lines of desalters/heater treaters upstream of

• Gas outlets from two-phase separators to

• Gas main to compressors (vertically down from near

• Close to bottom of tank, typically 0.5 meters from

• Not in downcomer inside tank or any other static

Saudi Aramco DeskTop Standards 7

TYPES OF CHEMICAL ANALYSIS

Several chemical analysis methods are available for assessing

• Water analysis – To determine the variations in ion

• pH – To monitor and adjust the degree of acidity for use in

• Deposit analysis – To determine the composition of

• Residual chemical – In certain cases, to determine the

• Gas analysis – In most cases, to determine concentration

• Oxygen analysis – To determine the content of dissolved

• Iron count – In most cases, to monitor inhibition programs

• Bacterial activity – To determine the activity of various

Saudi Aramco DeskTop Standards 8

Periodic analyses of water samples can indicate changes in

The chemical and physical properties of a water are greatly

On-site analysis of certain ions is desirable. Reactions can