SPE 94707

Accurate Measurement of the Hydrogen Sulfide Content in Formation Fluid

SamplesCase Studies
H. Elshahawi, SPE, and M. Hashem, SPE, Shell Intl. E&P Inc.
Copyright 2005, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2005 SPE Annual Technical Conference and
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Abstract
The Hydrogen Sulfide (H2S) content of subsurface
hydrocarbon reservoirs has a profound impact on completion,
surface production, and process design. The H2S content of
crude oil directly impacts the sale value of the produced
hydrocarbons, while the H2S content of produced water can
result in significant production problems, which can lead to
detrimental effects on hydrocarbon transport and sales
specifications.
In theory, the H2S content of reservoir fluids can be
determined from samples collected by wireline formation
tester tools. In practice, however, measurement is complicated
by the partial-to-total loss of the gas by absorption/adsorption
onto the metal components of the downhole tool, storage
bottles, and transfer/analysis system, particularly those made
from iron. H2S readily forms non-volatile and insoluble metal
sulphides by reaction with many other metals and metal
oxides, and analysis of the fluid samples can therefore
underestimate the true H2S content. Therefore, many practical
challenges must be overcome to accurately determine H2S
levels in formation tester samples. These include metallurgical
design considerations, sampling environment and system
selection as well as the timing and type of H2S analyses.
This paper details our successes in accurately measuring both
high and low concentrations of H2S in downhole formation
tester samples. It describes an integrated workflow by which
ultra low H2S concentrations can be captured and preserved in
formation tester samples until the tool is brought back to
surface where the samples can be analyzed. This workflow
includes a number of modifications to some commercial
formation tester tools and sample chambers to ensure that the
bulk of the H2S does not get absorbed by the time the tool
arrives to the surface. Downhole measurements made close to

the fluid entry into the sampling tool are used to cross check
and verify the surface measurements. Finally, on surface, a
number of techniques are used to measure H2S concentration
in the sample bottles as soon as practical after the formation
tester tool is brought to the surface. The paper demonstrates,
through a number of case studies, that by following this
comprehensive workflow, it is possible to capture and analyze
hydrocarbon samples with minimal loss of H2S, regardless of
the levels of H2S being measured.
Introduction
The presence of Hydrogen Sulfide (H2S) in the reservoir fluid
has a major effect on project economics as well as
occupational health, safety, and environment (HSE). The
accurate measurement of H2S concentrations in the reservoir
fluids is critical to the design of completion, surface, and
production facilities. With accurate determination of H2S
levels in the subsurface, the operator can hope to:
- Determine which (if any) HSE measures must be
implemented for dealing with H2S at the various stages of
exploration, appraisal, development, production, and
abandonment of a given prospect.
- Indicate the need for special metallurgical or process design
to deal with certain levels of H2S in the presence of various
other mitigating or accentuating factors.
- Detect the onset and evolution of reservoir souring upon the
implementation of water injection or other enhanced recovery
techniques.
The measurement of H2S concentrations in samples collected
by formation testers is complicated by the partial-to-total loss
of the gas by reaction of the metal components and the
drilling/completion fluids. Many practical challenges must be
overcome to accurately determine H2S levels in formation
tester samples. These include metallurgical design
considerations, sampling environment and system selection as
well as the timing and type of H2S analyses required.

Sources of H2S in the subsurface

Reservoir souring is quite prevalent in the oilfield. It is due to
uncontrolled activity of reservoir resident sulfur reducing

bacteria SRBs, which are capable of reducing sulfate to

sulfide. It occurs in all subsurface habitats that are conducive
to SRB growth, predominantly but not exclusively in fields
under seawater flooding. Scott et al. (1993) discussed the
formation of hydrogen sulphide by the action of SRB in oil
wells which co-produce waters containing high sulphate
concentrations. Some 70% of water-flooded reservoirs
worldwide have turned sour. The effect of souring typically
becomes noticeable when traces of H2S start appearing in
produced gas, on or closely behind the breakthrough front of
injected water.
The abundance of H2S in subsurface hydrocarbon reservoirs
results primarily from interactions between the ubiquitous
sulphate reducing bacteria and exogenous sulphate under
anaerobic conditions. Altogether there are three main
mechanisms responsible for H2S generation in petroleum
reservoirs:
1) Bacterial Sulfate Reduction
This reaction is mainly anaerobic and tends to occur at low
temperatures (lower than 80C) and is often triggered by
injection of seawater, which tends to be rich in sulfates. The
H2S concentrations generated are usually less than 5%, and
the chemical reaction takes the following form:
Sulfates + Organics + Nitrogen H2S
2) Theromochemical sulfate reduction (TSR)
TSR occurs primarily in carbonate reservoirs that are deficient
in iron and at temperatures above 100C. The H2S
concentrations generated are usually greater than 10%, and the
chemical reactions take one of the following forms:
Gas + Anhydrite H2S + Carbonate
Calcium Sulfate + Organic Material H2S + CaCO3
3) Thermal cracking
In these reactions, the H2S is generated by the thermal
alteration of the sulfur in the kerogen and occurs at
temperatures higher than 140C. The concentration of
thermally sourced H2S tends to increase with temperature, and
the H2S concentrations generated are usually less than 5%
(Hland et al., 1999).
The most common reaction products of BSR and TSR are
identical and include carbonate material, sulfides (usually as
base, or transitional metals, sulfur, H2S, and sulfurized or
oxidized hydrocarbons).
Although knowing the different potential sources of H2S
generation are critical in quantifying the abundance of H2S in
a given reservoir, understanding the processes leading to
removal of H2S from the system (e.g. reactions with iron if
available to form iron sulfides) is equally important.
Importance of Measuring H2S concentrations
H2S is an extremely hazardous, toxic compound that occurs in
a number of natural and industrial environments. Naturally, it

SPE 94707

can be found in coal pits, sulfur springs, gas wells, and as a

product of decaying sulfur-containing organic matter,
particularly under low oxygen conditions. Industrial sources of
H2S include petroleum and natural gas extraction and refining,
pulp and paper manufacturing, rayon textile production,
leather tanning, chemical manufacturing and waste disposal.
H2S is a colorless, flammable gas. It is approximately 20%
heavier than air and so tends to collect in depressions and
confined spaces in the ground. It has a very low odor
threshold, with its characteristic rotten egg smell easily
perceptible at concentrations well below 1 ppm in air. The
odor increases as the gas becomes more concentrated, with the
strong rotten egg smell recognizable up to 30 ppm. Above this
level, the gas is reported to have a sickeningly sweet odor up
to around 100 ppm. However, at concentrations above 100
ppm, a person's ability to detect the gas is affected by rapid
temporary paralysis of the olfactory nerves in the nose,
leading to a loss of the sense of smell. This means that the gas
may be present at dangerously high concentrations yet have no
perceivable odor. Prolonged exposure to lower concentrations
can also result in similar olfactory paralysis effects. Because
of this unusual property of H2S, it is very dangerous to rely on
the sense of smell to warn of the presence of the gas.
H2S is classified as a chemical asphyxiant, similar to carbon
monoxide and cyanide gases. It inhibits cellular respiration
and uptake of oxygen, causing biochemical suffocation.
Typical exposure symptoms include: Irritation of the eyes,
nose and throat (0 -10 ppm); headache, dizziness, nausea and
vomiting, coughing and breathing difficulty (10 -50 ppm);
severe respiratory tract irritation, eye irritation, acute
conjunctivitis, shock, convulsions, coma, and death in severe
cases (50-200 ppm). Prolonged exposures at lower levels can
lead to bronchitis, pneumonia, migraine headaches, pulmonary
edema, and loss of motor coordination (JPT Forum, 1971).
The presence of H2S in produced fluids can give rise to
critical safety problems. The exposure limit recommended by
the US National Institute for Occupational Health is 10 ppm
per 10 minutes of exposure, and most countries have legal
limits in force that govern the maximum allowable levels of
exposure to hydrogen sulfide in the working environment. The
only reliable way to determine exposure levels is to measure
the amount in the air. The human nose can detect
concentrations as low as 0.02 ppm with maximum sensitivity
at around 5 ppm and becomes increasingly unable to detect
H2S at concentrations of 150-200 ppm. Detection limits below
about 5 ppm are therefore desirable. Wherever possible,
exposure should be minimized by employing adequate
engineering controls and safe working practices. Where these
cannot adequately control levels of exposure, it may be
necessary to supplement them with the use of suitable personal
protective equipment (PPE) such as supplied-air respirators
(JPT Forum, 1971).
Typically, the sulphur content of crude oils is in the range 0.30.8% by weight and the H2S content of natural gas is in the
range of 0.01-0.4% by weight, but concentrations of H2S in
natural gas of up to 30% by weight have been reported

SPE 94707

(Carlson at al., 1996). There appears to be a systematic

increase in the sulphur content of crude oils over the past 1020 years and further increases in the concentration of
hydrogen sulphide in both oil and natural gas are anticipated.
Hland et al. (1999) report a correlation between the H2S
concentration of produced hydrocarbons from the Norwegian
continental shelf and reservoir temperatures in which the H2S
content of produced hydrocarbons is negligible below 110C
and increases exponentially with temperature above that
temperature.
Overall, it has been estimated that H2S alone is responsible for
about 20% of metal corrosion losses in the petroleum industry.
Sulfide stress cracking (SSC) is a form of hydrogen
embrittlement that occurs when a susceptible material is
exposed to a corrosive environment containing water and H2S
at a critical level of applied or residual tensile stress. SSC is
commonly observed in high strength or high hardness steels in
which the hydrogen is generated by the sulfide corrosion
process on the metal surface making the steel less resistant to
breakage and generally much weaker in tensile strength (Kane
et al., 1998). On a molecular level, hydrogen ions work their
way between the grain boundaries of the steel, where
hydrogen ions recombine into molecular hydrogen, taking up
more space and weakening the bonds between the grains. The
formation of molecular hydrogen can cause sudden metal
failure due to cracking when the metal is subjected to tensile
stress (Wilhelm et al., 1986).
To address the problem of hydrogen embrittlement, emphasis
is placed on controlling the amount of residual hydrogen in
steel, controlling the amount of hydrogen pickup in
processing, developing alloys with improved resistance to
hydrogen embrittlement, developing low or no embrittlement
plating or coating processes, and restricting the amount of insitu hydrogen introduced during the service life of a part. H2S
reacts with Fe from tubulars, valves, etc. to form iron sulfide
or "black water". It is important to note that in the last decade,
there has been a move away from chemical inhibition due to
environmental & engineering limitations (Williams, 2003).
The National Association of Corrosion Engineers (NACE) has
established guidelines for dealing with H2S in industrial
applications. The NACE Material Requirement standard
MR0175 defines the lower limit for sour service conditions in
which sulfide SSC could occur as 0.0003 MPa or 0.05 psia
partial pressure. Where partial pressure is defined as the
product of absolute pressure and concentration (Fig.1). For
example, 10 ppm of H2S at 16,000 psi is equal to a partial
pressure of (10/1,000,000)X16,000 = 0.16 psi-partial pressure.
There are actually quite a number of factors, other than H2S
partial pressure, that affect the susceptibility of a material to
sulfide stress cracking. Corrosion rates depend on H2S and
CO2 PP, pH, sand and water production, tubular metallurgy,
heat treatment, corrosion-inhibitor treatments, temperature,
fluid velocity, flow regime, etc (Tuttle, 1990 and NACE
2003). NACE MR0175 paragraph 1.3 lists the following
factors:
-Chemical

composition,

strength,

heat

treatment

and

microstructure of the material. Certain compositional elements

(for example, nickel in steels) have been identified as SSC
promoters. In general, for a particular alloy, as strength and
hardness increase, the susceptibility to sulfide stress cracking
increases.
-Hydrogen ion concentration (pH) of the process environment
(Fig. 2).
-Total tensile stress (accounting for both applied and residual
stresses).
-Process temperature.
-Exposure Time.
Accurate measurement of H2S concentration in sampled fluid
is critical to completion, surface production, and process
design. The impact on the cost structure is potentially huge.
As Fig.3 illustrates, typical completion costs increase by at
least one order of magnitude as we move from carbon steel
through 13-chrome to high Ni alloys (Kermani, 1995)
In theory, the H2S content of reservoir fluids can be
determined from samples collected by wireline fluid sampling
tools such as Schlumbergers Modular Dynamics Tester or
equivalent sampling tools. Fluid samples are usually collected
in metal containers, which can be maintained at Pressurevolume temperature (PVT) conditions that can be directly
compared to those at which the samples were collected.
However, the problem associated with sampling fluids
containing H2S is the partial-to-total loss of the gas by
reaction with components, particularly those made from ironbased metals. The H2S gas readily forms non-volatile and
insoluble metal sulphides by reaction with many metals and
metal oxides, and analysis of the fluid samples can therefore
underestimate the true H2S content.
Existing H2S Measurement Methods
The following methods exist for measurement of H2S in
hydrocarbon samples. Often, none of these is sufficient on its
own to provide a reliable measurement in low H2S
concentrations.
1) Conventional open-hole sampling: Taking samples in
openhole environments using formation testers has been
carried out for years. High quality PVT samples are
achievable with single-phase samplers in Low-shock mode,
and sample bottles have been successfully coated with both
PTFE and Sulfinert for sometime. However, because of the
several other potential sources of H2S loss in the flow paths
and pump as well as to the water used to fill the dead volumes
of the sampling chambers, open-hole sampling for the
determination of low-level H2S concentrations has until
recently been considered challenging at best. A combination
of lab testing, material improvements, and procedural changes
has enabled us to transform openhole sampling into the
method of choice for H2S sampling. Part of the improvement
has come from switching to a novel sampling technique
termed reverse-low shock sampling which avoids passing
the fluids through the pump altogether (Fig. 4). This will be
discussed in more detail later. Another part of the
improvement is the successful testing of the practical limits of

the tools with better coating and preparation for H2S

sampling.
2) Surface well testing: Surface separator PVT sampling is
another option for H2S analysis. Hence there is a large
potential for H2S in the produced fluids to react with the
metallic surfaces of the completion/DST string, surface testing
flow lines and/or test separator. Scavenging by the mud or
completion fluids and partitioning of the H2S into the various
phases is also likely. All this can lead to a large undetermined
loss of H2S by the time the produced reservoir fluids reach the
sample bottle. During extended well tests, where large
quantities of fluid are flowed, stability in H2S levels may be
achieved although cannot be guaranteed, especially for low
H2S concentrations. Onsite analysis during an extended well
test has the advantage of repeated measurements with large
volumes of liquid and gas to analyze.
3) Cased hole sampling: Capturing down-hole samples in a
cased-hole environment has advantages over the previously
mentioned methods. Down hole samplers can be positioned
very close to the reservoirs perforated intervals so scavenging
of H2S through contact with completions and surface
equipment is virtually eliminated. Down hole samplers can be
fired when the well is fully conditioned. This means highly
representative or fresh reservoir fluids can be captured for
analysis. The use of single-phase samplers avoids partitioning
of trace components between phases and allows controlled
flashing of the sample to obtain accurate measurements of
H2S in the gas, oil and water phases.
4) H2S coupons: H2S coupons are made of certain metal
alloys that corrode or discolor as a result of corrosion solely
due to the presence of H2S. The H2S coupon holder is a dropin replacement for the resistivity cell in the Schlumberger
MDT single probe module (Fig.5).

SPE 94707

5) H2S electrochemical sensor: This sensor is capable of

continuously detecting and measuring the H2S concentration
as the fluid is extracted from the formation into the sampling
tool. The sensor device is deployed along the flowline
immediately behind the probe to minimize reactive loss of
H2S. It is based on a molecular reaction system developed by
Oxford University, involving an electrochemical catalysis
mechanism in which the concentration of H2S is proportional
to the magnitude of a current function generated at the surface
of a diamond electrode (Parrillo et al., 1997). The sensor is
interfaced with the fluid flowline using a gas permeable
membrane, through which gas species dissolved in formation
oil such as methane, carbon dioxide together with hydrogen
sulfide will be allowed to enter the reaction chamber, but the
system is so specific that only the target species (H2S) will
trigger the specific chemical reaction and lead to the signal
output. The current design of the H2S sensor design is
probably sensitive to target species up to 100 ppm in
concentration.
Sampling and Measurement of Low level H2S
As mentioned before, it is a challenge to accurately measure
low (ppm) levels of H2S in formation fluids based on analysis
of formation tester samples. Many practical challenges must
be overcome to accurately determine H2S levels in formation
tester samples. Four key areas need to be addressed in order to
achieve this goal:
1. Metallurgical modifications and non-reactive coating
2. Sampling environment and system selection
3. Downhole Measurements
4. Timing and type of fluid analysis
By following a systematic approach, it is possible to capture
and analyze samples with very minimal loss of H2S.
Metallurgical modifications and non-reactive coating

From a visual inspection of the coupons upon retrieval to the

surface, it will be possible to tell if they have been exposed to
H2S. The discoloration results in a loss of the original shiny or
glossy finish. The metal turns brown, gray, or black, with a
flat matted finish.
A) The most sensitive coupon will turn black when exposed to
H2S in levels less than 0.005 psi partial pressure. This is 10
times less than the NACE corrosion limit, but is high enough
for human safety problems.
B) The mid sensitivity coupon will turn more of a brown color
when exposed to H2S levels in the 0.018-0.025 psi partial
pressure range. This is just below the level at which significant
sulfide stress cracking (a form of corrosion) will occur, but a
level at which there is a lethal health risk.
C) The least sensitive coupon will turn a brown color when
exposed to H2S levels in the 0.05-0.10 psi partial pressure
range. This is enough H2S to require special chrome alloy
materials to prevent sulfide stress cracking which then leads to
material failure.

Trace elements such as H2S, mercury or mercaptans are

known to react with the stainless steel walls of the sampling
tools and transportation cylinders. Even after a short period of
contact, without special precautions, a significant proportion
can be adsorbed on exposed metal surfaces, and the H2S will
not be detected at the correct level in field or laboratory
analysis. If, on the other hand, the reservoir fluid, were to
contain high levels (percentage levels) of H2S, then the metals
will remove a relatively small part of the H2S, such that the
lab analysis will still find high levels of H2S. In either case,
without truly effective and reliable non-reactive sample
transfer and analysis equipment, the accurate determination of
H2S is not possible. By implementing a holistic combination
of tool modifications, procedural changes, and improved
measurement techniques, it is possible to reduce H2S
scavenging levels to a levels close to nil and to preserve low
(ppm) levels of H2S until they are accurately and reliably
measured on surface.
Ideally, sample bottles should be made of an inert material,
but such materials are generally quite expensive. The Baker
Atlas RCI sample bottles are made of NP-35N, which is

SPE 94707

unique in its ultra low H2S absorption, but other commercially

available sample bottles, including the Schlumberger MDT
and Halliburton RDT chambers are typically made of Monel
steel or Inconnel which are not as inert. Special materials can
be used for bottle coating in order to render these types of
bottles inert or non-absorbing to H2S. A number of nonreactive surface coating technologies have been developed
over the last 5 years. These coatings allow standard sampling
bottles to be converted to non-reactive ones that can be used to
capture and store representative samples for H2S and other
sulphur compound analysis. PTFE derivatives have been used
for coating in the past with demonstrated efficacy. A sample
of 40ppm of H2S concentration introduced into a PTFEcoated bottle can generally be recovered after a typical
bottom-hole sampling cycle with a level of 38ppm. This
compares favorably with losses of 40% or worse if no special
precautions are taken. The main drawback of PTFE coatings is
that they do not survive multiple uses and that they are
rendered essentially ineffective by excessive friction with the
sampling and/or agitation piston(s).
Silicon-based coatings are the latest generation of non-reactive
coatings offering enhanced characteristics, even compared to
PTFE-derived coatings. Silicon-based coatings display a very
high level of inertness to H2S comparable with PTFE coatings
and have the advantage of being more durable. While singlelayer silicon-based coatings (e.g. Resteks Silcosteel coating)
already offer low ppm sulfur sample storage advantages over
PTFE coatings, multi-layered silicon-based coatings, such as
Resteks Sulfinert, are even more inert. The non-reactive layer
is integrated into the lattice of the sampling equipments steel
surface offering considerably improved durability. This fact,
along with increased hardness, dramatically improves the
reliability of a Sulfinert coating over its service life.
Independent laboratory tests confirm that Sulfinert multilayered silicon-based coating is effective with 98% retention
of approximately 50 ppm by volume H2S concentration after 6
days of sample storage (Fig. 6).
Sampling environment and system selection
The materials used in formation testers will react with H2S in
the flowing fluid from the formation. As a result, when a fluid
sample is subsequently analyzed, the measured concentration
of H2S is artificially depressed. If the original concentration in
the reservoir is sufficiently low (tens of ppms), the sampled
fluid may have no measurable H2S left. Many formation tester
tools make use of H2S-resistant materials that prevent the
formation of microcracks, which would otherwise weaken the
metal, but these materials may still react with the H2S. In
other words, inert materials are always H2S-resistant, but the
reverse is not always true.
The internal flow line is another item that warrants attention.
The internal flowline of formation testers is typically one-fifth
to one-quarter of an inch in internal diameter and is made of
Monel-K-500, Titanium, or Aluminum-Bronze. In a typical
formation tester tool string, the fluid may travel across a total
of 20-40 square inches of flowline at a relatively constant rate
of around 1 liter/minute while pumping. It has been shown by

experiments that both titanium and Inconnel are largely nonreactive compared to Monel, which is very reactive and allows
only a small fraction of the H2S (typically less than 20%) to
pass through. Elastomer seals can also contribute to H2S
adsorption, but are rather slow to soak up the H2S, and hence
are not a problem as long as pumping is fast enough and is
continued for sufficiently long period.
The pumping unit is the biggest culprit when it comes to H2S
absorption. Fluid movement across the internal surface of the
pump is intermittent. Typically, fluid is withdrawn into one
side of the pump in about half a minute while it is being
pushed out of the other, and then the sequence is reversed for
another half minute. Depending on when the fluid enters and
exits his leads to an average residence time of half a minute. In
Schlumbergers MDT Modular Dynamics Tester, the pump
displacement unit has a Monel K-400 surface area of slightly
over one hundred square inches and an Aluminum-Bronze
surface area roughly a quarter of that in addition to a magnet
used for switching the displacement unit travel direction. This
arrangement will generally scavenge upwards of 30% of low
H2S concentrations (less than 50 ppm) within the half-minute
average residence time (Fig.7).
To decrease the scavenging of H2S in the tool, non-reactive,
or inert, materials must be used. In our test well, the primary
sampling probe is equipped with a special flow line linkage
material. Parts especially made of Inconel or coated with
Sulfinert are used to replace certain components of the tool,
ordinarily made of Monel, that are in the flow line or
otherwise in the path of the fluid as it travels from the
formation to the sample bottle. Bottle coating also does not
address the problem of scavenging in the pump itself, which is
the major H2S scavenger in the tool and which cannot
generally be coated. To circumvent that problem, a dedicated
multi-sample module is placed immediately below the bottom
probe and used to sample the zones suspected of containing
H2S. The bottles in this multi-sample module are filled against
a water cushion rather than not using the conventional Low
Shock technique. A dedicated pump is used below the multisample module to pump the water cushion out and into the
wellbore in a controlled fashion, thus avoiding scavenging of
the H2S in the pump. Using this method, termed reverse low
shock sampling, control of the flow regime and prevention of
phase segregation upon retrieval to the surface are as good as
with conventional low shock sampling (Fig.4).
Downhole Measurements
H2S coupons and/or downhole H2S detectors can be used to
confirm that the concentrations measured on surface are
indeed representative. H2S coupons will react specifically to
the presence of low levels of H2S when exposed to fluids
entering from the formation. Since two single probes are
normally run in combination, one H2S coupon holder can be
run in each probe to allow another opportunity for H2S
detection (e.g. in another zone) or allows the backup probe to
be used for the most H2S-prone zone only while leaving the
main probe to detect the maximum overall H2S exposure
encountered in all the sampled zones. Alternatively, the

continuous measurement sensor can replace one or more of the

H2S coupons
In theory, H2S coupon discoloration is largely a function of
partial pressure and is weakly dependent on temperature and
exposure time. Reservoir waters with no H2S and drilling
fluids are not supposed to cause discoloration of these metals.
As a result, these alloys are said to be specific to the
presence of H2S. The reality is more complex, however, and
spurious results related to phase partitioning, adsorption,
and/or flow velocity could often be observed. Measurement of
discoloration in H2S coupons is somewhat subjective. For
instance, it is possible to obtain a tarnish of the metal rather
than true corrosion. This tarnishing in which the metal remains
glossy or shiny can potentially be misinterpreted as H2S
exposure. Moreover, H2S coupons are quite limited in the
range of measurement (up to 0.1 psi partial pressure) and are
only good for determination of maximum exposure levels seen
by a given coupon.
The H2S sensor appears to be a promising development. It
enables multiple insitu measurement of H2S concentration in
hydrocarbon and water samples; avoid problems of loss in
sample bottles. However, the performance of the sensor, most
importantly its accuracy and resolution, still needs to be tested
under downhole conditions, particularly at low concentrations.
For one thing, the relationship of H2S concentration in the
buffer fluid to concentration in flowline fluid maybe difficult
to determine under downhole conditions unless equilibrium
had been established. How long that would require is still
unknown. The exposure time and measurement lag time
needed as well as the possible effects of temperature, water,
mud and other contaminants are but examples of issues that
still need to be ironed out. It is our view that calibration of the
downhole measurement to widely accepted surface
measurement standards would still require time and effort to
complete. Even if fully tested and developed, it will still
require samples to be taken, much in the same way as other
downhole measurements of fluid properties still requires
samples to be collected for comparison and calibration. Rather
than obviating the need for H2S sampling, this sensor
complements and enhances the applicability of the H2S
sampling procedure described in this document and help
optimize its use by providing real-time H2S measurements
that can be used to estimate the H2S concentrations downhole
and to intelligently decide on the optimum depths and time
intervals to sample the fluid for H2S.
.
Timing and type of fluid analysis
Selecting the most appropriate time for any analysis to be
carried out and the most suitable type of analysis to be
performed will also have a very large bearing on the accuracy
of the results obtained. Several methods are used to detect the
H2S concentration on surface. The accurate determination of
the H2S content in a hydrocarbon sample is a very difficult
task given the reactivity of that compound. There is a clear
benefit for immediate onsite analysis with subsequent lab
analysis to support the onsite result. A precise measurement in
the PVT laboratory does not take into consideration what has

SPE 94707

been lost during transportation by adsorption, a reversible

phenomenon, and absorption, an irreversible chemical
reaction. (Bethea et al., 1973)
It is recommended that measurement of H2S contents of gases
and oils is carried out at the wellsite immediately after
sampling. Measurements carried out in the laboratory, after
sampling onsite, should only be used to provide approximate
lower bounds on the H2S concentration.
For onsite analysis, several methods are considered. The
accuracy of the methods is not equal and can lead to
significant differences. The ideal solution is to combine
several methods and operate according to a referenced
standard. This approach allows one to know how much one
can trust the results obtained.
- Multigas Monitors: Relies on electrochemical sensor, and
provides quick, easy to read digital output, limited to a max
concentration of 1000 ppm (Williams et al., 2003).
- Gas detection (length of stain) tubes: Uses the ASTM
D4810-88 standard (re-approved 1994) Method for Hydrogen
Sulphide in Natural Gas Using Length of Stain Detectors.
Gas detection tubes are quick, easy to use, and inexpensive.
Various manufacturers including Dragger, Kitagawa, GasTec,
etc. produce gas detection tubes that can be used in the range
of 0.5 ppm by volume to 40% by volume with reasonable
accuracy with appropriate range selection, use, storage, and
ambient corrections although the majority of these
applications will be on the lower end of this range (<120 ppm)
(Volkan et al., 1998).
- Potentiometric titration. Uses the following standards: UOP
163-89-H2S and Mercaptans in Hydrocarbon Liquid, IP
272/71 and UOP 212/77-H2S, Mercaptans and Carbonyl
Sulphide in Hydrocarbon Gases. The potentiometric titration
method is used to determine hydrogen sulphide, mercaptan
sulphur and carbonyl sulphur in hydrocarbon gas and liquid in
the 0.1 to 1-ppm level and the 1-ppm or higher level. UOP
212/77 can be used for H2S in both the gas and liquid phase.
while UOP 212/77/IP342 can be used to check the liquid
phase for any H2S left behind and non-volatile mercaptans.
Samples may be analyzed directly if viscosity permits
injection by syringe. Samples having a high content of sulfur
may be analyzed after dilution with a suitable solvent. Halides
in excess of 10 times the sulfur level, nitrogen content greater
than 10%, and heavy metals may interfere with the analysis.
This method is recommended to H2S concentrations that are
above 0.3 to several thousand wt-ppm, and is also used for
H2S and mercaptans in liquid above 1.0 ppm (Bethea, 1973).
- Iodimetric titration (ASTM D2385) uses the following
standards: ASTM D2385-81 standard (re-approved in 1990,
discontinued in 1995), IP 103/70 (re-approved proved 1978,
no later version currently available), GPA STD 2265-ASTM
D 2385-IP103. The technique uses cadmium sulphate
adsorption followed by iodometry. This method is very
accurate but is rather time consuming with each titration
taking 4-6 hours. The Cadmium sulphate method is applicable,

SPE 94707

according to the ASTM D2385, in the range of 0-5 grains of

H2S per 100cu-ft, corresponding to a range of 0-115 mg/mcu
or 80 ppm by volume (Bethea, 1973).
- Tutwiler method: Uses the UOP 9-59 standard. UOP 9-59 is
adapted to H2S concentrations that are above 5 grains/100 cuft which corresponds to 80 ppm by volume. It is a wet
chemistry method that takes over from the Iodimetric titration
method for concentrations above the limit of 80 ppmv.
- Gas Chromatography: uses the ASTM D 1945-91, GPA
2261-90 standard. The gas chromatography technique (ASTM
D 1945-91) is used to determine H2S content in gas. This
method is recommended for H2S concentrations above 20
ppm up to 40% by mol. Recent developments is micro-GC
technology appear promising in being able to extend the
applicability of GC methods to even lower concentrations.
For low H2S concentrations in the low tens of ppm range, it is
recommended that, as a minimum, gas chromatogrrahpy, gas
detection tubes and a wet chemistry method should be used at
the wellsite
When analyzing bottles on surface, some ordinary (noncoated) bottles are also analyzed to ensure that the
measurement that is made is indeed indicative of true H2S
concentrations and are not simply a measurement artifact. For
low tens of ppms levels of H2S, one should expect to find no
trace of H2S in the uncoated bottles.
Case I: Low PPM H2S Concentrations

Analysis results showed fluid from MRSC 097 (uncoated)

showed 0 ppm H2S (scavenged) and 1% CO2. Two subsamples from this chamber showed: OBM 35 wt% in STO,
API 42.34 and OBM contamination of 33 wt% in STL, and
API 42.3 and no H2S.
After that, 3510 cc were pumped over 30 min with the bottom
pump. This was followed by filling coated SPMC 226. No
H2S analysis was attempted on this coated bottle due to high
level of OBM contamination.
Second Sampling depth
Pumped 34515 cc in 49.3 min with bottom pump and filled:
two Sulfinert-coated bottles: coated SPMC 159 and coated
SPMC 118.
Analysis results showed coated SPMC 159 with 9 ppm H2S,
1% CO2, OBM contamination of 15.3 wt% in the STL, and
13.5 wt% in the live oil, contaminated gravity of 39.84 API,
and cleaned gravity of 38.45 API
After that, pumped 41535 cc in 43 min with top pump and
filled: MRSC 101, MPSR 1268, and coated SPMC 009.
Results: MRSC 101 sub-sample measured 9.04 wt% OBM
contamination in STL, 7.6% OBM contamination in live oil,
899 scf/bbl, and API 40.68. Another MRSC 101 sub-sample
yielded 8.42 wt% OBM, 906 scf/bbl GOR, 40.50 API, 0 ppm
H2S (all adsorbed), corrected gravity of 39.8 API, and
corrected GOR of 994 scf/bbl.

This example illustrates that it is possible to accurately

measure low (ppm) levels of H2S in formation fluids based on
analysis of downhole samples acquired by formation testers.
This test was performed in a well using a specially modified
MDT, coated SPMC Single Phase Multisample Chambers, and
a mobile analysis lab. The tool string is shown in Fig.8. Some
MDT components normally made of Monel were replaced
with Inconel ones to minimize H2S scavenging. Two pumps
were run, one above for standard low shock and another at the
bottom for reverse low shock (Fig.4). A dedicated
multisampler with Sulfinert-coated bottles placed at the
bottom of the string was used for H2S sampling. The bottles in
that multisampler were filled against a water cushion using the
bottom pump, thus avoiding H2S scavenging by the pump
displacement unit.

Third Sampling depth

In the description that follows, all chambers are uncoated

unless otherwise mentioned.

Fig.9 shows that the H2S coupons came up with exposures

that are highly consistent with the values measured on the
coated bottles. This provided confidence in the results. Note
also that, as expected, none of the uncoated bottles showed
any H2S, which demonstrates the value of the special
procedures used.

First Sampling depth

Pumped 4680 cc in 4.9 min + 12285 cc in 142 min and then
filled a few samples to secure a sample although real-time
contamination monitoring showed that OBM contamination
was still high. Thereafter, filled MRSC 097, MPSR 1932,
SPMC 022, SPMC 025, and MPSR 1943.

Pumped 51480 cc in 84.19 min with top pump and filled:

MPSR 458, MPSR 1155, and coated SPMC 113.
After than, pumped 13455 cc in 23.46 min with bottom pump
and filled coated SPMC 168 and coated SPMC 037
Analysis if coated SPMC 168 yielded 965 scf/bbl GOR, 41.2
API, 5.1% OBM contamination in STL and 4.6 wt% OBM
contamination in live oil. API gravity corrected for OBM was
40.8 API, and GOR corrected for OBM was 1019 scf/bbl.
SPMC 037 yielded 13 ppm H2S concentration, 1% CO2,
OBM contamination of 4.79 wt%, and 40.26 API.

Case II: Low H2S Concentrations

An H2S adsorption test was conducted by using a full Baker
Reservoir Characterization Instrument (RCI) string (Shammai,

2004). The tool was assembled as shown in Fig.10 and

consisted of the hydraulic section, the packer section (MB),
the 56cc pump (BB), the 500cc pump (RB), and the six tank
carrier (WA). Two pumps, a six-tank carrier, two stock
solutions (batch #1 and batch #2), and a vacuum pump were
used. The purpose of the experiment was to estimate the
amount of H2S adsorbed while pumping sample through an
RCI string. This was achieved by preparing 20 Liters of
standard solution of brine containing approximately 60 ppm of
H2S. The solution was then pumped through the tool to
simulate exposure to H2S. In this experiment two pumps were
used to pressurize the sub-samples in the six tank carrier to
3000psi and 5000psi.
Two sub-samples were collected from the tanks containing the
stock solution, designated as batch #1 and batch #2. These
samples were labeled sample number 7 and sample number 8
respectively. Batch#1 and Batch #2 stock tanks, were
connected by a Tygon tubing on the sample side.
Four single-phase tanks were prepared with 500psi of nitrogen
charged in two tanks (samples #1 and #3 as shown in the
above diagram) and 1000psi of nitrogen charged in the
remaining two (samples #2 and #4 as shown in the diagram).
Then all four tanks were loaded into the six-tank carrier.
Compressed air was blown through the tool to remove all
excess water from the sample line, and the tool was function
tested to make sure that the valves and the pumps will operate
without problems. The manual valves of the single phase and
the borehole tanks exit tanks were then opened, and the system
was evacuated for 2 hours. Diesel was then pumped through
the tool for 30 min to make sure air had been eliminated from
the system. For clarity, the experimental procedure could be
divided into two parts.
Part One
The 56cc BB pump was activated, and 4 liters of sample was
pumped from Batch #2 stock solution through the tool to
displace the diesel and expose the tool to the H2S solution
(Batch #1 remained closed at this step). 200c of sample was
displaced into the borehole exit tank. This sample was labeled
sample #5. 4 liters of stock solution batch #1 was then pumped
through the tool using the BB pump. The single-phase tank
filled with 500psi nitrogen pressure was opened, and enough
sample volume was pumped into the tank to produce a
pressure equal to 3000psi. This sample was labeled #1. The
single-phase tank, which contains 1000psi of nitrogen was
opened, and enough sample was pumped into the tank to
produce a sample pressure equal to 5000psi. This sample was
labeled #2. An attempt was made to collect a sub-sample from
the stock solution (Batch #2), but there was not sufficient
sample available.
The 500cc RB pump was activated and batch 1 stock solution
tank was opened. 4 liters of sample was pumped from Batch
#1 stock solution through the tool to displace the diesel in the
pump (Batch #2 remained closed at this step). 200cc of sample
was displaced into the borehole exit tank. This sample was

SPE 94707

labeled sample #6. 4 liters of stock solution Batch #1 was then

pumped through the too using the RB pump. The RB singlephase tank, which contained 500psi of nitrogen, was opened.
Then enough sample volume was pumped into the tank to
produce a sample pressure equal to 3000psi. This sample was
labeled #3. The single-phase tank, which contains 1000psi of
nitrogen, was opened. Enough sample was pumped into the
tank to produce a sample pressure equal to 5000psi. This
sample was labeled #4. A sub-sample was collected from the
stock solution (Batch #1). This sample was labeled #9.
As summarized in Fig.11 and in the top part of Fig.12, a total
of three samples were collected; one at the borehole exit with
final concentration of 60.3ppm, a second sample at 3000psi
with final concentration of 56.7ppm, and a third sample at
5000psi with final concentration of 56.6ppm. The results
indicated an approximate loss of 3ppm in the pressurized
samples and no loss in the borehole exit sample. The Delta
column in Fig.12 indicates the difference between the average
H2S concentration value of the stock solution (batch 1) and
the final H2S concentration in the samples collected during the
test. The stock solution in batches 1 and 2 contained 60ppm of
H2S. For Batch #1, two samples were collected one before the
test and one after the test. The results indicated that there was
no appreciable deterioration in H2S concentration during the
experiment. For Batch #2, there was not sufficient sample left
in the tank at the end of the experiment to collect a subsample.
Part Two
In the second part of the experiment, batch #2 was used along
with the 56 cc BB pump. Three samples were acquired; first
one at the bore hole exit with final concentration of 58.6ppm,
second a sample collected at 3000psi with final concentration
of 59.0ppm, and third a sample at 5000psi with final
concentration of 60.4ppm. The results shown in the lower part
of Fig. 12 indicated a loss of less than 2 ppm in the
pressurized samples and a loss of 1ppm in the borehole exit
sample. The Delta column indicates the difference between
the H2S concentration value of the stock solution (Batch #2)
and the final H2S concentration in the samples collected
during the test. H2S concentration in the stock solution
remains constant during the experiment.
After concluding the tests with the RCI, it was felt that enough
understanding of what the potential for loss of H2S was with
the RCI. Two jobs were attempted with the results in mind and
using the same analytical procedures described for Case I. One
job was carried with the RCI, samples yielded 23 ppm
compared to 28 ppm with from an extended well test. On
another well, 11 ppm was measured on the RCI samples vs. 15
PPM from a corresponding DST. As a result of the lab
experiments and the field trials, the following conclusions
were made:
1.

H2S adsorption in the RCI tool string and sampling tank

is not dependent on time, pressure, or temperature (up to
400F and 7 days).

SPE 94707

2.
3.

The Baker RCI is currently the most suitable for sampling

low level H2S because of its titanium construction.
Approximately 3 to 5ppm of H2S are adsorbed by the tool
string regardless of the original concentration of the H2S
in the sample.

Case III High Levels of H2S concentration

In this example, the MDT was run in two wells in the Middle
East and the measured H2S results were compared to ones
recorded on DSTs. Prior to conducting the tests, lab
experiments were conducted using a set-up similar to the RCI
setup described above. As expected and illustrated in Fig.. 7 ,
the experiments demonstrated that absorption of H2S in the
MDT pump unit is strong at low levels (<50 ppm). However,
since the interest in this project was to measure much higher
levels of H2S, the objective was primarily to find out what
quantity of a 1% H2S solution would be needed to saturate the
exposed surfaces of the tool such that no further loss of H2S
would occur over the course of the sampling. The experiments
revealed that the critical number to saturate a typical MDT
string is 35 gal for concentrations of 50,000 ppm or more. The
actual analysis results were in excellent agreement with the
expected results. In one of the test wells, 0.61% H2S was
observed in the sample compared to 0.62% in the well test,
while on the other well, 1.1% was observed in the MDT
samples compared to 1.12% in the well test.
Conclusions
We have demonstrated that different levels H2S
concentrations can be accurately measured in downhole fluid
samples. The key is in understanding the factors that affect the
measurement and in using a comprehensive process/workflow.
Depending on the H2S levels of interest, the process may
include a number of modifications and replacements to several
parts of the formation tester tool and to the sample chambers
themselves to ensure that the bulk of the H2S does not get
absorbed by the time the tool arrives to the surface. For low
(PPM) levels of H2S, the RCI seems to be the most suitable
tool because of its titanium construction. Moreover, MP35N,
the material used in the RCI single-phase tanks, is excellent
for preservation of low H2S concentrations. When using other
tools such as the Schlumberger MDT or Halliburton RDT, the
process must also include rearrangement of sampling modules
to eliminate H2S absorption in the downhole pump, which is
generally the major culprit for H2S absorption. On surface, a
number of techniques can be used to measure H2S
concentration in the sample bottles, but this must be done as
soon as possible after the formation tester tool is brought to
the surface. In addition, downhole measurements made close
to the fluid entry into the sampling tool are used to cross check
and verify the surface measurements. By using a holistic
systematic approach to H2S sampling and analysis, it is now
possible to capture and analyze subsurface fluid samples
which accurately represent the concentrations in the reservoir
fluid regardless of the original concentrations.

References
1. Bethea, R.M., Comparison of hydrogen sulfide analysis
techniques, J. Air Poll. Control Assoc., 23, 710-713
(1973).
2. Carlson, M.R. and Cawston, W.B., Obtaining PVT data
for very sour retrograde condensate gas and volatile oil
reservoirs: A multi-disciplinary approach, SPE Gas
Tech. Conf., Calgary, April-May 1996, SPE 35653.
3. Hland, K., Barrufet, H.P., Rnningsen, H.P. and
Meisingset, K.K., An empirical correlation between
reservoir temperature and the concentration of hydrogen
sulfide, 1999 SPE Intl. Symp. Oilfield Chem., Houston,
Texas, Feb. 1999, SPE 50763.
4. JPT Forum, H2S A toxic gas that can kill, Journal of
Petroleum Technology, March 1971, Paper SPE 3202.
5. Kane, R.D., Greer, G.B., Sulfide stress cracking of high
strength steels in laboratory and oilfield environments,
Journal of Petroleum Technology, Nov 1977, SPE 6144.
6. Kermani, M.B. and Harrop, D., The impact of corrosion
on the oil and gas industry, 1995 Middle East Oil Show
& Conference, Bahrain, SPE 29784.
7. NACE (2003), NACE Standard TM0177-96, Laboratory
Testing of Metals for Resistance to Specific Forms of
Environmental H2S Environments, (Houston, TX; NACE
International).

8. Parrillo, D.J., Thaeron, C. and Sircar, S., Separation of

bulk hydrogen sulfide hydrogen mixtures by selective
surface flow membrane, A.I.Ch.E.J., 43, 2239-2245
(1997).
9. Scott, P.J.B. and Davies, M., Souring of New Irian Jaya
wells traced to indigenous bacteria, Oil & Gas J., 91, 4750 (1993).
10. Volkan, M., Eroglu, T., Eroglu, A.E., Ataman, O.Y. and
Mark, H.B., A novel sorbent tube for ambient hydrogen
sulfide determination, Talanta, 47, 585-593 (1998).
11. Wilhelm, S.M. and Kane, R.D., Selection of materials
for sour service in petroleum production, Journal of
Petroleum Technology, October 1986, PP 1051.
12. Williams, J.M., Getting reliable on-site H2S and CO2
concentrations for anti-corrosion measures in gas wells,
SPE 13th Middle East Oil Show & Conference, Bahrain
Jun 9-12, 2003, SPE 81495.
13. Shammai, M et al., Optimum sampling techniques for fluid
samples containing H2S, presentation at the SPWLA Spring
Topical Conference, Taos, New Mexico, March 28 April 1st,
2004.

10

SPE 94707

RAW MATERIAL BAR STOCK

Fig.1 H2S Partial pressure plot from NACE MR0175-2000 standard

ALLOY

$/lb.

4130

1.0

4140

1.0

9Cr

1.5

410-13Cr

2.0

420 Mod.

2.0

17-4

3.0

304

2.5

316

3.0

S13Cr

5.0

450

6.0

918

5.5

Monel K-500

12

925

11.5

718

12

625M

20

725

20

C-276

50

MP35N

60

Fig.2 PH and H2S are related in the NACE MR0175-2000 standard

Fig.3 Comparative cost of raw material bar stock

Fig.4 Schematic of the reserves-low-shock sampling technique

SPE 94707

11

Before Exposure

most
mid
least
sensitive sensitive sensitive
After Exposure

H2S Concentration
(ppm)

Test 4.1 - Displacement Unit (Side 1)

with 50 ppm Test Gas
50.0
40.0
30.0
20.0
10.0
0.0
0.1

10

100

1000 10000

Time (minutes)

most
mid
least
sensitive sensitive sensitive

Fig.7 H2S Scavenging in MDT Pump Displacement Unit

Fig.5 H2S coupons shown before and after exposure to H2S

Fig.6 H2S absorption in different types of sample bottles

Fig.8 MDT Toolstring used in Case I

12

SPE 94707

Fig.9 H2S coupon exposure results for Case I

#4

5000psi

#2

5000psi

#3

3000psi

#1

3000psi

WA

RB

BB

EB

MB

Batch 1
# 7 and # 9
#6

#5

Bore-hole Exit Tanks

Batch 2
RB

BB

Vacuum Pump

#8

Diesel

Fig.10 RCI experimental setup Case II

Sample #

Batch # 1

BB pump
@3000psi
BB pump
@5000psi

Sample 1
Sample 2
Sample 3

RB Pump 3000psi

Sample 4

RB Pump 5000psi
BB pump
Borehole Exit

Sample 5
Sample 6
Sample 7

RB pump
Borehole Exit
Stock solution
before the test

Stock solution
after the test

Concentration
[ppm]

Delta

59.0

1.1

60.4

-0.3

56.7

2.95

56.6

3.05

58.6

1.5

60.3

-0.65

59.1
Stock solution
before the test

Sample 8
Sample 9

Batch # 2

60.1
60.2

Fig.11 RCI experimental results Case II, Part 1

Batch #1
500cc Pump @ 3000psi
500cc Pump @ 5000psi
500cc Pump@ Borehole
Exit
Stock Solution Before
the Experiment
Stock Solution After
the Experiment

Concentration [ppm]
56.7
56.6
60.3

Batch #2
56cc Pump @ 3000psi
56cc Pump @ 5000psi
56cc Pump@ Borehole
Exit
Stock Solution Before
the Experiment
Stock Solution After
the Experiment

Concentration [ppm]
59
60.4
58.6

Delta
2.95
3.05
-0.65

59.1
60.2

Delta
1.1
- 0.3
1.5

60.1
Insufficient
sample

Fig. 12 Summary of RCI Experimental Results Case II, Parts 1

and 2