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Pipeline Corrosion
Corrosion Basics:

Metals are normally found in nature in one their lowest energy states - usually as oxides,
sulfides, chlorides, etc. In reducing and refining metals to produce useful alloys (such as the
carbon and low alloy steels used in gas and oil transmission pipelines), significant amounts of
energy are consumed and “stored” within the reduced metallic structures. Subsequent corrosion
of steel pipelines thus represents the natural tendency of the iron in the pipe to return to a
preferred, lower energy state (usually as an oxide, carbonate or sulfide).

Corrosion of steel - at the relatively low temperatures (less than 200 degrees F.) normally
encountered in pipeline operations – takes place by an electrochemical process. This process, in
turn, requires the presence of anodic and cathodic areas on the surface of the pipe and the
presence of a suitable, conductive aqueous environment that contacts both the anodic and
cathodic areas. For buried pipe, the external corrosion environment will usually consist of moist,
relatively high conductivity soil. Internal corrosion can occur if water exists within the line and
is allowed to accumulate at low spots in the line. Significant internal corrosion also usually
requires the presence of a significant partial pressure of carbon dioxide and/or oxygen within the
line.

The consumption of the steel pipe occurs at the anodic areas on its surface by oxidation of the
iron of the pipe wall. The anodic portion of the corrosion process can thus be represented by
equation (1):

Fe → Fe++ + 2e- (1)

The cathodic portion of the electrochemical corrosion process may reportedly occur by one of
several reactions, depending upon the conditions of the environment:

O2 + 2H2O + 4e- → 4OH- (2)

O2 + 4Η+ + 4e- → 2H2O (3)

2H2O + 2e- → 2OH- + H2 (4)

H+ + e- → _ H2 (5)

The ultimate fate of the Fe++ ion from equation (1) also depends upon the environment. The Fe
may stay in solution as the ion or it may be precipitated as Fe(OH)2 or as FeCO3. For external
corrosion in moist soils, the ultimate corrosion product is usually Fe(OH)2, while internal
corrosion involving carbon dioxide often results in FeCO3 as a corrosion product.

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The kinetics of the electrochemical process can be shown schematically using the diagram in
Figure 1. The open circuit potentials of the local cathodes and anodes, Φc and ΦA , are shown on
the diagram, along with the polarization paths for the cathodes and anodes that result as
increasing amounts of current are produced by the local electrodes. The over-all (average)
corrosion potential for a surface covered with small, adjacent local anodes and cathodes (in a
solution with moderate to high conductivity) thus occurs where the polarization curves for the
electrodes approach one another, as shown in Figure 1.

A similar diagram, as shown in Figure 2, can be used to illustrate the basic characteristics of
corrosion prevention using cathodic polarization. The diagram in Figure 2 shows the
continuation of the cathodic polarization curve that occurs as increasing amounts of positive
current are forced onto the initially freely corroding sample surface (line c – e – f).

Consider the situation at point e. At this point, the total current being supplied to the surface, Ie ,
consists of the sum of the current being supplied from local anodes, Ib , and the current being
supplied from an outside voltage source, Ie – Ib .

As the cathodic polarization of the sample surface is increased to point f, all current from the
local anodes has been shut off and all of the current flowing to the sample surface is coming
from the external applied voltage source.

It should be noted that at point e, the sample surface is experiencing only partial protection from
the applied current, I e – Ib , that is being forced onto its surface. Some corrosion (as indicated by
the anodic current, Ib ) is still occurring on the sample surface. The sample becomes fully
protected only after the polarized potential of the sample has dropped to ΦA and the anodic
contribution to the total sample current has dropped to zero.

It should also be noted, however, that continued polarization of the sample surface, to potentials
more negative than ΦA, has no additional beneficial effects in preventing corrosion and may,
instead, cause difficulties due to hydrogen-induced disbonding of coatings and hydrogen induced
cracking of the steel of the pipeline.

Corrosion Prevention:

External corrosion

The principal methods used to prevent external corrosion of pipelines are coatings and cathodic
protection (CP) of the lines. In recent installations, coatings and CP have normally been used
together in a complimentary fashion, since high quality coatings substantially reduce the CP
current requirements and the application of a functioning CP system allows some relaxation in
the requirement for 100% “holiday” (defect) free coatings.

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Coatings:
The NACE Standard RP0169-96 [1] lists most of the desirable characteristics of a pipeline
coating. These include the following:

1. The coating should have a high electrical resistance and high dielectric strength.

2. The coating should be an effective moisture barrier.

3. The coating should be reasonably easy to apply and the application process should not
change the properties of the pipe.

4. The coating should exhibit good adhesion to the pipe.

5. The coating should be resistant to chemical and physical damage/degradation during

installation and service.

6. The coating should be reasonably easy to repair in the field.

7. The use of the coating should not present any environmental or health risks.

Pipeline coatings have been used for more than 70 years and numerous systems have been
developed. The coating systems that are currently being applied include the following:

1. Coal tar enamels containing embedded glass fiber mats.

2. Mill-applied tape systems.

3. Extruded polyethylene and polypropylene coatings.

4. Fusion – bonded epoxy (FBE) coatings.

5. Multi-layer, FBE under extruded polyethylene or polypropylene.

The last three coating systems listed above are reportedly currently experiencing increasing
acceptance by consumers and their future use should therefore expand.

Cathodic Protection:

The electrochemical basis for cathodic protection systems was presented briefly above in the
Corrosion Basics section (see Figure 2). The current used to cathodically polarize the sample to
be protected can typically come from an “impressed current” system using an external, D.C.
power supply that supplies current to the pipe by way of a remote anode “ground bed”.
Alternatively, the protective current can come from a reactive, “galvanic” anode or group of

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anodes. Galvanic anodes are typically located within ten to twenty feet of the spot on the pipe to
be protected.

A schematic representation of a typical impressed current, cathodic protection system is shown

in Figure 3. The anodes in the ground bed are usually made of graphite or high alloy cast iron
rods. The rectifier that serves as the source of the polarizing current may have a voltage range of
10 to 100 volts and an available D.C. current range of 5 to 200 amperes.

Since positive current flows from the positive to the negative terminal of the power supply in an
external circuit that is connected to a D.C. power supply, it is critical that the pipeline to be
protected be connected to the negative terminal of the rectifier. Connection of the pipeline to the
positive terminal of the rectifier would result in greatly accelerated corrosion of the line (instead
of the planned reduction/elimination of corrosion).

The kinetics of the cathodic protection process when using a sacrificial, ganvanic anode are
illustrated in Figure 4. The sacrificial or galvanic anodes are typically fabricated of relatively
pure zinc or magnesium or alloys of these reactive metals. The polarized potential of typical
zinc anodes is approximately –1.1 volts (as measured using a saturated copper – copper sulfate
reference electrode - CSE). The polarized potential of a typical magnesium alloy anode is, on
the other hand, approximately –1.50 to –1.55 volts vs. a CSE. The available driving potentials
from the sacrificial anodes for polarizing steel structures are, therefore, relatively limited, and the
length of pipe that can be protected using sacrificial anodes is relatively small.

The three primary inspection criteria currently used to assess if appropriate levels of cathodic
protection (CP) are being supplied to protected piping by a CP system are also described in
NACE Standard RP0169-96. These criteria are:

1. A piping potential of –850 mV vs. a CSE, measured with the CP system in operation.

2. A polarized piping potential of –850 mV vs. a CSE, as measured within approximately 1/2 to
1 second after (simultaneously) turning off all sources of direct current to the piping.

3. 100 mV of polarization with respect to the native corrosion potential of the pipe. The
polarized potential used in this evaluation criterion is the same “instant off” polarization used
in criterion 2.

In using criterion #1, it is recognized by NACE that there are IR drop errors in the potential
measurements that must somehow be estimated and evaluated in applying this criterion. There
are no firm guidelines presented, however, on how this estimation and evaluation should be
performed.

In making the measurements involved in criteria #2 and #3, the IR drop errors caused by the flow
of D.C. current to the protected structure are eliminated by measuring the polarized potential of
the structure or piping within a half to one second after simultaneously shutting off all D.C.

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current sources to the structure or piping. There may, of course, be considerable difficulty and
expense in finding and arranging for the simultaneous interruption of all D.C. currents to the
piping and failure to eliminate these sources of current will result in errors in the measurements.

In using criterion #3, the measurement or estimation of the “native” corrosion potential of the
existing pipe or structure may also present some difficulties. For new piping that has not been
previously protected by a CP system, it is only necessary to measure the initial “native”
corrosion potential and then turn the CP system on and wait for the potential of the piping to
drop to a stable value. At this point, switching off the source of all D.C. currents allows the
measurement of the “instant off” polarized potential of the pipe and the shift in potential with
respect to the original native potential.

For existing piping that is currently under the protection of a CP system, shutting off all D.C.
currents will allow the measurement of the “instant off” polarized potential of the pipe. A
considerable waiting period (and some significant opportunity for error) may, on the other hand,
be encountered in obtaining an estimate of the “native” corrosion potential in this case.
Unfortunately, previously used piping systems that have been under the influence of a CP system
for some extensive period are typically the objects of a CP system evaluation.

Care must be taken during the installation and/or adjustment of CP systems to insure that the
applied CP voltage is neither too low nor too high.

Applied voltages that are too low could, of course, result in some corrosion to the piping. Also,
there is some evidence that the high pH, stress corrosion cracking that is sometimes seen on the
external surfaces of pipelines occurs in the range of lower polarized potentials (from
approximately –0.50 and –0.85 volts vs. a CSE).

In addition, elevated temperatures in the pipe are known to promote corrosion of the pipe. For
piping or piping areas that operate at temperatures significantly above the surrounding earth
temperature, an operating CP potential of –0.95 volts or more should be considered. The
presence of bacteria in the soil may also promote the presence of microbiologically induced
corrosion (MIC) on the outside surface of pipelines. In areas where MIC is suspected or
confirmed, a CP potential of -0.95 volts or more should be considered.

On the other hand, CP voltages that are larger than approximately –1.05 to –1.10 volts are
thought to cause hydrogen induced cracking of some pipeline steels (particularly older steels
containing higher levels of sulfur and phosphorus). This hydrogen induced cracking appears to
be greatest in hard spots produced in the pipe during manufacture and in the heat affected zone
of welds where small, localized hard areas may be present.

Finally, elevated CP voltages may cause hydrogen-induced damage of coatings. It is generally

recommended that CP voltages larger than approximately –1.10 volts be avoided in order to
minimize the possibility of coating damage due to evolution of hydrogen.

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Internal Corrosion

Internal corrosion in a pipeline requires the presence of liquid water within the line. In gas
transmission lines (the only pipelines that will be discussed in this document), internal corrosion
also usually signals the presence of significant partial pressures of carbon dioxide and/or
hydrogen sulfide in the line.

It is also known, however, that on a weight percentage or weight fraction basis, dissolved oxygen
is more corrosive to ordinary steels than either carbon dioxide or hydrogen sulfide. Although the
probability of having appreciable concentrations of oxygen inside a gas transmission line is
apparently quite low, it should be remembered that even small partial pressures of oxygen can
produce surprisingly high internal corrosion rates in steel pipes that also contain liquid water.

One method to reduce the danger of internal corrosion by the acid gases, carbon dioxide and
hydrogen sulfide, is to reduce the concentration of the acid gases in the gas transmission stream
by a process known as “gas sweetening”. Many gas sweetening processes have been developed
and used. These include, for example:

1. Solid bed absorption (using iron sponge, mole sieves or zinc oxide),

2. Chemical solvents (such as mono ethanol amine, di ethanol amine, potassium carbonate, etc),

3. Proprietary physical solvents,

4. Conversion of hydrogen sulfide to sulfur,

5. Distillation.

Water can form in a pipeline if there has been no attempt to dehydrate the gas prior to its
introduction into the line or if the gas dehydration process that was used did not produce water
contents in the gas that were low enough to prevent condensation of liquid water in the line. If
the gas temperature drops below its water dew point, liquid water will probably form. Liquid
water that is produced in the line will, of course, tend to accumulate in the low points in the line.
Here, the water will equilibrate with carbon dioxide and/or hydrogen sulfide in the gas and can
produce local areas of high internal corrosion rates.

A second effective method used to prevent internal corrosion of gas transmission pipelines is
thus dehydration of the gas prior to its introduction into the line. The aim of the dehydration
process is to reduce the water content of the gas to a low enough level that the water will not
condense in the line under the lowest pressure and temperature that the gas will experience in the
line.

By far the most common dehydration process for natural gas involves contacting the gas with a
hygroscopic liquid such as a glycol. The most common glycol used for gas dehydration is

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triethylene glycol. The dehydration process takes place in a multi-tray column known as a glycol
contactor. The glycol is “regenerated” before recycling to the contactor by heating to drive out
the absorbed water. Glycol dehydration can usually easily reduce the dew point of the gas to the
level required to prevent water condensation during transmission.

The use of gas sweetening in conjunction with gas dehydration will, of course, minimize the
chance of problems with internal corrosion in gas pipelines.

Early work by de Waard and coworkers at Shell [2,3,4,5] resulted in what has come to be known
as the “Shell” model for predicting the corrosion rates of steel by carbon dioxide. For example,
the “Nomogram for CO2 Corrosion”, shown in Figure 5, allows easy estimation of the predicted
corrosion rate of steel at various temperatures and carbon dioxide partial pressures. The
combined effects of temperature and carbon dioxide partial pressure on the anticipated corrosion
rates are shown in Figure 6. It should be pointed out that the “Shell” model is generally felt to be
moderately to substantially conservative. For example, the model was developed for “clean”
systems (containing no oil or other liquid hydrocarbons) and the presence of condensed
hydrocarbons may substantially reduce the observed corrosion rates.

In contrast to the weight loss corrosion problems produced by carbon dioxide, hydrogen sulfide
(at the relatively low temperatures encountered in gas pipeline operations) generally causes
environmental cracking (sulfide stress cracking, SCC) problems rather than weight loss
corrosion. Guidelines for the selection of candidate materials for use in hydrogen sulfide
environments (sour environments) are given in NACE Standard MR0175-2000 [6]. The
concentrations of hydrogen sulfide above which the gas stream should be considered “sour” (and
the threshold concentrations which will thus probably cause SCC) are also defined in NACE
MR0175-2000 (see Figure 7 below).

Corrosion Monitoring:

External Corrosion

Survey methods that are commonly used to evaluate the external corrosion conditions of
pipelines include:

1. Pipe-to-soil potential measurements,

2. Soil resistivity measurements,

3. Measurements of D.C. currents flowing along the pipeline,

4. “Bellhole” examinations of the pipe.

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Pipe-to-soil potential measurements are typically made using a saturated copper-copper sulfate
(CSE) reference electrode that is placed in contact with the soil directly over the line. The
potential measurements are made with a high input impedance voltmeter. Hooking the negative
terminal of the voltmeter to the CSE electrode and the positive terminal to the pipeline gives
readings with the normally used sign convention (e.g., the native corrosion potential of bare steel
in moist soil will normally read between –0.1 and –0.5 volts).

In pipe-to-soil potential surveys of pipe that is not under cathodic protection (and that has been
allowed to reach its “native” corrosion potential prior to starting the measurements), the points
on the line with the largest negative potential values will normally be the areas with the highest
corrosion rates. Newly installed pipe (and pipe sections) will, however, usually have pipe-to-soil
potentials that are substantially more negative than older sections of line and the pipe-to-soil
potentials of new pipelines (without CP) will usually tend to decrease in magnitude (become less
negative) with the passage of time.

In applying pipe-to-soil potential measurements to pipelines under CP, one of the three primary
acceptance criteria given in NACE Standard RP-01-69 (and discussed above) can be used. An
example of actual pipe-to-soil potential measurements taken from the literature [7] is given in
Figure 8. As shown by the upper curve in Figure 8, the section of pipeline represented in the
figure would have satisfied criterion # 1 (-0.850 V vs. CSE with the CP system on). The pipeline
would not, however, have satisfied criterion # 2 (a -0.850 V, “instant off” polarized potential).
This criterion is represented by the intermediate curve in Figure 8. As can be seen, the section of
the pipe between 0 and approximately 150 meters in the plot had a polarized potential that was
smaller (less negative) than the required – 0.850 V vs. CSE. By subtracting the bottom curve
(the native corrosion potential curve) from the intermediate curve (the instant off polarized
potential curve), it can be seen that most of the pipeline also failed to meet criterion # 3. The
calculated differences between the intermediate curve and the lower curve in the figure appear to
generally be smaller than the 100 mV required by criterion # 3.

Soil resistivity measurements can be made using either two terminal or four terminal meters.
Either an A.C. or D.C. power supply can be used in conjunction with an instrument that
accurately measures the current and potential between the test electrodes. Four terminal
instruments are usually used when larger soil areas are examined or when resistivities at a greater
depths are desired.

Corrosion rates of buried pipes are generally higher in lower resistivity (higher conductivity)
soils. Guidelines correlating observed corrosion rates with soil resistivities have been developed.
These guidelines are documented in Table 1. Because of the possibility of errors caused by
voltage drops in the soil due to the flow of CP currents, it is recommended that soil resistivity
measurements be made with CP systems shut off.

Line current measurements are typically made using test stations that are installed at the time the
pipe was laid. Electrical leads are connected to both ends of the pipe test span and these leads
are subsequently used to measure the voltage drop across the test span. The electrical resistance

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of the test span is then either estimated or measured and the net electrical current in the test span
is calculated using Ohm’s law. The sign of the voltage drop indicates the direction of the current
flow through the test span. In order to eliminate the effects of any active CP system, line current
measurements should be made with those systems shut off.

The currents detected in line current measurements are “long-line” currents that are typically
caused by widely separated “macro” electrodes (e.g., different soil conditions along the line) or
by interferences from “foreign” D.C. fields in the earth (such as those caused by an adjacent,
unconnected CP system). “Long-line” currents are not caused by the local anodes and cathodes
that produce the corrosion normally observed on the line. However, at the location(s) where
“long line” currents leave the pipe, the resulting corrosion rates can be very high. For example
calculation shows that, if only 10 milliamps of D.C. current leaves a pipe over an area of 1
square inch on the pipe surface, a corrosion penetration rate of approximately 700 mils (or about
0.7 inches) per year would be observed at that location.

Internal Corrosion

Successful monitoring of internal corrosion of pipelines is apparently significantly more difficult

than monitoring of external corrosion, as discussed above. One method that may yield valuable
information concerning the general internal condition of a line is to periodically run scraper pigs
through the lines. Evaluating the quantity and composition of material that is removed from the
line by the scraper pig may be useful in evaluating whether or not significant internal corrosion
has been occurring in the line.

The development and use of “smart pigs” may soon allow the successful simultaneous detection
and monitoring of both external and internal corrosion/damage in pipelines. Measurement
techniques that have been considered and/or used in previous “smart pig” development efforts
include:

1. Multi-“finger”, mechanical calipers that detect and record the effective internal radius of the
pipe,

2. Magnetic flux-leakage tools that may be configured to respond to both longitudinal and
circumferential defects in the pipe. These tools may also include high frequency eddy
current sensors that can differentiate between internal and external damage,

3. Ultrasonic tools that couple directly to the pipe wall through a surrounding liquid and that
may measure either the internal radius or the wall thickness of the pipe,

4. Ultrasonic tools that use electromagnetic acoustic transducers (EMATS) to evaluate the
condition of the pipe wall. These transducers use electromagnetic signals to generate

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ultrasonic signals in the pipe wall. Future use of EMAT technology may eliminate many of
the difficulties and short comings with direct coupling ultrasonic tools.

Corrosion Economics:

A recent review [8] of the economic effects of corrosion upon the U. S. economy has been
published. The results of this review indicate that corrosion of metals and alloys costs U. S.
companies (and consumers) a total of approximately $300 billion per year. The authors of this
review (scientists at Battelle Institute and the National Institute of Standards and Technology)
also concluded that approximately one third of these total costs (approximately $100 billion per
year) could be significantly reduced or eliminated by the use of current best available corrosion
prevention techniques and materials.

In the review, it was estimated that the pipeline industry accounted for something less than 1
percent of the total industry-wide corrosion costs. This would thus probably put the total costs
for corrosion in the pipeline industry somewhere in the range of $2 billion to $3 billion per year.
It also thus seems possible that the use of improved materials and corrosion prevention
techniques in the pipeline industry might reduce the total costs of corrosion in this industry by as
much as $600 million to $900 million (by ~ 30%).

In the case of the pipeline industry, as in several other industry segments, the authors of the
review felt that, although the need for corrosion-related repairs and re-coating had apparently
gone down in the recent past, the savings due to the drop in repairs had been essentially balanced
by the use of more expensive original materials of construction.

In our opinion, the development of more sensitive and more accurate inspection techniques (such
as improved “smart pigs”) and the possible regulatory requirement for the use of these more
sensitive inspection techniques could substantially increase the repair costs associated with the
future operation of aging gas transmission pipelines.

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References

1. NACE RP0169-96 “Control of External Corrosion on Underground or Submerged Metallic

Piping Systems”.

2. C. de Waard and D.E. Milliams, Carbonic Acid Cirrosion of Steel”, Corrosion, Vol. 31,
1975.

3. C. de Waard, U. Lotz and D.E. Milliams, “Predictive Model For CO2 Corrosion Engineering
in Wet Natural Gas Pipelines”, Corrosion, Vol. 47, 1991.

4. C. de Waard and U. Lotz “Prediction of CO2 Corrosion of Carbon Steel”, Corrosion 93,
Paper 69, 1993.

5. C. de Waard, U. Lotz and A. Dugstad “Influence of Liquid Flow Velocity on CO2

Corrosion”, Corrosion 95, 1995.

6. NACE MR0175-2000 “Sulfide Stress Cracking Resistant Materials for Oilfield Equipment”.

7. “Peabody’s Control of Pipeline Corrosion”, NACE, 2001.

8. “Economic Effects of Metallic Corrosion in the United States: a 1995 Update”, Battelle
Institute, 1996.

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TABLE I

Corrosion of Steel in Soil

Corrosion
Area Corrosion (mpy) Severity Resistivity (Ω- cm)

Ave. of Several 61 Moderately 1000 to 2000

Soils Corrosive

Tidal Marsh 100 Corrosive 500 to 1000

Clay 137 Very Less than 500

Corrosive

Sandy Loam 21 Mildly 2000 to 10000

Corrosive

Desert Sand 5 Noncorrosive Above 10000

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