Soil Chemistry Analysis and

Affects on Corrosion Rate

> AGA Operations Conference

Corrosion Committee
Chicago, IL

April 27, 2005

Daniel Ersoy, GTI

daniel.ersoy@gastechnology.org
Corrosion Rates in General

> When one calculates remaining life (half life) it is inversely

proportional to the corrosion growth rate (GR) assigned.

½ Life = (constant) • (Safety Margin) • (Nominal Wall Thickness)/(Growth Rate)

> Therefore the corrosion GR is very important in determining

the reassessment interval based on engineering analysis.
However, corrosion growth rates are difficult to predict and
measure and should be done with caution.

> Actual rates may be obtained from direct measurement of

wall thickness as a function of time (excavations, ILI runs,
etc.). However, this is the exception rather than the rule.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Corrosion Initiation Time

> Assuming external corrosion started at the time of

installation may result in a non-conservative rate estimate
since a coating system may delay onset of corrosion.

> On the other hand, corrosion rates often drop with time due
to corrosion film build-up which slows diffusion rates.

> Look for evidence of coating damage from installation.

Rock impingement or backfill damage probably happened
during install. Third party damage along the top of the pipe
may also be easy to identify and assign a date to.

> It is difficult to estimate the time period that a coating

provided an efficient barrier.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Growth Rate Estimation - General

> Time periods when CP systems are out-of-service or not

functioning normally are important to know to estimate
growth rates.

> The more surface are inspected, the more likely a larger pit
may be found leading to a higher growth rate.

> Pitting at a localized coating defect is usually more

aggressive than on bare pipe due to the cathode to anode
ratio.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Growth Rate Estimation - Default

> 16 mils per year (mpy) is the recommended rate (NACE RP

0502) for re-inspection intervals. This rate represents the:
– 80% confidence level of
– Maximum pitting rates for
– Long-term exposure (17 yr) for
– Underground corrosion test of
– Bare steel pipe coupons
– Without CP
– In a variety of soils.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Growth Rate Estimation - Default

> The RP states that 16 mpy can be reduced to 12 mpy if one

can show that CP levels of the pipeline had at least 40 mV
of polarization (considering the IR drop) since installation.

> The RP also allow statistically valid methods based on data

to be used for corrosion rate estimation.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Analysis and Default Rate Modification

> It is therefore very important to understand why certain soil

characteristics or properties are measured at each dig site.

> Corrosion Rates may be justifiably developed by:

– Collecting all the important soil parameters and comparing

them to historical/pre-assessment data on the pipeline; and

– Comparing the soil/pipe environment to already published/peer

reviewed data for underground/soil corrosion of steel.

> The operator can then make an informed decision as to an

appropriate corrosion rate and state the reasoning behind
the decision.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Corrosion in Soils

> Metal corrosion in undisturbed soils is generally very low

regardless of the soil composition, e.g. metal piles driven
into the soil.
> Corrosion of metal (steel) in disturbed soils (e.g., buried
pipelines that are backfilled) is strongly affected by soil
conditions as noted earlier.
> Soil changes its chemical and physical nature continuously
over time and seasonally.
> Factors contributing to the changes include precipitation,
plant growth and decay, roads, power lines, farming factors,
road salting, etc.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Characteristics to Consider

> Consider the following soil characteristics and environment

variables to assist in estimating corrosion rates:

– Chloride level
– Moisture content
– Oxygen content/Redox potential
– Soil permeability/texture
– pH/Acidity
– Temperature
– Soil resistivity
– Drainage characteristics
– Sulfate and Sulfite ion concentrations
– Microbiological activity
– Stray currents
– Spillage of corrosive substance/pollution

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Classification/Texture
> There are numerous ways to classify soils.
> Broad classifications by material are:
– Mineral Soils (<15% organic matter)
– Organic Soils
> Muck: 15-50% organic Matter
> Peat: >50% organic Matter

> Particle size classes include sands, clays, gravels and

stones, silts, loams, etc.
> By particle size:
– Gravel and Stones > 2 mm
– Fine Gravel 1-2 mm
– Sand 0.05-1 mm
– Silt 0.002-0.05 mm Loams (friable)
– Clay <0.002 mm

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Classification/Texture
> Clay has the finest particle size which reduces movement of air
(oxygen) and water, i.e. low aeration when wet. This may lead to
very low general corrosion, but increase local (pitting) corrosion by
setting up differential aeration cells.
> However the high plasticity (stickiness) of clay during shrink-swell
of the soil can pull off susceptible coatings.
> Clay also is susceptible to cracking during wet-dry cycling which
can help transport air and moisture down to the pipe surface.
> Sand promotes aeration and moisture distribution. Soluble salts
and gases (air/oxygen) can are more easily transported to the
metal surface. This may lead to greater general corrosion but also
produce less pitting.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Classification/Drainage
> Drainage can be affected by the soil texture, lay of the
land/inclination, seasonal precipitation, and the water table
height and variation.
> The affect of drainage on general corrosion and maximum
pitting rates has been studied for buried steel and is presented
below:

Drainage Class General Crsn Max Pitting Rate

(relative level) (mil/yr) (mil/yr)
Very Poor 2.3 > 17.7
Poor 1.5 9.1
Fair 2.5 12.2
Good 0.86 7.1

[Romanoff, M., Underground Corrosion, NIST 1957]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil pH
> For most soils, the acidity or alkalinity is generally stable due
to the buffering nature of the soluble minerals.
> Soils range in pH in the U.S. from pH 5 to 10. Surprisingly the
pH has a relatively small effect on pitting and general
corrosion compared to other variables.

pH of Soil Corrosivity Acid/Alkaline

< 5.5 Severe Acidic Soil
5.5-6.5 Moderate Slightly Acidic
6.5-7.5 Neutral (low) Neutral
> 7.5 None (low) Alkaline Soil

[Romanoff, M., Underground Corrosion, NIST 1957]

> Alkali Soils refer Alkaline soils with sodium and potassium
ions.
> Calcareous Soils refer to Alkaline soils due to calcium
carbonate.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil pH
> A study looked at 7590 underground sites and for pH found:

pH % Occurrence
< 4.0 0.1
4.1-6.0 5
6.1-7.0 10
7.1-8.1 27
8.1-10.0 55
> 10.0 3

[Kroon, D.H., Integrity Assurance Program for Underground Storage Tank Systems, NACE Conf. Paper CP-13, California, 1987]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Electrical Resistivity
> Soil electrical resistivity is a function of nature (class of soil),
amount of soluble salts, and moisture content.
> Ions (e.g., hydrogen, hydroxyl, and soluble salt cations and
anions) must migrate in the soil (the electrolyte) to permit the
completion of the corrosion reaction.
> Soil resistivity measures how easily ions move through the soil.
> Therefore a high soil resistivity suggests a low corrosion rate
because the rate of ion diffusion is low.
Soil Res. (ohm-cm) Corrosivity Rating of Buried Steel
> 20,000 Non-corrosive
10,000-20,000 Mildly corrosive
5,000-10,000 Moderately Corrosive
3,000-5,000 Corrosive
1,000-3,000 Highly Corrosive
<1,000 Extremely Corrosive
[Roberge, P.R., Handbook of Corrosion Eng. McGraw-Hill, 1999]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Electrical Resistivity
> A second and third study are presented below:

Soil Res. (ohm-cm) Corrosivity Rating of Buried Steel

> 10,000 Very Low
5,000-10,000 Low
2,000-5,000 Moderate
1,000-2,000 High
<1,000 Very High
[Miller, Foss, and Wolf, ASTM STP 74, 1981]

Soil Res. General Crsn Max Pitting Rate

(ohm-cm) (mil/yr) (mil/yr)
> 12,000 1.4 10.2
5,000-12,000 1.3 9.1
1,000-5,000 2.3 > 17.7
<1,000 2.48 12.2
[Romanoff, M., Underground Corrosion, NIST 1957]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Electrical Resistivity
> A fourth study looked at 7590 underground sites:

Soil Res. (ohm-cm) % Occurrence

< 3,000 16.1
3,000-9,990 37.1
10,000-19,900 20.7
20,000-49,900 16.5
>50,000 9.6

[Kroon, D.H., Integrity Assurance Program for Underground Storage Tank Systems, NACE Conf. Paper CP-13, California, 1987]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Conductivity
> Soil Conductivity is another measure of the electrical resistance
of the soil. It is measured in a solution of water.
> A high conductivity suggests a high corrosion rate (efficient
electrolyte).
> It is measured in Siemens/centimeter (S/cm), sometimes S is
referred to as “mho” since 1S = 1(Ohm)-1, and sometimes the
“/cm” is dropped.

Soil Conductivity (millimho/cm) Soil Corrosivity

< 0.1 Very Low
0.1-0.2 Low
0.2-0.4 Moderate
0.4-1.0 High
> 1.0 Very High

[Miller, Foss, and Wolf, ASTM STP 74, 1981]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Conductivity

> Another study looked at 7590 underground sites and found:

Conductivity (millimho/cm) % Occurrence

< 0.020 0.1
0.020-0.049 2.6
0.050-0.099 10.7
0.100-0.999 21.2
> 0.999 6.9

[Kroon, D.H., Integrity Assurance Program for Underground Storage Tank Systems, NACE Conf. Paper CP-13, California, 1987]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry - General

> Mineral soils are a group of primarily inert

combinations of oxygen, aluminum, silicon, and
iron (and other metals).
> The primary constituents of over 80% of soils are:
– Poly silicates: (Si3O84-) + K, Al, or Na
– Orthosilicates: (SiO44-) + K,H,AL,Ca, Fe, or O
– Metasilictes: (SiO32-) + Ca, Mg, or H
– Oxides: (SiO2, Fe2O3, Fe3O4)
– Calcite: (CaCO3)
– Hydrous Aluminum Silicates (Clays): (AlxOHy) (SixOy)
> Organic matter is another constituent

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry - General

> In well aerated soils the iron compounds are

generally in the Fe3+ state and produce red,
yellow, and brown colors.
> In poorly aerated soils the oxygen content is low
and the soils are gray in color due to the reduced
state of the Fe.
> Organic matter is usually limited to humid regions.
> For corrosion one is interested in the constituents
that are soluble in water:
– Basic forming elements: Na, K, Ca, Mg (raise pH).
– Acid forming elements: Carbonate, Bicarbonate,
Chloride ion, Nitrate, and Sulfate (lower pH).

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry - Chlorides
> Chlorides are of great concern for several reasons.
> Iron chloride is soluble and its formation promotes anodic
dissolution of iron or steel.
> The chloride ion can act as a catalyst and participate in the
corrosion process many times.
> Chlorides are known to also breakdown protective oxide
layers and they are a cathodic depolarizer.

Chloride (ppm) Corrosivity

>5,000 Severe
1,500-5,000 Considerable
500-1,500 Corrosive
100-500 T Threshold
[modified ACI-318 Building Code]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry - Chlorides
> A study looked at 7590 underground sites and found:

Chloride Conc. (ppm) % Occurrence

0-9 43.4
10-19 19.9
20-49 16.3
50-99 7.8
>100 12.6

[Kroon, D.H., Integrity Assurance Program for Underground Storage Tank Systems, NACE Conf. Paper CP-13, California, 1987]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry – Sulfates/Sulfide
> FeSO4 corrosion product is soluble but less aggressive than
the chloride iron for steel corrosion.

Sulfate (ppm) Soil Corrosivity

>10,000 Severe
1,500-10,000 Considerable
150-1,500 Detectible
0-150 T Negligible

[modified ACI-318 Building Code]

Sulfate is tied to the presence of Sulfate Reducing Bacteria

(SRB). This anaerobic bacteria reduces the sulfate:

SO42- + 8 Hads Æ S2- + 4H2O

Depolarizes
Cathode
Combines with Fe
and forms FeS

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry – Sulfates/Sulfide
> Unaerated soils with high SO42- and neutral pH breed SRB.
> Sulfide presence indicates possible FeS and SRB.
> A study looked at 7590 underground sites and found:

Sulfide Conc. (ppm) % Occurrence

0.000 66.2
0.001-0.999 23.9
1.000-4.999 8.0
>5.000 1.9

[Kroon, D.H., Integrity Assurance Program for Underground Storage Tank Systems, NACE Conf. Paper CP-13, California, 1987]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry – Moisture Content
> Moisture content contributes to the amount of soluble ions in
solution, resistivity, conductivity, etc.
> Generally, >20% moisture content is considered more
aggressive.
> A study looked at 7590 underground sites and for moisture
content found:
% Moisture Content % Occurrence
< 5.0 15.2
5.0-9.9 48.3
10.0-14.9 27.0
15.0-19.9 7.6
20.0-24.9 1.2
>25 0.7

[Kroon, D.H., Integrity Assurance Program for Underground Storage Tank Systems, NACE Conf. Paper CP-13, California, 1987]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry – Redox Potential
> Oxygen content in soils is important because:
– SRB require anaerobic conditions to thrive.
– Differential oxygen content in adjacent sections of soils can create
oxygen concentration cells and localized corrosion.

> Soil “Redox” (reduction-oxidation) potential [also called ORP or

oxidation-reduction potential) is measured with a probe that
contains a Pt electrode and a standard calomel electrode
(Hg/Hg2Cl2/KCl).
> The potential difference between the electrodes indicates the soil’s
dissolved oxygen.
> A more positive Redox potential (standard H scale) indicates more
aeration.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry – Redox Potential

Redox Potential
(standard H Scale) Aeration Soil Corrosivity
Negative not aerated Extremely severe
0 to 100 mV none to weak Severe
100 to 200 mV weakly aerated Moderate
200 to 400 mV aerated Slight
> 400 mV strongly aerated Noncorrosive
[Bradford, S., CASTI handbook of corrosion in soils, CASTI, 2000]

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Some Thumb rules to Help
Determine Growth Rates
> A general set thumb rules from the stated data can be developed:

SOIL CORROSIVITY FOR BURIED STEEL

Low Moderate Severe
pH >6.5 5.5-6.5 <5.5
Resistivity (ohm-cm) >20,000 5,000-10,000 <3,000
Conductivity (mS/cm) <0.2 0.2-0.4 >0.4
Chloride (ppm) <100 100-1,500 >1,500
Sulfates (ppm) <150 150-1,500 >1,500
Sulfides (ppm) Not Detectable 1-5 >5
% Moisture (% wt) <20% >20% >20%
Redox (mV Std. H) >200 100-200 <100

The affects of Soil Classification, Texture, and Drainage are difficult to quantify.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
 Summary
> It may be possible to combine:
– The data in this presentation and the thumb rules stated; with
– The direct observations and analysis of the soil conditions and
observed corrosion for a pipeline segment; and
– Prehistory from the Pre-Assessment
> And form a reasonable justification for a reduced corrosion rate
below the 16 mpy default rate.
> Recall that the 16 mpy is at a confidence level that indicates that is
is very likely that the value will be between ± 20% of the stated
value and that the value is the maximum pitting rate for long-term
corrosion of steel samples without CP.
> Therefore if the majority of one’s conditions fell in the “low” area of
the thumb rules and the observed corrosion on the line reinforced
this low growth rate, the assigned rate should be able to be
lowered below the 16 mpy by a justifiable amount based on the
particular situation.
> The more data collected and analyzed, the more reliable the
assigned corrosion rate will be, and the easier to justify.

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
 QUESTIONS ???

AGA Operations Conference – Corrosion Committee Meeting – April 27, 2005 Chicago, IL
Soil Chemistry Analysis and
Affects on Corrosion Rate

> AGA Operations Conference

Corrosion Committee
Chicago, IL

April 27, 2005

Daniel Ersoy, GTI

daniel.ersoy@gastechnology.org