PCA R&D Serial No.

3016

Test Methods for Water-Soluble Sulfate

in Soils

by Cyler F. Hayes

©Portland Cement Association 2007

All rights reserved
KEYWORDS
Chemical tests, codes, concrete durability, outdoor exposure, soil tests, specifications, sulfates,
sulfate attack, sulfate soils, testing

ABSTRACT
ACI 318 “Building Code Requirements for Structural Concrete” contains requirements on
constituent materials and mix designs for concrete structures in sulfate soils. The requirements
set exposure classes and mitigation methods based on the level of soluble sulfates in the soil.
However, the test method for determining the level of sulfates is not specified. This same
situation exists in other standards for concrete structures. The objective of this project was to
provide data on water-soluble sulfates in soils measured using four commonly referenced test
methods. These data were used to evaluate the potential assignment of exposure class based on
the test method used. Five soil samples were selected for evaluation to represent a range of
sulfate levels. For a given soil, the range of results found by the four methods varied significantly
relative to specified soluble sulfate limits, such that the same soil could be assigned a different
exposure class based on the test method used. This confirms that specification of sulfate
requirements should include reference to a standard test for soluble sulfates in the soil. It is
recommended that ASTM C1580 “Test Method for Water-Soluble Sulfate in Soil” be adopted as
the reference test method. Based on the findings in this test program, suggested improvements to
ASTM C1580 are outlined.

REFERENCE
Hayes, Cyler F., Test Methods for Water-Soluble Sulfate in Soils, SN3016, Portland Cement
Association, Skokie, Illinois, USA, 2007, 13 pages.

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TABLE OF CONTENTS
Page
Introduction 1
Objective and Scope 2
Test Program 3
Sample Acquisition and Preparation 3
Comparison of Test Methods 4
Test Results 6
Implications of Test Results 8
Observations on the Test Methods 8
Recommendations 9
Acknowledgements 10
References 10

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 Test Methods for Water-Soluble Sulfate
in Soils
by Cyler F. Hayes*

INTRODUCTION
American Concrete Institute (ACI) 318, Building Code Requirements for Structural Concrete,
contains requirements on constituent materials and mix designs for concrete structures in sulfate
soils (Table 1). The requirements set exposure classes based on the level of soluble sulfates in
the soil. However, the test method for determining the level of sulfates is not specified. This
same situation exists in other standards for concrete structures.

Table 1. ACI 318-05 Table 4.3.1 Requirements for Concrete Exposed to Sulfate-Containing
Solutions

Minimum design
Water-soluble Sulfate
Sulfate compressive
sulfate (SO4) in (SO4) in Cement type Maximum w/cm
exposure strength, f'c, MPa
soil, % by mass water, ppm
(psi)

No special
Negligible < 0.10 < 150 — —
type

II,
IP(MS),
150 to IS(MS),
Moderate 0.10 to 0.20 0.50 28 (4000)
1500 P(MS),
I(PM)(MS),
I(SM)(MS)

1500 to
Severe 0.20 to 2.00 V 0.45 31 (4500)
10,000

Very severe > 2.00 >10,000 V + pozz 0.45 31 (4500)

The ACI 318 sulfate exposure classifications apparently have their genesis in work of the
U. S. Bureau of Reclamation (USBR). The USBR’s extensive testing for sulfate resistance of

*
Senior Chemist, Materials Testing and Analysis, CTLGroup, 5400 Old Orchard Road, Skokie, IL, 60077-1030
USA (847) 972-3164, chayes@ctlgroup.com, www.ctlgroup.com.

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concrete resulted in requirements that have been published in their Concrete Manual for many
years (Fig. 1). It is generally assumed that, in establishing their published table limits, the USBR
determined soluble sulfates in soils using test procedures similar to their “Method of Test for
Determining the Quantity of Water-Soluble Sulfate in Solid (Soil and Rock) and Water
Samples,” the current version of which is dated May 1, 1973. However this is not fully
documented.

Figure 1. USBR Concrete Manual, 6th Edition, 1956.

As other organizations such as ACI adopted requirements based on the USBR table they
have not consistently associated the table limits with the USBR test method for water-soluble
sulfate in soils. Other test methods for water-soluble sulfates have been developed, but their
relationship to the USBR method has not been established.

OBJECTIVE AND SCOPE

The objective of this project was to provide data on water-soluble sulfates in soils as measured
using four commonly referenced test methods. These data were used to evaluate the potential
assignment of exposure class based on the test method used. Five soil samples were selected for
evaluation to represent a range of sulfate levels.
The five soils were evaluated for water-soluble sulfate content by the USBR method and by
three other test methods commonly used to assess exposure for sulfate attack on concrete placed
in direct contact with soil:
• United States Bureau of Reclamation, “Method of Test for Determining the Quantity of
Water-Soluble Sulfate in Solid (Soil and Rock) and Water Samples,” 1973.

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 • Canadian Standards Association (CSA) Test Method A23.2-3B, “Determination of Total
or Water-Soluble Sulphate Ion Content of Soil,” 2000.
• California Department of Transportation (Caltrans) Test Method 417-99, “Testing Soils
and Waters for Sulfate Content.”
• ASTM International (ASTM) C1580-05, “Test Method for Water-Soluble Sulfate in
Soil.”

TEST PROGRAM

This study consisted of the following tasks:

• Obtain representative samples of naturally occurring soils to represent a range of sulfate
content levels.
• Screen submitted soil samples for total sulfate content.
• Select five soils that potentially represent the breadth of sulfate exposure categories as
listed in the ACI 318-05 table.
• Evaluate the selected soils by the four test methods in triplicate.
• Report the findings.

Sample Acquisition and Preparation

Requests for samples were sent to a number of contacts in areas around the country with
emphasis on those areas reported to have soils with high sulfate contents1. The requests included
the following sampling procedures:
• Remove and set aside soil and vegetation that represents the top foot of soil. Samples
should be taken approximately one foot below ground level.

• Take a sample of at least five kilograms. If possible remove large rocks, roots, etc.
Double bag the soil in plastic and enclose in the plastic bucket provided. Label the
container.

• Although moist soil is acceptable, avoid areas that are excessively wet (greater than 20%
water or very wet liquid mud). Do not dry the soil prior to shipment.

• Do not add preservation materials such as methanol (commonly used for VOC and other
volatility studies).

• Do not homogenize the entire sample as this is to be done in the laboratory.

• Ship the sample within two days of sampling.

1
For protection against spread of invasive species and for pest management, the U.S. Department of Agriculture
regulates the movement of soils from designated areas of the country. This placed some restrictions on available
sites for soils with high sulfate contents.

3
 Upon receipt, large rocks, vegetation, and foreign debris if visibly present were removed
from submitted soil samples by hand. For each soil sample, a sub-sample was oven-dried at 45°C
for 24 hours and the percent volatile loss was determined. A portion of this oven-dried sample
was passed through a 50-mesh sieve. The total sulfate content was determined on the sieved
portion using the CSA test method. This screening procedure was used to insure that a range of
sulfate levels could be evaluated. If selected for continued study, the remaining oven-dried
sample was split into appropriate portions for each test method. Samples were prepared for
USBR and Caltrans test methods by passing through a No. 10 (2-mm) sieve. Samples were
prepared for the ASTM C1580 test method by continued oven drying at 110°C for another
24 hours prior to passing the sample through a No. 30 (0.6-mm) sieve. The percent volatile loss
for drying at 110°C was also determined (see Table 3).
A total of eleven soil samples were received from various locations throughout the United
States. After the prepared samples were screened for total sulfate content five were selected for
full evaluation.

Comparison of Test Methods

Key characteristics of the four test methods are given in Table 2. A primary factor is the
extraction ratio, and this is a point of debate in selecting and evaluating test methods for sulfate
in soils (Rebel et al. 2005). The USBR method is often quoted as having a water-to-soil
extraction ratio of 10:1 (mL/g). However, the method also states “Soil samples containing
gypsum may require a higher than 10:1 water-to-soil ratio to insure complete solution of all
gypsum present. If all gypsum is not in solution, the sulfate content of the extract will not reflect
the true percentage of sulfate in the soil.” There is no maximum limit on the extraction ratio
permitted, but guidance in the method indicates it is a function of total sulfate as estimated by
electrical resistivity testing. The CSA method also bases the extraction ratio on total sulfate,
specifically, nine times the determined acid-soluble SO4 to one part soil. The Caltrans method
uses a 3:1 ratio. The ASTM C1580 method uses two extraction ratios (~ 8:1 and ~ 80:1) and the
% SO4 is determined based on a combination of results for both solutions.
The duration of extraction also differs by test method. Temperature during extraction is
not clearly defined in the methods except that it is reasonable to assume standard laboratory
environments are intended as the default condition.
The methods also differ regarding sample preparation prior to testing, specifically soil
drying conditions. For this program all samples were initially dried at 45°C for 24 hours. This
was done to provide a consistent basis for comparison. ASTM C1580 has a specific drying
requirement which was followed prior to testing by that method.
Only the ASTM method contains a precision statement.2 The single operator coefficient
of variation of 4.4% indicates the results of two tests by the same operator on the same material
should not differ by more than 12.4% of their average. The multilaboratory coefficient of
variation of 21.2% indicates that results of two different laboratories on identical samples of a
material should not differ by more than 60% of their average. While it can be argued that this is a
rather imprecise method, the precision of the other methods is not documented.

2
It is assumed that the turbidimetric method was used for determination of the precision statement, but this is not
stated in the method.

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Table 2. Characteristics of Test Methods for Water-Soluble Sulfate in Soils
Test Method Sample Drying Measurement Extraction Ratio Precision and
Method Technique Water:Soil Bias
(mL:g)
USBR Air dry Electrical resistivity 10:1 (or higher if N/A
(May 1, 1973) (total sulfate screen) gypsum is
and present) agitated
Gravimetric for at least 6 hr.
CSA A23.2-3B Air dry at room Gravimetric (total [9 x (%SO4 by N/A
(2000) temperature and SO4 screen and acid-soluble
humidity soluble sulfate) method)]:1
agitated for 6 hr.
Caltrans 417 Not stated in test Turbidimetric* or 3:1 agitated for N/A
(March 1999) method Gravimetric (soluble 15 min.
SO4)
ASTM C1580 18 to 24 h @ 110°C Turbidimetric or ~8:1 and ~80:1 4.4% COV-S
(April 2005) ASTM C 114 agitated for one 21.2% COV-M
(soluble SO4) hr.
* A new edition of Caltrans 417, issued Nov. 2006, replaces the turbidimetric method with ion
chromatography

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TEST RESULTS
A total of eleven soil samples were received from various locations throughout the United States.
The prepared samples were screened for total sulfate content by CSA Test Method A23.2-3B
§5.1 (2000) which was run in triplicate. Five soil samples were selected for this study based on
their total sulfate content.3,4 Test results for total sulfate content of these samples are given in
Table 3 along with the standard deviation calculated from the three replicate tests.

Table 3. Soil Samples Selected for Full Evaluation

Volatile Loss Average Total SO4
After Oven Content of Oven- Standard
Sample
Drying at 45°C, Dried Soil, % by Deviation
% by Mass Mass
1733006 8.8 0.01 0.01
1733005 18.5 0.02 0.02
1733002 3.0 0.19 0.03
1733001 28.3 0.25 0.02
1825101 19.1 3.49 0.24

Each of the selected soil samples was tested for water-soluble sulfate by the four test
methods. Tests were run in triplicate. The results are given in Table 4 along with the standard
deviation of the three test results. The turbidimetric method was used for the Caltrans and ASTM
C1580 tests. Also, the CSA method permits total acid soluble SO4 to be reported for water-
soluble SO4 when the total SO4 is 0.2% or less.

3
Total sulfate contents for the six samples not selected for further testing were either negligible or non-detectable.
4
While the original intent was to obtain a greater number of soils with higher levels of soluble sulfate, this did not
materialize. Samples from several locations of anticipated high sulfate soils tested in the negligible range. Also, even
though the soil sample 1733001 had a total sulfate content that would rate its exposure as potentially “Severe,” the
measured water-soluble SO4 content was “Negligible” by all test methods. Consideration was given to “spiking”
samples with sulfate compounds, but there is no accepted practice for such an approach, especially when evaluating
differences in test methods.

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Table 4. Summary of Water-Soluble Sulfate Results for Selected Soils
Total Water-Soluble Sulfate Content, % SO4 by Mass of Soil
Volatile ASTM USBR CSA Caltrans
Sample
Loss, % Std. Std Std Std
by Mass Avg. Avg. Avg. Avg.
Dev. Dev Dev Dev
1733006 10.3 0.02 0.00 0.01 0.00 N/A N/A 0.01 0.00
1733005 20.8 0.02 0.00 0.00 0.00 N/A N/A 0.00 0.00
1733002 4.1 0.18 0.00 0.14 0.01 0.11 0.01 0.11 0.00
1733001 30.3 0.02 0.00 0.01 0.00 0.00 0.00 0.00 0.00
1825101 N/A 1.71 0.19 1.32 0.01 2.06 0.16 0.43 0.01

Based on these test results, the exposure class for a concrete placed in direct contact with
these soils was determined by the ACI 318 table limits and is shown in Table 5.

Table 5. Sulfate Exposure Based on Test Method

Average Water-Soluble Sulfate Content
Expressed as %SO4 by Mass of Soil
(ACI Exposure Class)

Sample ASTM USBR CSA Caltrans

0.02 0.01 0.01* 0.01

1733006
(Negligible) (Negligible) (Negligible) (Negligible)

0.02 0.00 0.02* 0.00

1733005
(Negligible) (Negligible) (Negligible) (Negligible)

0.18 0.14 0.11 0.11

1733002
(Moderate) (Moderate) (Moderate) (Moderate)

0.02 0.01 0.00 0.00

1733001
(Negligible) (Negligible) (Negligible) (Negligible)

1.71 1.32 2.06 0.43

1825101
(Severe) (Severe) (Very Severe) (Severe)

* Total acid-soluble sulfate per the CSA method.

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DISCUSSION

Implications of Test Results

Several observations can be made regarding these results. The ASTM method gave consistently
higher water-soluble SO4 results than the USBR method, although the differences were not
significant enough to impact selection of exposure class according to ACI 318-05 for the samples
tested. The Caltrans method gave consistently lower results, again with no impact on the
selection of exposure class.
Actually, Table 5 indicates the exposure class designation for all samples was relatively
consistent based on the different test methods even though the range of water-soluble SO4 values
for a given soil sample could be significant. With the exception of the sample 1825101, there
were no differences in exposure class based on test method. This reflects the relative large range
of water-soluble SO4 values specified for each exposure class as much as it does any close
correlation between methods. It also was somewhat fortuitous in that results for the samples
tested fell within classification brackets, and were not “borderline.”
Even considering the above discussion, it is quite possible that results based on the
different methods could have resulted in assignment of a different exposure class for the samples
tested. Consider sample 1733002 for example. Within the precision of the ASTM test method,
the sample could have tested higher at 0.20% SO4, which would have moved it to the “Severe”
classification. Assuming a similar precision for the Caltrans method, the sample could have
tested at 0.09% SO4, which would have moved it to the “Negligible” classification. It is very
likely that samples “on the border” of classification ranges would be impacted by the test
method, particularly if one laboratory used ASTM C1580 while another laboratory used Caltrans
417.
Clearly a test method should be specified when sulfate requirements such as those in ACI
318-05 are invoked. One of the questions that instigated this test program was whether the test
methods being used are consistent with the USBR method that served as the basis for the
exposure classifications in ACI 318 and other standards. None of the methods used in this project
gave identical results to the USBR method, but there was general consistency between methods.
Given that it is a consensus method that can be readily updated; the ASTM method
appears to be promising as a reference test for sulfate exposure requirements. The ASTM test
results, although somewhat higher, were reasonably consistent with the USBR method test
results over the range of soils tested. Within the practical application of such tests, it would be
reasonable to use the ASTM method in conjunction with the ACI 318 sulfate requirements
without change to the table limits.

Observations on the Test Methods

The legacy USBR test method was developed for internal use at the Bureau and is not well suited
to current general specifications for concrete structures. Critical provisions are not defined in
“specification language” that would be enforceable in contracts or clear in dispute resolution
cases. Also, the method permits extraction at higher water-to-soil ratios than the 10:1 standard
extraction ratio. While this is not technically unjustified, the method does not have a limit on the
extraction ratio, nor does it require reporting of the ratio used.

8
 The Caltrans method (California Test 417) is an internal method developed by the
California Department of Transportation. As such it is consistent with California DOT
specification requirements. The 3:1 extraction ratio is the lowest of all the methods conducted in
this program and consistently gave the lowest results for water-soluble SO4.
The CSA method (A23.2-3B) is a consensus method used in Canadian standards for
concrete structures. It includes a “built in” screening mechanism whereby total acid-soluble
sulfate is first measured. If the total sulfate value is 0.2% or less, no further testing is required.
This screening method is efficient and useful, although such screening can be included in a
specification or practice, and is not essential to a test method. The extraction ratio is variable,
defined as a function of the total sulfate level.
The ASTM method (C1580) is also a consensus method, and was developed relatively
recently with the first edition published in 2005. As such, it is consistent with use in current
specifications. The method uses two extraction ratios with limiting ranges for values determined
at the different extraction and aliquot levels based on sulfate solubility calculations. An
advantage of the ASTM method is that sample preparation, especially the drying temperature,
which can have a significant impact on the sulfate content of a soil, is clearly defined. ASTM
C1580 allows both turbidimetric and gravimetric measurement techniques to be used. However,
because turbidimetric measurements can “drift” from the actual value over time, the results must
be corrected with standards (turbidity blanks) periodically. The ASTM method does not require
periodic correction checks, which makes it susceptible to drift. The gravimetric method is not
susceptible to drift because it measures the weight of barium sulfate formed.

RECOMMENDATIONS
Based on the test results from this project the following recommendations are made:
• ASTM C1580 should be proposed as the standard test method for determination of water-
soluble SO4 levels in soil for assignment of sulfate exposure limits in ACI 318-05 or
similar standards.
• ASTM C1580 should be revised to:
o Discontinue the use of the turbidimetric measurement technique as the default
method and require gravimetric measurements (or qualified ASTM C114
methods) as the default.
o Clear provisions should be added to require correction of readings to account for
drift of the instrument if the turbidimetric technique is used as an alternate
method.
o Update the precision and bias statement based on revisions to the measurement
techniques.
o Add a note to recommend that total acid-soluble sulfate values be used for
screening.

ACKNOWLEDGEMENTS
The research reported in this paper (PCA R&D Serial No. 3016) was conducted by CTLGroup
with the sponsorship of the Portland Cement Association (PCA Project Index No. 05-10). The
contents of this report reflect the views of the author, who is responsible for the facts and

9
accuracy of the data presented. The contents do not necessarily reflect the views of the Portland
Cement Association.
Staff of California Portland Cement Co., Holcim (US), and TXI were instrumental in
providing soil samples for this project. The author would like to thank Raja Naamane, Cecylia
Wedzicha, Linval Williams, and Rick Stevenson of CTLGroup for their contributions to this
project.

REFERENCES
Rebel, B.; Detwiler, R.; Gebler, S., and Hooton, R., “The Right Sulfate Test Makes a
Difference,” Concrete International, February, 2005, pages 49 to 52.

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