~George R.
Alther1
Methylene Blue Test for Bentonite Liner Quality Control
REFERENCE: Alther, G. R., "The Methylene Blue Test for Bentonite
Liner Quality Control," Geotechnical Testing Journal, GTJODJ, Vol.
6, No. 3, Sept. 1983, pp. 128-132.
ABSTRACT: An in-situ procedure for evaluating the quality of soil and
soil/bentonite admix liners is described. The methylene blue (MB) test
is based on the principle that cationic dyes base exchange in proportion
to the clay content in soils or clay slun-ies. The number of exchangeable
ions present is determined by replacing these ions with methylene blue.
The MB test is the accepted standard of measurement of clay levels
in bentonite bonded molding sands used in the foundry and steel indus-
tries. Lab tests have shown that the methylene blue method is useful to
test the quality of bentonite liners, bentonite slurries, and soil bentonite
'/- backfills forslurry tynches.
~ i t y contL.ol,slu~mes, so~lls,clay, porosity
The purpose of this article is to (1) determine the usefullness of
the methylene blue (MB) test for quality control of soil/bentonite
liners, soil/bentonite backfills (for slurry trenches), and bentonite
slurries and (2) compare the dispersing properties of sulfuric acid
and tetrasodium pyrophosphate (TSPP).
When landfills, water, or waste lagoons are designed, bentonite
is often included as a liner. Its function is to decrease the porosity
of the natural soil, thereby, preventing water or other liquid wastes
from entering the groundwater. When such liners are installed, it
is necessary to check the quality of the installation procedure to in-
sure that the amount of bentonite specified is deposited and mixed
properly. One method of testing is the methylene blue adsorption
test. A statistical sampling design may be carried out by using the
method outlined in Ref 1 with subsequent testing of the methylene
blue uptake of the specimens. Until now, the dispersant used for
the methylene blue test was sulfuric acid. In the foundry industry it
has long been recognized that TSPP is a better dispersant than sul-
furic acid. The two methods were run side by side to substantiate
these claims.
Finally, the sulfuric acid version of the methylene blue test has
been used for many years to determine the amount of bentonite in
drilling muds in accordance with ASTM Test for Methylene Blue
Index of Clay (C 837), because it eliminates the influence of organ-
ics on the test. In order to facilitate the testing of bentonite slurries
and soil/bentonite backfill mixes, the use of TSPP as a dispersant
was investigated.
1Geologist, International Minerals and Chemical Corporation, 17350
Ryan Rd., Detroit, MI 48212.
0149-6115/83/0009-0128502.50
128
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Scope
The MB test is a useful tool to quickly and accurately determine
the amount of bentonite in a soil/bentonite mix. It has been described
for the testing of clays in ASTM C 837 and American Petroleum In-
stitute (API) RP 13B. The test is based on the principle that cationic
dyes, such as methylene blue, will exhibit a base exchange in propor-
tion to the bentonite content in a dispersed clay-soil suspension. The
number of exchangeable ions present is determined by replacing
them with methylene blue dye. Monolayer coverage of the clay as de-
termined by the MB uptake at complete clay flocculation differs
from the concentration at which adsorption of the MB cation is
equivalent to the cation exchange capacity, thus, the MB test cannot
be substituted for this test [2].
The test involves weighing out 5 g (dry weight) of the soil/benton-
ite mixture and adding it to a 2% solution of TSPP, heating it, and
vigorously mixing it with a magnetic stirrer to form a slurry. Then
adding known quantities of methylene blue until a drop of the
slurry, placed on a filter paper, allows a light blue halo to bleed into
the paper around the drop. This end point indicates that the benton-
ite has taken up all of the methylene blue that it can hold and that
there is now no free methylene blue in the suspension. The TSPP
acts as a dispersant and replaces most of the exchangeable cations
with sodium, making it homogenous and monoionic. The simple
nature of this test makes it easy to adapt to field test conditions.
Materials Required
The methylene blue crystals should be zinc free United States
Pharmacopeia (USP) grade having a formula weight of 373.9. 2
Varying the grade of MB crystals will undoubtedly affect the result-
ing answer. A description of solution preparation is included in the
Appendix.
A balance, heater, magnetic stirrer plus magnets, a titration
setup, and Wattman's filter paper (hardened No. 50) are needed for
the test (Fig. 1).
Testing Procedure
1. Using a triple beam balance (sensitivity = 0.02 g), a carefully
prepared, oven dried, representative soil or soil/bentonite specimen
weighing 5 g is placed into a 125 to 250 mL Erlenmeyer flask. The
specimen should be sieved with the 4.75-mm (No. 4) and 212-#m
2Zinc free MB crystals can be obtained from Matheson Coleman Bell of
Norwood, OH.
©1983 by the American Society for Testing and Materials
 ALTHER ON THE METHYLENE BLUE TEST 129

ditional 2 min. Place another drop on the filter paper. If no halo ap-
pears, follow the previous procedure. If the halo persists, then the
end point has been reached. The test result is the number of milli-
litres of MB solution required to reach the end point.
8. The test should first be conducted on native soil specimens
from several locations of the excavated and prepared site to establish
the background and then on a mixture of soil-bentonite (that is, the
desired percentage of bentonite versus soil. The specimens should
be oven dried at ll0°C for 3 h, and ground to 75-#m (No. 200) mesh
size, if necessary, to increase the accuracy of the test. A forced air
dryer could also be used, whereby, the specimen is dried for 5 min at
130°C. With a typical microwave oven setup, drying time is also 5 to
10 rain. After mixing in and compacting the bentonite/soil liner,
specimens are then retrieved from the same sites as the background
specimens and tested with the MB test to establish if the appropriate
percentage of bentonite has been applied. Organic material such as
twigs, roots, and leaves should be removed as much as possible be-
fore grinding the specimens to reduce interference with the test. If
the soil contains clays, the blank (untreated soil) may require a con-
siderable amount of MB solution to reach an end point. This can be
anticipated by first running a liquid limit test on the soil. If the soil is
already rich in clay, that is, it has a high liquid limit, only 2 g of soil
should be tested.
9. Organic matter will interfere with the test and may render it
useless if it is not dealt with properly. The amount of organics is us-
ually low in soils used for landfill liners, but the situation could arise
in certain remote locations. It may be advisable to run a loss on igni-
tion on the soil while the lab work is conducted to determine whether
FIG. 1--Field setup for the methylene blue (MB) test. hydrogen peroxide extraction is required. Hydrogen peroxide ex-
traction is done the following way:
(No. 70) sieve, and the particles should be separated with a rubber
Take 10 to 20 g of soil and place it in a 500 mL beaker. Add 50 to
pestel and mortar.
100 mL of 30% hydrogen peroxide and start boiling the solution.
2. A 2%, 50-mL hydrated TSPP solution is added to the S-g
Watch that the solution does not overflow, and stir occasionally.
specimen, and the slurry is thoroughly dispersed with a magnetic
Boil off most of the hydrogen peroxide, then add 50-mL distilled
stirrer.
water, mix it with the soil, and boil it off. This will ensure that no
3. The TSPP clay slurry is placed on a hot plate, and after the in-
hydrogen peroxide remains to interfere with the MB test.
itial boil is reached, is boiled for 5 min. A slow rolling boil is sug-
gested so that an excessive amount of water is not lost. The flask 10. To insure accuracy of the test, a supply of weii mixed benton-
should be checked for clay that may be sticking to the flask sides ite soil should be stored to be used for quality control.
from the reaction.
If clay adheres to the flask, the flask should be swirled and vigor- Results and Discussion
ously shaken to force the clay into the solution. An ultrasonic scrub-
ber could also be used, whereby the specimen is scrubbed for 5 min Lake Michigan sand with a porosity of 35% was mixed with sev-
[3]. Tests have shown the use of heath to be superior, however. eral different amounts of bentonite, and an MB test was then per-
4. Remove the flask and cool to room temperature. formed. This was to simulate a liner or slurry wall backfill situation.
5. Place the flask on a magnetic stirrer, add a stirring bar, and The data are presented in Table 1 and are shown graphically in Fig. 2.
mix the solution for 30 to 60 s. In Table 1 the calculated data are shown first. These calculations are
6. Begin titration of MB solution. Make sure that the filter paper based on the fact that MB uptake for the bentonite alone is 92 mL/g
does not lie on any surface by placing the paper over a beaker and us- and is zero for the sand (using TSPP as dispersant). If we take 1%
ing just the edge of the paper that overhangs the beaker. Add enough bentonite in 5 g of soil, this amounts to 0.05 g, which is 1/20of 1 g,
MB solution until the color of the mix turns from a greenish blue to a and 92 mL/20 g = 4.6 mL/g, and so forth.
dark blue. For most soils this will represent at least S to 30 mL of MB A comparison of calculated values versus measured values (Table
solution. 1) was made by using the standard error of measurements proce-
7. After the first addition of MB solution, allow the slurry to mix dure. Since all calculated values fell in a relatively straight line, and
on the magnetic stirrer for 2 rain. With the use of an eyedropper, the intercept of the line is at zero, a linear regression was not neces-
pull a few drops from the slurry and place one drop on the filter sary, and the calculated results were used instead. The standard er-
paper. Deposit any excess back into the flask. Watch for a light blue ror of estimate turns out to be 2.14 mL, which is large at the low
halo. If no halo appears, add 1 additional mL of MB solution. Mix percentages but becomes much smaller at the high percentages.
for 2 min and repeat above. If and when a blue-green halo appears, Since in a soil of pure sand the admixture is usually at least 7%,
do "not" add more MB solution but allow the slurry to mix for an ad- where the MB uptake would be 32 ___2 mL, this error is acceptable.

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130 GEOTECHNICAL TESTING JOURNAL

TABLE 1--Methylene blue exchange data on sand~bentonite mix. TSPP is evidently a much better dispersant in a soil/bentonite mix
than sulfuric acid (see Table 1) giving a consistently higher MB
Calculated Measured Measured MB uptake, For this reason the relationship of pH to MB uptake was
Bentonite, Bentonite in 5-g MB Uptake, MB Uptake Uptake (sulfuric
% Soil/Bentonite, g mL (TSPP), mL acid), mL investigated.
Table 2 and Fig. 3 show the MB uptake for western (swelling so-
1 0.05 4.6 4 2 dium) and southern (nonswelling calcium) bentonite with increas-
2 0.1 9.2 9 5 ing pH (Curves a and b). The reason both types of bentonites are
3 0.15 13.8 13 6
4 0.2 18.4 18 11 shown is because MB uptake of swelling bentonite cannot be deter-
5 0.25 23 20 16 mined accurately between a p H of 6 and 9 because the clay platelets
6 0.3 27.6 24 22 would aggregate rather than disperse, causing low results. This
7 0.35 32.2 32 24 graph shows clearly that the MB uptake, and, therefore, cation ex-
8 0.40 36.8 34 26 change capacity, increases with increasing pH to a peak at a pH of
9 0.45 41.4 42 28
10 0.50 46 44 31 10, followed again by a decrease. At a low pH there are more un-
11 0.55 50.6 50 33 dissociated hydroxyl groups, resulting in a low cation exchange ca-
12 0.60 55.2 52 35 pacity. A high pH causes more hydroxyl ions to dissociate, increas-
13 0.65 59.8 62 40 ing the number of negatively charged clay platelets and resulting in a
14 0.70 64.4 64 43
15 0.75 69 71 44 higher cation exchange capacity. The acidic pH was achieved with
sulfuric acid, and the alkaline pH with TSPP. To achieve a pH of t2,
NOTE: The methylene blue uptake of 1-g bentonite is 92 mL, and of 1-g some sodium hydroxide had to be added. For Curve c hydrochloric
sand is zero. The standard error of estimate iss = x/~ (yi -- y i ' ) 2 / n -- 2 = acid and sodium hydroxide were used instead of sulfuric acid and
2.14.
TSPP. Hydrochloric acid causes higher readings, suggesting it has a
less damaging effect on the edges of the clay platelets then sulfuric
acid. It may also disperse the platelets better than sulfuric acid (the
reason sulfuric acid is used in the industry is to destroy the influence
of organics). Sodium hydroxide is not a dispersant, but only strips
the surface of the clay platelets, which is why the MB uptake with so-

TABLE 2--Methylene blue uptake of sodium and calcium bentonites,

variations with p H and reagent.

Calcium Bentonite,
Sodium Bentonite, Calcium Bentonite, mL/0.5 g (used
mL/0.5 g (used mL/0.5 g (used hydrochloric acid
sulfuric acid and sulfuric acid and and sodium
pH TSPP) a TSPP)" hydroxide)"

2 27 18 28
4 34 19 31
GO- 5 40
6 ,.. "34 iii
8 36
D 9 ;;
, gO' 10
11
53
40
56 34
29
12 25 30 ...
4O-
aTo obtain a pH of 12 some sodium hydroxide had to be added.

30-

50
SOD~UW(o)~. CALCU
I M~b)
ZO- - - AVERAGE STRAIGHT L I N E
THROUGH MEASURED DATA.
THIS LINE FITS STRAIGHT
THROUGH THE CALCULATED
POINTS.
20"

10- d
't \h
0
~4
pH

°./o BENTONITE IN l 8ENTONITE/LAK~Z MICHIGAN SAND MIX

FIG. 3--Methylene blue uptake of sodium and calcium bentonites as
related to p H and reagent. For Curves a and b, sulfuric acid and TSPP
FIG. 2--Graph showing methylene blue equivalence versus percent of were used to adjust the pH. For Curve c, hydrochloric acid and sodium
bentonite, based on 5-g bentonite. hydroxide were used.

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 A L T H E R ON T H E METHYLENE BLUE TEST 131
dium hydroxide is lower than with TSPP. It required much more A e
stirring action when hydrochloric acid, sulfuric acid, and sodium
hydroxide were used than with TSPP. It is concluded that the ion ex- 30

change capacity (or MB uptake) is a function of pH, the reagent used, z5 Z~

and the dispersive action of the reagent.

m t~
r5
Field Example
~,o ,o

The value of the MB test is illustrated by the following hypotheti- 5

cal field example. The design mix using the Lake Michigan sand re-
quires a 5% bentonite admix. Referring to Table 1, this corresponds
to a theoretical MB uptake of 23 mL/g. Based on the results of three
tests at one location, the measured uptake is only 20 mL/g. Accord-
mud content using TSPP as dispersant and (B) relationship between M B
ingly, the actual bentonite/soil composition is only 2o/23 × 5% or
uptake and various percent bentonite in the mud.
43% and this indicates the need to increase the bentonite content in
the mix.
Table 3 shows a variety of soils where, when possible, the liquid
limit was also determined. It was difficult to predict the MB uptake
that could be expected, even by hydrogen peroxide washing, be-
cause there appeared to be other interferences with the MB test.
However, the method can be useful if performed properly. There is a
correlation between MB uptake and liquid limit, which is expected
because MB uptake increases with increasing liquid limit; in other
words, as the amount of clay in the soil increases, so does its ion ex-
change capacity.
It is important to realize that if a specimen from a soil/bentonite
liner is collected, it should be extracted with a soil sampling tube
penetrating the liner, and then mixed. This will assure that a vertical
distribution profile of the bentonite in the liner is obtained.
Use of TSPP Instead of Sulfuric Acid for Bentonite Muds
I
O 2 4 6 B tO
°/aI~IENTONITEMUD
MILLILITERS BENTONITE MUD
FIG. 4--(A) relationship between MB uptake and increasing bentonite
The test methodology included the following:
Drilling mud was made using the API RP 13B, that is, 22.5-g
bentonite was mixed with 350 mL of water (6.43% bentonite).
Several different quantities were then extracted and mixed into a
50-mL TSPP solution (I, 2, 3, 4, and 5 mL). Figure 4 shows that
the relationship between MB uptake and increasing mud content
of the TSPP is that of a straight line. In Fig. 4, instead of keeping
the percent bentonite constant (6.43%), it was varied to determine
that relationship. With a syringe, the necessary amount (2 cm 3)
is extracted and put into the TSPP solution and dispersed with a
magnetic stirrer. Again a straight line resulted. The data closely
followed a straight line and suggest that the TSPP method can also
be used to test bentonite slurries during slurry wall construction.

Until now, the percentage of bentonite in a drilling mud, and,

therefore, in slurries used for slurry wall construction, has been de- Conclusion
termined with the use of sulfuric acid as a dispersant. Tests were The methylene blue test, using TSPP as a dispersant, is a useful
therefore performed using TSPP to test the value of this revised MB method to determine the methylene blue uptake of soils. Therefore,
method for mud application. the methylene blue test can be used as a means for controlling the ac-
curacy of bentonite additions in soil liners and slurry wall backfills.
The method is also useful to determine the percent bentonite in a
TABLE 3--Examples of soils with and without organics (used 5-g bentonite slurry such as a drilling mud or slurry wall mud.
soil unless otherwise h~dicated). The accuracy of the MB uptake and the level of cation exchange
capacity are dependent on the dispersant and stripper that is used.
MB Uptake TSPP when added to distilled water to raise the pH to 10 gave the
5% Soil/ highest Cation Exchange Capacity (CEC), much more so than so-
Liquid Straight Soil, Bentonite Mix, dium hydroxide, hydrochloric acid, and sulfuric acid at pH's rang-
Sample Identification Limit, % mL/g mL/g ing from 2 to 12.

St. Louis, MI 18 15 36
St. Louis, MI 15 12 32
Allen Park, MI 24 22 41 APPENDIX
Backyard soil ... 16 53
(LOI ------16.8%) ~ (+8% bentonite)
St. Louis MI (10-g . .. 10 33 Preparation of Methylene Blue Solution
sand) (+8% bentonite)
St. Louis, MI ... 20 62 The MB crystals purchased should be USP grade and have the
(sand, used 10g) (+8% bentonite) formula weight of 373.9, and the label on the bottle should specify
Backyard soil ... 10 33 that it is zinc free. Varying the grade of MB crystals will vary the re-
(LOI = 7.3%) ... sultant answer. Keep the crystals of MB out of direct light.
Michigan (2-g "63" "36" 48 For each litre of solution desired carefully weigh out 3.739 g of MB
soil)
crystals, USP grade, on a Mettler balance. Using a clean funnel,
aLOI is loss on ignition. transfer the cyrstals to a 1000-mL volumetric flask. Add approxi-

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132 GEOTECHNICALTESTING JOURNAL
mately 500 mL of distilled water. Stir for 1/2 h with a magnetic stir-
rer. Accurately fill the flask to the calibration mark with additional
distilled water. Remove stirring bar during this measurement. Stir
for another 1/2 h.
If a magnetic stirrer is not available, mixing can be done in a con-
ventional 1000-mL beaker. Care must be taken to avoid loss of solu-
tion because of splashing during the mixing process. The solution
should be transferred back to a volumetric flask after the first mix-
ing cycle for the accurate addition of distilled water to the 1000-mL
level.
Transfer the solution to a dark brown glass container for storage
and allow to stand for 12 h before using, and maintain stirring. Keep
the prepared solution out of direct light and away from temperatures
above 32.2°C (90°F). The storage life of MB solution is approx-
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imately three months. The solution should be stirred for 30 min be-
fore every run (that is, every morning).
References
[1] Grossman, M. A., Goodwin, B. A., and Breemer, P. M., "Statistical
Analysis of Trace Metal Concentrations in Soils at Selected Land Treat-
ment Sites," in Land Disposal: Hazardous Waste: Proceedings of the
Seventh Annual Research Symposium, EPA-600/9-81-002b, En-
vironmental Protection Agency, Cincinnati, OH, 1981.
[2] Van Olphen, H., An Introduction to Clay Colloid Chemistry, Wiley,
New York, 1977. p. 318.
[3] Graham, A., "How to Perform a Methylene Blue Test," Modern
Castings, May 1982, p. 53.