Published July, 1961
DIVISION II-SOIL CHEMISTRY
Buffer Methods for Determining Lime Requirement of
Soils With Appreciable Amounts of Extractable Aluminum1
H. E. SHOEMAKER, E. O. McLEAN, AND P. F. PEATT2
ABSTRACT
Studies were conducted to determine why certain soil
test methods fail to indicate the actual lime requirement
in many Ohio soils. Samples of 14 soils from various areas
of the State were collected for study. The soils were
incubated with various rates of applied CaCO3 to deter-
mine actual lime requirement of each soil. Attempts were
made to find laboratory methods that would accurately
indicate the lime requirement of each. For these soils
the Woodruff method had indicated only about half the
amount of the actual lime requirement. The Mehlich
triethanolamine method indicated accurately the amount
of lime required for the unlimed acid soils. However,
this method indicated too high a lime requirement on
soils partially limed. Subtraction of the acidity measured
above pH 6.8 by the triethanolamine method and then
addition of the extractable Al, gave a very good indication
of lime needs on all soils not limed above neutrality
regardless of lime additions. Addition of extractable Al
to total bases and triethanolamine-measured acidity to
pH 6.8 gave nearly constant cation-exchange capacities
of soils regardless of lime additions. These studies have
led to development of an improved soil test buffer method
for rapid routine laboratory analyses. It appears to be
adequate for indicating lime needs of soils regardless of
extractable (soluble) Al present.
M cLEAN ET AL. (3) OBSERVED that the Woodruff buffer
method (9, 10) for determining the lime requirement
of acid soils did not give an accurate indication of the
actual lime needed to bring certain Ohio soils to a
favorable reaction for plant growth, i.e., pH 6.4 to 6.8.
Initial investigation and observation suggested that the
soils which gave the greatest discrepancy between actual
lime needs and test-indicated needs were those with the
most extractable Al in them (3).
'Published with the permission of the Director of the Ohio
Agr. Exp. Sta. as Journal Article No. 65-60. Presented before
Div. II, Soil Science Society of America, Lafayette, Ind. Aug.
6, 1958. The results were used in part by the senior author in
partial fulfillment of the requirements for the Ph.D. degree
in 1959 from the Ohio State University. Received Aug. 18,
1960. Approved Nov. 23, 1960.
2
Extension Agronomist and Professor, Ohio State University,
and former Assistant Professor, Ohio State University, now
Associate Chemist, California Agr. Exp. Sta., Riverside, respec-
tively.
The objectives of this study were: (1) to determine some-
of the reasons why certain soil test methods fail to measure
adequately the lime requirement of many Ohio soils, (2)
to examine in some detail the Mehlich triethanolamine
method in relation to extractable Al, and (3) to develop
an improved buffer method of rapid testing for lime
requirement of acid soils whether high or low in ex-
tractable Al.
MATERIALS AND METHODS
Fourteen relatively acid Ohio soils were chosen for study.
Genetic and acidic properties of these soils are listed in
table 1. The soils were predominately Gray Brown Podzolic-
and hydromorphic soils. They represented a range in pH
from 5.1 to 4.3, in lime requirement from 3.1 to 16.7 tons
per acre3, and in extractable Al from 1.4 to 8.0 me. per 100'
g. of soil.
To aliquots of each of these soils was added CaCO3 at
rates of 0,2,4,6,8,10,12, and 14 tons per acre. Each treatment
was applied to duplicate samples. After thorough mixing, the
soils were moistened to field capacity and placed in open
glass containers. Additional water was added frequently to
replace that which evaporated. Periodically the soils were
allowed to air-dry; clods were crushed, and water was again
added to bring the soils to field capacity. This cycle of
wetting, moist incubation, drying, crushing, and rewetting
was continued for 17 months. Then the soils were air-dried,
crushed, and stored in closed containers.
The various soils with the different levels of liming, those
limed above pH 7 excluded, served as a basis for evaluating
several different methods of determining soil acidity. The pH
of each soil was determined by means of the glass electrode in
a soil/water ratio of 1. The resulting pH was plotted against
the amount of CaCO3 added to a given soil. The amount
of CaCOa in tons required to bring 2,000,000 pounds of a.
soil to pH 6.8 was arbitrarily defined as the lime requirement
in tons per acre by the CaCOs incubation method.
Each of the soils with and without lime was also analyzed
for acidity by the triethanolamine (TEA) buffered BaCL
method of Mehlich ( 6 ) . Since this TEA method involves
equilibrating the buffer and soil at or slightly below pH 8.0,
considerable acidity is neutralized above the pH 6.8 which
was arbitrarily chosen as the basis for computing lime require-
ment. This additional acidity results from the pH-dependent
charges resulting from SiOH dissociation (8) among others
(2). This acidity (between pH 6.8 and 8.1) was determined'
graphically by difference between the TEA indicated value at
pH 8.1 and the actual value at pH 6.8 on the CaCO3 titration
curves. These quantities were then deducted from the regular
Mehlich TEA values to give values designated as Mehlich
TEA adjusted to pH 6.8.
The extractable Al was obtained by extraction with NH4OAc
at pH 4.8 and determined by the thioglycolic acid adaptation
'Acre is herein used to designated 2,000,000 pounds of
oven-dry soil.
 SHOEMAKER ET AL.: BUFFER METHODS FOR DETERMINING LIME REQUIREMENT OF SOILS HIGH IN AL 275

(a) Limed and Unlimed Soils (b) Unlimed Soils

4 8 12 16 0 4 8 12 16
Lime requirement (CaCOi •+• i n c u b a t i o n ) — '^

(d) Limed and Unlimed Soils

Figure 1—Titration curves for representative soils used

in this study. pH after 17 months moist incubation
vs. lime added.
f?,l2
•of the aluminon method as described by McLean et al. (3)
and Chenery (1), respectively.
Exchangeable Ca, Mg, and K (total bases) were determined
by extraction with l.OIV neutral NH4OAc, ashing, removal of
Fe and Al by precipitation and filtration, removal of PO4 by
adsorption on anion resin, and finally determination of the ^ 4
Regular TEA pHS.I o
•cations in a Beckman D.U. flamephotometer. Acidity >pH 6.8 -
A new buffer mixture was developed which gave a near- deducted in
j
linear depression in pH with the degree of acidity of the 0 4 8 12 16 0 4 8 12 16
soils as determined by CaCO3 incubation. The new buffer
Lime requirement (CaC03 + incubation) - VA
is much weaker than cither the widely used Woodruff or the
Mehlich buffers (5). Hence, it does not react with as much Figure 2—Acidity of the various soils determined by the
of the soil acidity as the other two buffers, but the fact that regular and adjusted Mehlich TEA methods compared
this buffer is weaker makes it change pH more readily in
response to the acid reacting with it. The result is a much to the lime requirement determined by CaCO3 incuba-
more accurate rapid test than the Woodruff ApH method and tion.
•one that is equally as good as the much slower Mehlich
(titration) method (5). data for a representative number of the soils are plotted
A procedure for rapid testing of soils for lime requirement in figure 1. Of the soils for which data are not plotted, the
using the new buffer mixture was also developed. Except results may be summarized as follows: Soils 5, 3, and 6
for the method and time of mixing (i.e., constant shaking gave titration curves similar to soil 1; soils 4, 13, and 7
for 10 minutes) and the buffer used, the mechanics of the
method are not unlike those of the Woodruff method (9, 10). gave curves similar to soil 2; and soils 11 and 10 gave
Since the development of this new method was a major curves little different from soil 14.
•objective of this study, the method as now used is presented It is evident from the data in table 1 and the curves in
under the section on Results and Discussion. figure 1 that great differences in the lime requirements,
amounts of extractable Al, and buffering capacities of the
RESULTS AND DISCUSSION soils are represented by the soils included in the study.
The amounts of soil acidity determined by the Mehlich
Acidity by TEA Method vs. Lime Requirement by TEA buffer method on all of the limed and unlimed soils
CaCO3 Incubation. are plotted against the lime requirement by CaCO3
The lime requirements of the various soils as determined incubation in figure 2a. As a whole the points indicate
lay the CaCO3 incubation and Mehlich buffer methods good correlation between the two quantities, but con-
.are indicated in table 1. The CaCO3 incubation (titration) siderable scattering of the points indicates appreciable

Table 1—Genetic and acidic properties of the soils used in this study.
Soil Soil type Horizon Great soil groups* County pH Lime requir 3ment, tons/acre Ext. Al. Acidity
No. or depth site Mehlich me. /lOOg > pH 6. 8t
CaCOj
incubation buffer roe. /lOOg
1 Clermont s. 1. Ap Planasol (I) Brown 5.1 3.3 3.0 1.6 1.7
A
5 Condit s. 1. 2' B i Planasol (We) Licking 5.0 3.4 3.4 1.5 3.0
3 Bethel s. 1. 0-7 inches Planasol (We) Miami 5.0 3. 1 3.5 2.5 1. 7
6 Miami s. 1. B£ G. B. Podzolic (We) Champaign 5.1 3.7 4.2 1.4 4.1
4 Bennlngton s. 1. A ; -B( G. B. Podzolic (We) Huron 5.0 4.7 5.2 1.6 4.1
13 Mahoning s. 1. Bj G. B. Podzolic (Wca) Lorain 4.9 5.3 5.4 2.9 4.3
7 Wooster s. 1. Ap G. B. Podzolic (Wca) Wayne 4.3 5.1 5.4 3.7 3.8
2 Fincastle s. A, -B, G. B. Podzolic (We) Warren 4.7 5.4 5.9 2.6 3.2
12 Ellsworth s. A 2 -B, G. B. Podzolic (Wca) Lorain 4.6 6.6 6.3 3.4 3.5
8 Mahoning s. Ap G. B. Podzolic (Wca) Trumbull 4.5 8.9 7.6 4.9 3.4
11 Mahoning s. Ap-B, G. B. Podzolic (Wca) Ashtabula 4.7 10.0 9.2 5.7 4.4
10 Trumbull s. AP Low Humlc Gley (Wca) Ashtabula 4.4 10.9 10.9 7.2 6.1
14 Fries S. cl. Ap Humic Gley (Ls/a) Erie 4.3 10.3 11.0 7.3 5.5
15 Unclassified 1 » 0-8 inches Lithosol (Ls/a) Erie 4.3 16.7 16.7 8.0 8.2
Average - - - 7.0 7.0 3.9 4.1
* I = Illinoian calcareous till, We = Wisconsin calcareous till, Wca - Wisconsin slightly calcareous to acid till, and Ls/a = lacustrine silt over acid shale.
t Acidity measured above pH 6.8 by the Mehlich buffer. Although they were obtained graphically, the values are essentially the amounts which would have been measured by this buffer
when the soils were limed to pH 6.8.
% This Is a relatively young soil which has not yet been correlated.
276 SOIL SCIENCE SOCIETY PROCEEDINGS 1961
8 12 16 20
CaCO, added — tn.e./IOOg.
Figure 3—Basic and acidic cations determined in the
Fries soil (No. 14) at various rates of liming.
departure from a linear relationship. When these data for
the unlimed soils alone are plotted in figure 2b, it may
be noted that the points are much closer to the line
than where the limed soils were also included.
Examination of the points plotted in figure 2a reveals
that the points which systematically deviate more from
the line as they approach the y axis are those for a given
soil with increasing amounts of lime (decreasing lime
requirement). The data for three of the soils plotted in
figure 2a are plotted, and the individual points connected
in figure 2c. It is evident that with increasing rates of
liming the amounts of soil acidity by Mehlich TEA
method are progressively greater than the actual lime
requirement. This suggested that the component of acidity
above pH 6.8 which is measured by the TEA method
should be deducted from the total value obtained. These
data with the acidity above pH 6.8 deducted for all of the
limed and unlimed soils are also plotted in figure 2c. The
points form a much more linear relationship in figure 2c
than in figure 2a. But the slope of the line is less than
unity with the acidity by this adjusted TEA method
being only about three-fourths as great as that indicated
by the lime requirement from CaCO3 incubation.
The amounts of Al (me. per 100 g. of soil) extracted
from the soils with NH4OAc at pH 4.8 were added to
the amounts (me. per 100 g. of soil) obtained with the
adjusted TEA method. These total quantities were plotted
against the lime requirement by CaCO3 incubation in
figure 2d. A close linear relationship with slope of unity
resulted.
Several empirical relationships are evident from the
above results. First there was a component of soil acidity
above pH 6.8 which was measured by the regular TEA
method. This component by chance or otherwise was on
the average about equal to the extractable Al in the
unlimed soils (see figures 2b and 2d and table 1). In-
dividual soils, however, varied considerably in this respect.
Second, by inference a component of acidity below pH
6.8 was not measured by the TEA method because when
the acidity above pH 6.8 was deducted, it was necessary
to include the values for the extractable Al in order to
obtain the correct lime requirement. Third, since the
amounts of acidity determined in the limed (or partially
limed) soils by the TEA method exceeded the actual
amounts indicated by CaCO3 incubation, the unmeasured
acidity component (equivalent to the extractable Al)
must have been markedly decreased by liming relative
to the acidity measured by the TEA above pH 6.8. For
these reasons, deducting the amount of acidity above
pH 6.8 measured by the TEA method and adding to the
result the amount of extractable Al gave the correct lime
requirement whether or not the acidity had been partially
or largely neutralized by lime additions.
Extractable Al as a Factor Affecting Exchangeability
and Exchange Capacity for Cations.
Further justification for the addition of the extractable
Al to the acidity measured by the TEA method adjusted
to pH 6.8 is illustrated by the data for the Fries soil (No.
14) plotted in figure 3. The total bases (Ca, Mg, and K)
determined by flame photometry, the acidity determined
by the adjusted TEA method, the acidity by adjusted TEA
plus extractable Al, and cation-exchange capacities (CEC)
by four different methods are all plotted against lime
added. When the CEC was determined by addition of
the total bases to the acidity by adjusted TEA method,
the CEC increased markedly with lime addition. However,
when the CEC was determined by addition of total bases
to the acidity by adjusted TEA plus extractable Al, the
values for the amounts obtained were only slightly in-
creased by liming. The values for the CEC determined
by the BaCl2 and NH 4 OAc methods are also included in
figure 3 for comparison.
The tendency for the CEC values by all methods to
increase slightly with level of liming (and pH) is consistent
with results and explanation for the phenomenon by
Schofield (8). The fact that the sum of bases plus acidity
measured by the TEA method was markedly increased by
lime addition suggests as did the above results that in the
acid soil there were cations present which occupied ex-
change sites which were not measured by this method.
Since the added Ca was almost quantitatively recoverable,
the unmeasured cation seemed most likely to be acidic.
There seemed to be no reason to expect H ions not to
react quantitatively with the buffer. This left Al as sus-
pect. As indicated before, the acidity determined by
plotting pH vs. lime added indicated that the extractable
Al reacted with the lime. Yet these results suggested that
the Al did not react with the triethanolamine buffer. This
apparent tendency for the Al to react with the lime and
not to react with the buffer may result from the fact
that when lime is added to the soil (moist), the CaCO3
reacts slowly with the Al causing only a gradual change
in pH. Under this condition, all of the Al might eventually
be displaced from the exchange sites and react quantita-
tively with the lime added. In contrast, when the TEA
buffer at pH 8.1 is added to the soil, there is an almost
instantaneous change in pH of the soil to that of the
soil-buffer mixture (~pH 7.8 to 8.0). This may well cause
a major portion of the unreacted Al to be trapped inside
the clay lattice by a relatively small amount of insoluble
A1(OH)3 formed. Paver and Marshall (7) have suggested
this as an explanation for the decreased CEC when base
was added to Putnam clay to which A12(SO4)3 had been
added. If most of the extractable Al occupies exchange
sites and much of it does not react with the TEA buffer
due to a mechanical obstruction, then theoretically the
true CEC of the soil should result from the addition of
the extractable Al to the sum of the bases plus the acidity
to pH 6.8 by TEA. Since NH4OAc at pH 4.8 extracts
some Al in addition to that which is exchangeable, it is
perhaps unexpected that the amount extracted is the
precise amount required to give the near-constant values
for the CEC of the soil under different levels of liming.
Although the extracting solutions for Al and the pH for
adjusting the TEA values were different, the acidity
component below pH 6.8 and that above pH 6.8 are
probably related to the "permanent charge" and pH
dependent CEC of Coleman et al. (2).
 SHOEMAKER ET AL.: BUFFER METHODS FOR DETERMINING LIME REQUIREMENT OF SOILS HIGH IN AL 277
A New Test for Lime Requirement of Soils. Table 2—Lime required to bring the soil to an indicated
Since the above methods for determining lime require- pH according to soil-buffer pH.
ment of soils are not rapid enough for use in the routine Soil-buffer Lime required to bring soil to indicated pH,tons/acre
soil testing laboratory, a new buffer method was developed pH Pure CaCO3 Agricultural ground lime*
based on change in pH of the buffer by the soil. The (to nearest half ton)
above soils both limed and unlimed with known lime pH 6.8 pH 6.4 pH 6.0 pH 6.8 pH 6. 4 pH 6. 0
requirements served as reference points for adjusting 6.7 1.4 1.2 1.0 2.0 1.5 1.5
indicated lime requirements to actual values. It appeared 6.6 1.9 1.7 1.4 2.5 2.5 2.0
6.5 2.5 2.2 1.8 3.5 3. 0 2. 5
from an analysis of the Mehlich and Woodruff buffer 6.4 3.1 2.7 2.3 4.5 4.0 3.0
6.3 3.7
methods that the buffer should be much weaker, if a 6.2 4.2
3.2
3.7
2.7
3.1
5.0
6.0
4.5
5. 0
4.0
4. 5
plotting of the change in pH of buffer against the acidity 6.1 4.8 4.2 3.5 6.5 6. 0 5. 0
6.0 4.7 3.9 7.5 6.5 5.5
present was to indicate accurately the amount of lime 5.9
5.4
6.0 5.2 4.4 8.5 7. 5 6. 0
required to neutralize soils with appreciable amounts of 5.8 6.5 5.7 4.8 9.0 8. 0 6. 5
active Al (5). 5.7 7.1 6.2 5.2 10.0 8.5 7.5
5.6 7.7 6.7 5.6 10.5 9.5 8.0
Extensive investigation of various combinations of a con- 5.5 8.3 7.2 6.0 11.5 10.0 8.5
5.4 8.9 7.7 12.5
siderable number of buffers led to the buffer mixture and 5.3 9.4 8.2
6.5
6.9 13.0
10.5
11.5
9.0
9.5
testing procedure presented in some detail in the following 5.2 10.0 8.6 7.4 14.0 12.0 10.0
section. The selected buffer mixture gave both adequate 5.1 10.6 9.1 7.8 14.5 12.5 11.0
5.0 11.2 9.6 8.2 15.5 13.5 11.5
change in pH and nearly linear relationship to soil acidity 4.9 11.8 10.1 8.6 16.5 14.0 12.0
4.8 12.4 10.6 17.0
in the soils studied (5). This method would likely indicate 9.1 14.5 12.5
* Agricultural ground lime as used here is a grade of lime with sieve analysis show-
somewhat more lime required than would be needed if Ing at least 95% passing an 8 mesh screen and 40-59% passing a 100 mesh screen
the amount of acidity were large and predominantly H and an average neutralizing power 90% as great as pure CaCO3.
ions instead of Al (4). However, for the above 14 soils
with the various levels of liming the method was highly
satisfactory for indicating lime requirement. The correla- soil-water suspensions of ^ pH 6.3. Stir well.
tion coefficient between the actual values obtained by 8. Shake continuously4 for 10 minutes or stir inter-
CaCOc. incubation and that indicated by the test is 0.97. mittently for 20 minutes.
Since the relative amount of error is greatest for soils re- 9. Read pH of soil-buffer suspensions immediately.
quiring little lime, it is recommended that a minimum 10. Use table 2 to determine the amount of lime to
practical application of 2 tons of lime be made for any recommend.5
soil (1 ton for sands) of pH below 6.5—unless more is
indicated by the buffer. "A time-clock controlled shaker equipped with plastic-coated
In another recent study the lime requirements indicated foam rubber cushioned top which clamps tight over the cups,
by the new buffer method was compared to that indicated permits simultaneous shaking of 44 samples.
by Ca(OH) 2 titration. One hundred soils ranging from "Although not a part of this study, the following guides may
4 to more than 15-ton lime requirements were included. be useful in making lime recommendations. For soils with
excessive lime needs, i.e., 10 tons per acre or more, add lime
The average amounts indicated by the two methods were initially not to exceed pH 6.4. When indicated rates exceed
not only similar, but the correlation coefficient between 4 to 6 tons per acre, split the applications to facilitate spread-
the two methods was 0.93. As a result of these studies, the ing and mixing with the soil. On established pastures, apply
method is now used in the Ohio State University, Soil only half the indicated amount with a maximum of 4 tons
Testing Laboratory as a routine test, the results of which per acre added on the surface at any one time.
serve as a basis for recommendation of lime applications
to acid soils.
Shoemaker, McLean, and Pratt Buffer Method of
Determining Lime Requirement of Soils
I. BUFFER MIXTURE (amounts per liter of solution)
1. Para-nitrophenol 1.8 g.
2. Triethanolamine 2.5 ml.
3. Potassium chromate (K2CrO4) 3.0 g.
4. Calcium acetate Ca(CO,CH3)o 2.0 g.
5. Calcium chloride (CaCl2-2H26) 53.1 g.
Mixture is adjusted to pH 7.5 with NaOH.
II. TESTING PROCEDURE ADOPTED
1. Weigh or measure 5 g. of soil into small paper cups.
2. Add 5 ml. of distilled water.
3. Stir well and read pH with glass electrode.
4. If the reading is pH 6.6 or above, recommend that
no lime be added for most crops.
5. If the reading is pH 6.0 to 6.5, recommend that
2 tons per acre of agricultural ground lime or its
equivalent, be added to silt loams and finer textured
soils and 1 ton per acre be added to sandy soils.
(Soil to pH 6.8 basis.)
6. As a double check on the pH measurement, over-
lap the above group partially by running the lime
requirement by the buffer procedure on all soils
showing soil-water pH of 6.3 or lower. If more than
a 2-ton application is indicated, recommend that
amount.
7. Add 10 ml. of the above buffer mixture to the