CATION EXCHANGE CAPACITY

AND EXCHANGEABLE BASES

DETERMINATION
TENDAYI TAKESURE – AFRILAB
Vice-chair
LESEGO MOOKETSI-SELEPE – AFRILAB chair
 INTRODUCTION
• Cation exchange capacity (CEC) is the total number of cations that a soil can hold
thus a measure of number of negative charge binding sites.
• These adsorb (hold) positively charged ions by electrostatic forces following negative
sites created by weathering process e.g. isomorphous substitution in clays or pH
dependent charges from hydroxyl groups on clays and oxides or carboxyl groups on
SOM.
• Cations are bound in reversible chemical reactions to neutralize the negative charge
in the soil created as conceded.
• It can be expressed in terms of milliequivalents/100 g of soil (meq/100 g) or
centimoles of positive charge per kg of soil (cmol(+)/kg) or cmolc/kg, which is
numerically equal to meq/100 g (me%).
• Since a soil’s CEC comes largely from clay and OM present, CEC of a soil can be
estimated from texture and soil colour i.e increases with soil pH due to the greater
negative charge development on organic matter and clay minerals such as
illite/smectites due to deprotonation of functional groups with increased pH
(Sumner and Miller, 1996) See Fig 1. pH versus CEC.
 INTRODUCTION

Fig 1. DEFINING Cation Exchange Capacity and Exchangeable Bases of a Soil

 Cation exchange capacities of
INTRODUCTION Table 1. Cation exchange capacities of different textural classes and
some different soil types at pH 7.0 organic matter
at pH 7.0

• Clay content, organic

matter, and root CEC (cmolc/kg) Soil Texture CEC (cmolc/kg)
Clay Type
surfaces all have a
direct relationship with Kaolinite 3-15 Sand 1-5
soil CEC because they
Illite 15-40 Fine Sandy Loam 5-10
act as seats for
negative charge. Montmorillonite 80-100 Loam 5-15

Clay Loam 15-30

Clay >30

Organic matter 200-400

 INTRODUCTION
• CEC is a fundamental property for Cations (+) symbol Anions (-) symbol
assessing soil fertility used to predict
plant nutrient availability and Calcium Ca2+ Nitrate NO3-
retention in the soil.
Magnesium Mg2+ Phosphate H2PO4-;
• The term “exchangeable bases” or HPO42-
“total exchangeable bases” refers to
the sum of the concentration of the
bases (calcium, magnesium, Potassium K+ Sulphate SO4-
potassium, and sodium) in
exchangeable form. Sodium Na+ Chloride Cl-
• Under normal management Hydrogen H+
practices, higher CEC soils will show
changes in soil pH much more slowly Aluminium Al3+
than low CEC soils as cations are lost
owing to high buffering capacity will
also influence rate of liming etc.
 Methods for CEC Determination

• The more widely adopted methods of CEC determination are classified as

follows:
• Cation summation
• Direct displacement
• Displacement after washing
• Radioactive tracer
• Alternate methods use extractants that are either buffered (usually pH 7 e.g.
Ammonium acetate or BaCl2 (pH 8.2) or unbuffered (field pH).
• The GLOSOLAN SOP is based on the displacement after washing principle
 SCOPE AND FIELD OF APPLICATION- IN VIEW OF INTERFERENCES
• As a number of methods are available for measuring CEC, it is very important to
compare CEC and exchangeable bases where the same laboratory method has
been used. GLOSOLAN thus have adopted presently the buffered 1N Ammonium
Acetate method as one of the most popular methods available to facilitate
Proficiency Testing and Regional comparison of data.

• For ideal method of CEC, it is important to know in the first place the intended use of the
data. For soil classification a soil’s CEC is often measured at standard pH value of which
selected method of Ammonium Acetate is recommended.

Often Soil testing laboratories, knowing the importance of CEC but in bid to cut expenses
do not provide a direct measure of CEC but use CECsum based on summation of quantities
of Ca, Mg and K (sodium most often being usually in negligible quantities).
 APPLICABILITY, ADVANTAGES / DISADVANTAGES
• Ideal when soil pH is >7.3 and the soil has not been limed in the last 6 months or have
not been fertilized by Ca, K or Mg fertilizers, CECsum can be a reasonable estimate of CECe
• On the other hand above pH 7.5 significant quantities of free salts or unreacted lime
may have been just dissolved in the extracting solution used for leaching

ADVANTAGES OF pH 7 buffered AMMONIUM ACETATE

• It is rapid and cost effective hence can be easily implemented by many laboratories
• May underestimate CEC of tropical peats.

DISADVANTAGES OF AMMONIUM ACETATE CEC buffered method

The major problem with this method is that it buffers soil pH at 7.0 . So will only approximate a
soil’s CECe if a soil’s pH is 7.0 otherwise the results obtained can be a large overestimation of CECe
Of many acid soils (common in Africa). If soil pH is < 5.5 then Al3+ which might be present might
not be measured accurately by the exctractants hence need to use alternative e.g. KCl.
The harmonized GLOSOLAN SOP
 SCOPE AND FIELD OF APPLICATION - OVERVIEW
• This procedure outlines the process for the determination of cation exchange capacity
(CEC) and exchangeable bases (calcium, magnesium, potassium and sodium) in soil using
1N ammonium acetate buffered at pH 7.
• The method gives an estimation of plant-available exchangeable bases.

• It should be noted though that when a soil is extracted at higher pH, this induces weakly
acidic components to dissolve and liberate H+ which are measured as exchangeable acidity.

❖ This method overestimates the CEC of ❖ The method underestimates the CEC of soils
acidic soils as additional negative containing carbonates or gypsum because
charge is developed on colloidal the release of calcium carbonates or sulfates
exchange sites after the addition of from the soil into the ammonium acetate
ammonium acetate solution having solution limits the saturation of exchange
pH 7 (i.e at pre-determined pH). sites by ammonium ions.
 SCOPE AND FIELD OF APPLICATION
• The unbuffered method (just in passing) allow exchange at soil pH often referred to as
ECEC and the pH will be at a lower value than buffered extractant salt solutions as it does
not include latent acidity.

• Caution should be exercised in using this method for soils dominated by vermiculite and
mica clays because ammonium ions are fixed between the layers of these clays. This
methods thus causes the layers to collapse and the fixed ions can no longer be exchanged
by sodium ions.

• In relation to the exchangeable bases, for soils in the presence of gypsum (calcium
sulfate), extraction with ammonium acetate only allows the quantification of
exchangeable magnesium, sodium and potassium, since the calcium content is
affected by the excess calcium in the gypsum
 SCOPE AND FIELD OF APPLICATION
• Likewise, in soils containing calcium and magnesium carbonates, extraction with
ammonium acetate only allows the quantification of exchangeable sodium and
potassium, since the content of calcium and magnesium is affected by the excess of
ions from the carbonate

• Similarly when lime has recently been applied, carbonate will liberate calcium which
will bind to new site and this will result in an increase in ECEC. So direct soils CEC for
the just amended fertilizer/lime should be taken with caution and better avoided.

• Another problem arises in soils affected by salts, because the soluble cations (from
the salts) are extracted together with the exchangeable bases

• Hence EC is a crucial guide in soils suspected to be salt affected

PRINCIPLE AMMONIUM ACETATE (buffered at pH 7.0) SOP
• This SOP describes the most widely used method for agricultural soils.

• The soil is treated with 1 normal ammonium acetate solution buffered

at pH 7.0 to remove exchangeable cations from the exchange sites of
the soil colloids as conceded in introduction of CEC and to saturate
them with NH4+ ions.
 PRINCIPLE (continued)
• Then the exchangeable cations in the leachate are then quantified using
different instrumental methodologies that are available (Atomic
Absorption/Emission spectrometry, flame emission or Inductively
Coupled Plasma or MP-AES) etc.

• In the sediment, the excess of ammonium ions in the soil samples are
removed by washing with ethanol. Then the adsorbed ammonium ions
on soil sample are extracted using acidified sodium chloride and
measured by distillation and titration.
• In saline soils, one of the options is to pre-wash samples with 70%
alcohol to eliminate the salts (soluble bases)
 APPARATUS -1
1. Reciprocal shaker
2. Precision balance
3. Centrifuge
4. Volumetric dispensers
5. Filter funnels and qualitative fine
porous filter paper
6. 100 ml volumetric flasks
7. pH meter and buffer solutions
 APPARATUS -2

8. 50 ml Plastic tubes/centrifuge tubes

with screw on caps
9. Graduated or automatic burette
10. Steam distillation unit
11. 250 Kjeldhal distillation tubes
12. Erlenmeyer flasks 250 and 100 ml
13. Stirrer and magnetic bar
14. Flame or Plasma spectrophotometer
15. Atomic absorption
 MATERIALS
1) Deionised/distilled water 8. Sodium chloride(NaCl) solution
2) Concentrated Ammonium hydroxide 10%(m/v), pH 2.5
(NH4OH,AR) 9. Sodium hydroxide (NaOH) solution 10
3) Glacial acetic acid (CH3COOH 99.5%, mol/l
AR) 10. 1N Hydrochloric acid/Sulphuric acid, AR
4) Ammonium acetate (NH4CH3COO, AR) 11. Boric acid (H3BO3) AR
5) Methyl orange 12. Boric acid (H3BO3)solution 4%m/v
6) Sodium chloride (NaCl, AR) (4g/100ml)
7) Concentrated hydrochloric acid (HCl, 13. Ethanol (95 – 96%)
32-36%) 14. Gases (as determined by instruments)
 HEALTH AND SAFETY
• Personnel safety • Chemical hazards
• Metal salts used in this procedure • concentrated HCl, NaOH and
are extremely corrosive and may be H2SO4 to be used under a fume
fatal if ingested hood
• Use protective clothing: lab coats, • Neutralize spilled acids with
aprons, gloves and eye protection dilute solution of sodium
face shield, goggles or safety glasses bicarbonate or cover with sand
• Alcohol is flammable
• Ammonium acetate is corrosive
• Refer to MSDS
 PROCEDURE - 1
1. Weigh 5g of <2mm sieved soil in a 50 mL container/extraction tubes;
NOTE: Include a blank and reference sample in every batch
2. Add 33ml of 1N ammonium acetate pH 7.0
3. Shake 15 min in a reciprocal shaker
4. Centrifuge and filter the supernatant in a clean 100 mL volumetric flask
with qualitative fine porous filter paper. Repeat steps 2 to 3 two more
times to obtain a total of approximately 100 mL at the end. Fill up to the
100 mL mark with ammonium acetate and mix well.

N.B. For CEC determination Keep the soil sample in the 50 mL

extraction/centrifuge tubes for Procedure 3 step 6.
 PROCEDURE- 2
5. Analyze the leachate for Ca, Mg, Na and K by Atomic Absorption flame or plasma
spectrophotometry. Following the manufacturer’s guide for the elements required:
Some of the suitable spectral lines for Atomic Absorption Spectrophotometer are:

Ca = 422.7 nm;
Mg = 285.2 nm;
Na = 589.0 nm;
K = 766.5 nm.

Ca2+ and Mg2+ are measured on dilute extracts, whereas, extracts of Na+ and K+ analysis are
only diluted if over range. For plasma, suitable wavelengths are: Ca = 430.25 nm; Mg = 285.2
nm; Na = 588.96 nm; and K = 766.49 nm. While It is suggested to use AAs/flame photometer
if available an ICP-OES can also be used.

The range of standards presented in table 1 is recommended.

 TABLE 2 - Recommended standard guide range

Ca Mg Na K

100 ml Vol. of Final Vol. of Final Vol. of Final Vol. of Final

flask 100mg/l conc. 100mg/l conc. 100mg/l conc. 100mg/l conc.
mg/l mg/l mg/l mg/l

Flask 1 0 0 0 0 0 0 0 0

Flask 2 2 2 1 1 5 5 5 5

Flask 3 4 4 2 2 10 10 10 10

Flask 4 6 6 3 3 15 15 15 15

Flask 5 8 8 4 4 20 20 20 20

Flask 6 10 10 5 5 25 25 25 25
PROCEDURE – 3: CEC ANALYSIS ON AFTER LEACHATE SEDIMENT
6. To displace the adsorbed ammonium ions ; Place the sediment into the
leaching apparatus and add 50 mL of 95-96 % Ethanol and leach wash.
7. Decant and repeat the process of leach washing with ethanol with another
fresh 50 ml portion and decant thereafter.
8. Add 33 mL of a 10% NaCl solution to the sample, stopper and shake for 15
minutes.

9. Centrifuge and filter into a clean 100 mL volumetric flask.

10. Repeat step 8 two more times to obtain a total of approximately 100 mL of
NaCl solution at the end. Fill up to 100 mL with NaCl and mix well.
 PROCEDURE – 4 DISTILLATION AND TITRATION
10. Transfer 50 mL of aliquot NaCl extract into the distillation tube and connect
to the distillation unit.

11. Add 10 mL sodium hydroxide and distilled water cautiously after set up of
boric acid receiver have been set up with 25 ml in an Erlenmeyer flask in place if
instrument does not have automatic addition of reagents in place.

12. Titrate the distillate with 0.01N H2SO4 or HCl to the indicator end point.
CALCULATIONS – for CEC
1. Calculations for CEC in cmolec/kg soil
Sample weight = 5 g
Extract = 100 mL
Aliquot = 50 mL
HCl concentration = 0.01 N

CEC cmolec/ kg or meq/100g soil = (HCl used for sample - HCl used for
blank) * HCl concentration * 100/5 * 100/50
 CALCULATIONS – FOR EXCHANGEABLE BASES
Ca cmol(+)/kg soil = (Sample concentration in mg/l - blank concentration
in mg/l) x 100/1000 x 1000/5 x 2/40.08 x 1/10 x dilution factor

Mg cmol(+)/kg soil = (Sample concentration in mg/l - blank concentration

in mg/l) x 100/1000 x 1000/5 x 2/24.31 x 1/10 × dilution factor

Na cmol(+)/kg soil = (Sample concentration in mg/l - blank concentration

in mg/l) x 100/1000 x 1/10 x 1/22.99 x 1000/5 x dilution factor
100/1000 conversion to L
K cmol(+)/kg soil = (Sample concentration in mg/l - blank concentration in
mg/l) x 100/1000 x 1/10 x 1/39.098 x 1000/5 x dilution factor 1/10 conversion to
centimol
% Exchangeable base saturation
Is given by 100 (Ex Ca + Ex Mg + Ex K + Ex Na)/CEC 1000/5 conversion to Kg
 QUALITY ASSURANCE/QUALITY CONTROL
a) Precision Test
• Perform replicate analysis on one sample at every 10 (or 20) samples in
batch tests in a single run on a single day
• Calculate the Percent Relative Standard Deviation (%RSD) to determine
if the replicate analysis is out of the control.

b) Accuracy Test
• Participate in Inter-laboratory Proficiency Test (either national
or international)
• Analyse CRM or QRM
 QUALITY ASSURANCE/QUALITY CONTROL
c) Quality Control Chart
• Analyse at least a duplicate of the check sample (Internal
Quality Control sample, IQC) or Internal Reference Material
(IRM) in every batch.
• Plot the results in a control chart.
 REFERENCES
AOAC Peer-Verified Methods Program, Manual on Policies and Procedures (1998) AOAC
INTERNATIONAL, Gaithersburg, MD.

Blakemore, Leslie Clifford. "Methods for chemicalanalysis of soils." NZ Soil Bureau Sci. Rep.
80 (1987): 72-76.

Chapman, H.D.,1965 "Cation-exchange Capacity,", in C.A. Black (ed.),

Method of Soil Analysis, Part 2: Chemical and Microbiological Properties, Am. Soc. Agron.,
Madison, Wisconsin. pp. 891-900.
 REFERENCES
Kalra, Y.P., Maynard, D.G., 1991. Methods Manual for Forest Soil and Plant Analysis. Northern
Forestry Centre, Edmonton, Alberta.

Sumner, M. E., & Miller, W. P. (1996). Cation exchange capacity and exchange coefficients.

In “Methods of Soil Analysis, Part 3. Chemical Methods” (D. L. Sparks, Ed.), Soil Sci. Soc. Am.
Book Ser. 5, pp. 1201–1229. Soil Sci. Soc. Am.,

Madison, WI. van Reeuwijk, L. P. (1986). Procedures for soil analysis

Donald S. Ross and Quirine Ketterings. Recommended Methods for Determining Soil Cation
Exchange Capacity
THANK YOU!!!