Methods For Chemical Analysis of Soils

A.
METHODS FOR CHEMICAL ANALYSIS OF SOILS
Bv L.C. BLAKEMOREJ P.L. SEARLEJ B.K. DALY
Soil Bureau, Department of Scientific

and Industrial Research, Lower Hutt
N-EW ZEALAND SoIL BUREAU Sc1ENTIF1c REPORT lOA

Department of Scientific and Industrial Research, New Zealand
1981
(
First printed 1972
Revised 1977
Revised 1981
c
Bibliographic Reference:
BLAKEMORE, L.C.; SEARLE, P.L.; DALY, B.K. 1981:

A. Methods for Chemical Analysis of Soils.
New Zealand Soil Bureau Scientific Report lOA.
(
ISSN 0304-1735
P.D. HASSELBERG, GOVERNMENT PRINTER, WELLINGTON, NEW ZEALAND - 1981 ( ....

CONTENTS
page
Introduction
Al Soil pH Al. l
A. pH in H2 0 and chloride salt solutions Al. l
B. pH in NaF solution Al.4
A2 Moisture factor A2.l
A3 Carbon A3. l
A. Determination of total carbon using high frequency
induction furnace equipment A3.2
B. Colorimetric determination of organic carbon A3. 7
A4 Nitrogen A4.l
A. Total nitrogen determination where nitrate is
present in trace amounts A4.l
B. Total nitrogen determination where nitrate content
is high A4.7
c: AS Phosphorus
A. Truog-soluble phosphorus determination
AS.l
AS.2
B. 0.5 M H2 S0 4 -soluble phosphorus determination AS.6
C. Phosphate retention determination AS.9
D. Organic phosphorus determination ignition method AS.11
E. Total phosphorus determination AS.13
A6 Cation exchange properties A6.l

A. Leaching procedures A6.4
B. Determination of individual exchangeable bases A6.6
C. Determination of total exchangeable bases by
titration (TEBtitn) A6.8
D. Calculation of total exchangeable bases by
summation (TEBsum or ~ bases) A6.9
E. Determination of cation exchange capacity (CEC) A6.10
F. Calculation of percentage base saturation (%BS) A6.12
G. Semi-micro leaching A6.13
H. KCl-Extractable Aluminium A6.14
I. Exchange Acidity A6.15
A7 Reserve potassium (Kc) and magnesium (Mgr) A7.l
A. Determination of Kc value A7 .1
B. Determination of Mgr value A7.3
AS Extractable iron, aluminium and silicon AS.l

A. Oxalate-extractable iron, aluminium and silicon AS.S
B. Pyrophosphate extractable iron and aluminium AS. 7
C. Dithionite-citrate extractable iron and aluminium AS.Cl
A9 Soluble salts A9.l

A. Measurement of conductivity A9.2
B. Determination of water-soluble cations A9.3
C. Determination of water-soluble anions A9.4
AlO Calcium carbonate AlO.l

A. Gasometric carbon dioxide method AlO.l
B. Differential method Al0.3
C. Correcting exchangeable calcium for calcium
carbonate-calcium Al0.4
All Phosphate extractable sulphur All. l
Al2 Analyses of plant litters, peats and compost Al2.l
Al3 Presentation and rating of results Al3. l

l
A. Ratings for chemical properties Al3.3
C.
INTRODUCTION
In 1956, "Methods of Chemical Analysis for Soil Survey Samples" by

A.J. Metson was published. This comprehensive account of the chemical
analytical methods that were being used by Soil Bureau at that time provides
background information on the purpose of the determinations and on the
technical details of the methods.
In common with all scientific disciplines, soil chemistry has made

tremendous advances over recent years and many new analytical techniques
have been developed. Not only have these new techniques of measuring
soil properties improved the speed and accuracy of standard analytical
procedures, but they have also facilitated measurement of a wider range
of properties. It seems probable that this progress, with its consequent
improvement in analytical methods, will continue.
These methods have been written with a minimum amount of explanatory

information on the principles of the methods and application of the results.
They describe new methods or new techniques that have been developed since
1956 and they may require modern and expensive equipment. If this
equipment is not available the basic methods described in Metson (1956) may
be used with confidence.
Mr A.J. Metson and the staff of the Soil Analysis Section, Soil Bureau
are thanked for their help in developing several of the methods, and for
their helpful criticism of the manuscript.
c 1972
REFERENCE
METSON, A.J. 1956:

Methods of chemical analysis for soil survey samples.
New Zealand Soil Bureau Bulletin 12. 208 p.
This 1977 revised edition incorporates recent developments in instrumental

methods within the Soil Analysis Section. Also, some changes to procedures,
and to the ratings for chemical properties have been made in light of recent
knowledge. The opportunity has been taken to express most concentrations
in moles/litre, except for standard solutions in cation exchange properties
where measurements are expressed in terms of milliequivalents, as this unit
is still used in most soil literature. The following expressions for cation
exchange and related properties are used:
1 me.% =
1 m mol per 100 g oven dry (105°C) soil
charge on free ion
c 1 mg% = 1 mg per 100 g oven dry (10S°C) soil

This second rev1s1on (1981) includes several changes to technique and
terminology. Some are relatively minor but those concerning determination
of extractable sulphur and oxalate extractable Al, Fe and Si, are quite
major. Another area of important change is the determination of exchangeable (--
bases - both in terminology (bases and cations) and in the extent of dilution
before measurement. This is to allow a more convenient range to be used
during flame spectrometry for most soils.
The use of 'Soil Taxonomy' for classification of soils by Soil Bureau,

on a trial basis, has made it necessary for this laboratory to carry out several
additional analyses to those listed in the first revision. These comprise
pH NaF, KCl-extractable Al, exch. acidity, dithionite-citrate Fe and Al,
pyrophosphate extractable Fe and Al. Details of methods for these determina-
tions are given.
c
Al.l
Al. SOIL PH
Al.A PH IN H20 AND CHLORIDE SALT SOLUTIONS
INTRODUCTION
The measurement of soil pH is usually regarded as one of the simplest

determinations used in soil chemistry. However, even a cursory inquiry
into the factors involved will show that many complications and difficulties
are involved.
Several of these difficulties are caused by the fact that the pH theory
applies to dilute solutions of simple electrolytes (Bates 1964). Although
measurements may be made quite easily on soils and soil suspensions, there
is considerable doubt about the significance of the results obtained in
terms of hydrogen-ion activities. Available evidence indicates that the
apparent pH of soil obtained by use of a glass electrode pH meter reflects
hydrogen-ion activities in the bulk solution surrounding the electrodes,
rather than hydrogen-ion activities in the ion atmosphere around the soil
particles. However, the values obtained by carrying out pH measurements
on soils do provide useful correlations with other soil properties and it
is important to give considerable thought to choice of conditions for making
the measurements and to realise the limitations of these conditions when
interpreting results. The use of glass electrodes with calomel half-cells
is almost universal for measurement of pH and details of use of the instrument
are adequately dealt with in the relevant literature and in manufacturers'
brochures.
(
FACTORS INFLUENCING pH MEASUREMENT
Choice of conditions for measurement of pH in soils involves the

following factors:
Moistness of soil to be tested,

Suspension medium,
Ratio of soil to suspension medium,
Degree of stirring,
Positioning of electrodes.
MOISTNESS OF SOIL TO BE TESTED. The choice is between air-dry soil

(as prepared for chemical analysis) and soil in its natural state of
moisture. The principal objection to using air-dry soil is that the
drying process can cause changes in pH values (e.g., through oxidation of
sulphides), while the main objection to using naturally moist soil is the
added difficulties in obtaining a representative sample and weighing out
the naturally moist material, and the effects of biological activity on pH
during storage of moist soil. At Soil Bureau, we have found that these
effects can be most important and now routinely use air-dry soil.
(
Al.2
SUSPENSION MEDIUM. Ideally, measurement of soil pH should be made in

soil in its natural condition but for several reasons, e.g., fragility of (
the glass electrode, this is not possible and, in practice, the soil is
usually suspended in sufficient liquid to enable measurement to be taken.
In New Zealand laboratories water has usually been the suspension

medium for pH determination for both pedological and agricultural measure-
ments. However, electrolyte solutions are often preferred because the
results are more reproducible, they are not influenced by the salt content
of the soil, and the values obtained are less dependent on the positioning
of the electrodes. 1 M KCl and 0.01 M CaCl2 are the most commonly.used
salts.
When 1 M KCl is used, extensive ion exchange takes place, including

the release of aluminium. Hydronium and other proton donors are brought
into solution, influencing the glass electrode and lowering the measured
pH (Black 1968). It is not to be expected that the pH values obtained
with 1 M KCl will represent those of soil solutions but Black has suggested
that they may approach the pH values in the ion atmospheres of the original
soil.
Peech (1965) advocated use of 0.01 M CaC1 2 as the suspension medium

because it is similar in electrolyte composition to soil solutions found
at optimum moisture conditions for plant growth in "non-saline" soils
(i.e., soils of low salt concentration). He noted that this medium is
independent of dilution over a wide range of soil:suspension medium ratios.
At Soil Bureau, limited experience with 0.01 M CaC1 2 has shown that it has
some advantage over water as a medium for measuring soil pH because results (_
are more easily reproduced.
The overall effect of using salts is to lower the measured pH values.

With KCl the effect varies considerably and the pH is often more than
1 unit lower than results obtained with water. For New Zealand soils,
results with CaC1 2 are about 0.5 to 1 pH unit lower than with water.
RATIO OF SOIL TO SUSPENSION MEDIUM. Because soil pH values decrease

with increasing electrolyte concentration, it is to be expected that the
electrolyte effect would significantly change with different dilutions of
soil with water. In practice it has been found that the dilution effect
varies considerably from soil to soil, and in order to render measurements
of different investigators comparable, the International Society of Soil
Science committee on soil reaction measurements (1930) adopted a standard
dilution ratio of 1 part (by weight) of soil to 2.5 parts of water. This
ratio was chosen for convenience of pH measurement in mineral soils. Other
ratios have from time to time been recommended but it has been decided at
Soil Bureau that standardisation is important and that the international
1:2.5 ratio should be used. However in soils which are very high in organic
matter content (peats), it has been found necessary to use wider ratios (
(1: 5 or 1: 10) in order to obtain a workable slurry. ,,
Al.3
DEGREE OF STIRRING. Because it has been found that pH levels for

some soils vary with degree of stirring during preparation of soil suspen-
( sions, it has been made standard practice to stir the suspensions vigorously
using a mechanical stirrer or homogeniser.
POSITIONING OF ELECTRODES. Electr0des can be positioned to be in

contact with the supernatant liquid or with the sediment.
When water or 0.01 M CaC1 2 is used as the suspension medium, the
position of the calomel electrode is most important. A potential
difference is apparently set up at the junction of the soil and the KCl
bridge. As the potential difference varies with the concentration and
nature of the soil in the contact area, standardisation is better
achieved by positioning the calomel electrode in the supernatant
liquid.
Although the positioning of the glass electrode is not of such

importance it is preferable to place it in the sediment zone where the
system is more strongly buffered and hence less susceptible to minor
disturbances such as carry-over from the previous sample.
PREP~RATION OF REAGENTS
pH 6.5 BUFFER: CONCENTRATED BUFFER. Dissolve 89.7 g disodium hydrogen

phosphate (Na 2HP0 4 .2H 20) A.R, and 158.4 g potassium
dihydrogen phosphate (KH2P04) A.R.,in distilled water.
( Make up to one litre with distilled water.
WORKING BUFFER. Pipette 20 ml concentrated buffer

into a 500 ml volumetric flask and make to volume with
distilled water.
pH 4.0 .BUFFER: 0.05 M ~OTASSIUM HYDROGEN PHTHALATp. Dissolve 5.106 g

COOH.C 6 H4 .COOK in distilled water and make up to 500 ml
with distilled water.
1 M POTASSIUM CHLORIDE. Dissolve 74.56 g KCl, A.R., in one litre of

distilled water.
0.01 M CALCIUM CHLORIDE. Dry CaCh (anhydrous) at 110°C and dissolve

11.1 g in 10 litres distilled water.
PROCEDURE
PREPARATION OF SAMPLE. Weigh 10 g of air-dry soil into a 100-ml

beaker and add 25 ml distilled water, or 0.01 M CaC1 2 .
Stir vigorously with a homogeniser or high-speed stirrer.
Leave to stand overnight.

NOTE: When wider soil:suspension medium ratios are needed to achieve a
workable slurry (e.g., for peats), record the ratio used.
Al.4
MEASUREMENT OF pH. Position the electrodes so that the contact point (

of the calomel electrode is approximately 1 cm higher than the centre-point
of the sphere of the glass electrode (Fig. A.1.1). Combined electrodes
are suitable providing the bulb is positioned in the sediment when the
calomel outlet is in contact with the supernatant.
Adjust the pH meter so that correct pH readings are obtained for two
buffer solutions of widely differing pH (e.g., pH 4.00 and 6.50). Thoroughly
wash the electrodes with distilled water. Position the soil sample on the
instrument so that both electrodes are well-covered. Without stirring,
measure and record the pH. Carry out duplicate determinations on separate
subsamples. Replicate determinations should give results within 0.1 pH unit.
-Calomel electrode
~---...... Liquid level

(water or O·OlM CaCl 2 )
_(or M KCI) -
Glass
electrode
(
Fig. Al.1. Positioning of electrodes.
Al.B PH IN NAF SOLUTION

INTRODUCTION
This method is based on that of Fieldes and Perrott (1966) and is used
as an indication of the presence of active aluminium. It is the basis of a
"Fluoride field test" in which a portion of soil is reacted with NaF and the
resultant high pH (if 'allophane' is present) is shown by phenolphthalein
soaked filter paper turning red. High pH NaF values are found in soils
derived from volcanic ash and in the illuvial horizons of podzolised soils.
The method depends ·on active aluminium sorbing fluoride ions with consequent
release of hydroxyl ions.
PREPARATION OF REAGENT
SODIUM FLUORIDE, saturated (approximately 1 M). Add 4 R. distilled
water to 180 g NaF, A.R., in a 4 R. plastic bottle. Shake well, and let
stand for 2 days with occasional shaking. After excess NaF has settled,
check that the pH is between 7.2 and 8.1. Take 50 ml aliquot, heat to
boiling, add 5 drops of 0.25% phenolphthalein and titrate with 0.01 M NaOH (
to a pink end-point while hot. If the solution has a pH of more than 8.1
or if the titratable acidity exceeds 0.25 me. per litre (more than 1.25 ml
0.01 M NaOH for 50 ml aliquot), discard and try another sou:rce of NaF.
This laboratory uses Fisons A.R. grade.
Al.5
(- PROCEDURE
Weight 1 g soil (air-dry and < 2 mm) into a 100-ml beaker, add 50 ml
NaF reagent and stir vigorously for 1 min. Place pH electrode/s in suspension
and swirl gently. Read pH exactly 2 min. after adding reagent, ensuring that
the suspension is well stirred immediately prior to taking reading.
REFERENCES
BATES, R.G. 1964:

"Determination of pH; Theory and Practice". Wiley, New York. 435 p.
BLACK, C.A. 1968:
"Soil-Plant Relationships". 2nd ed. Wiley, New York. 792 p.
FIELDES, M.; PERROTT, K.W. 1966:

The nature of allophane in soils. Part 3. Rapid field and laboratory
test for allophane. N.Z. Journal of Science 9: 623-9.
INTERNATIONAL SOCIETY OF SOIL SCIENCE COMMITTEE ON SOIL REACTION MEASUREMENTS,

1930:
Part 1. Results of Comparative Investigations on the Quinhydrone
Electrode Method. Soil Research 2: 77-139
(
PEECH, M. 1965:
Hydrogen-ion activity. Agronomy 9: 914-26.
c
(_
A2.1
A2. MOISTURE FACTOR

(
INTRODUCTION
Most results should be reported on an oven-dry basis (see Section

Al3), but as oven drying causes changes in several chemical properties of
soils, analyses are carried out on air-dried samples (i.e. dried at temp-
eratures of no more than 30o C). In order to convert results to an oven-
dry basis, a moisture factor is applied (see Section Al3).
PROCEDURE
Weigh 10 g to 20 g soil (air-dry, < 2 mm) into a weighed dish with

0
lid (a labelled, aluminium dish is recommended), dry in an oven at 10s c
for 8-24 hours.
Remove from oven, fit lid, cool and reweigh (all weighings should be
made to the nearest 10 mg). Because oven-dry soil picks up water from
the atmosphere very rapidly (even in some desiccators), it is necessary to
reweigh without delay. In practice this can either be achieved by
weighing with a top-loading balance as soon as the dish is cool enough to
handle, or after cooling in an efficient desiccator.
CALCULATION OF RESULTS
1. weight air-dry soil (g) =Moisture Factor (M.F.)

weight oven-dry soil (g)
c
c
A3.1
A3. CARBON
c
INTRODUCTION
At Soil Bureau, two methods for determination of carbon in soils are

in current use.
The method more often used is the induction furnace method, in which
the carbon is converted to carbon dioxide and this is measured volumetrically.
This method has the advantages of being rapid, convenient for most soils, and
accurate. Its main disadvantage is that it measures total soil carbon content
which includes that of any carbonate, charcoal, or live root material present.
The alternative is a colorimetric method which has the advantage that

it is more specific to humified organic carbon. This method involves a
wet oxidation of the carbon by dichromate, and the measurement of the
amount of reduced chromium present. The disadvantage of this method is
that direct calibration is not possible. Therefore calibration is made
against amounts of sucrose which have the same reducing power on dichromate
(measured colorimetrically) as have known amounts of soil carbon. The
relationship between sucrose carbon and soil carbon is calculated from
figures found by previous experience with Metson's (1956) adaption of the
Schollenberger (1927a, b, 1931, 1945) and Allison (1935) methods, and the
dry combustion method.
c Methods of determining organic carbon in soils have been reviewed by
Metson et al. (1979).
(_
A3.2
A3.A : DETERMINATION OF TOTAL CARBON USING

HIGH FREQUENCY INDUCTION FURNACE EQUIPMENT
c
INTRODUCTION
The following method refers particularly to the equipment produced by

the Laboratory Equipment Corporation (Leco), St Joseph, Michigan, U.S.A.
The method involves the purification and measurement of carbon dioxide
(C0 2) evolved when a sample is heated in a stream of oxygen. The heat is
produced by a high frequency electrical flux induced in a mixture of the
sample and of a conducting matrix of iron chips, and temperatures in
excess of 1400°c can be attained. The carbon dioxide is purified by
passing it in turn through a dust trap, through precipitated silver to
remove chlorine, through a converter furnace to convert any carbon monoxide
(CO) to carbon dioxide, and through manganese dioxide (Mn0 2) to remove
sulphur dioxide (S0 2). The measurement of carbon dioxide is carried out
by passing the remaining gases (C02 + 02) into a calibrated burette in
which 5% H2SO~ is displaced. The gases (C0 2 + 0 2) are flushed through
concentrated potassium hydroxide solution which absorbs the carbon dioxide.
The difference between the original volume of gas in the burette and the
volume of carbon dioxide-free gas is equal to the volume of carbon dioxide
evolved from the sample. After correction for temperature and pressure,
the carbon content of the sample is calculated. ~
This method measures total carbon and the result obtained will be
directly affected by the presence of calcium carbonate, undecomposed wood,
charcoal, etc.
There are many details of operation of the induction furnace and

associated equipment which are adequately described by the makers and are
therefore not included here. The following method concentrates on details
required for soil analysis.
REPARATION OF REAGENTS
IRON CHIPS. Leco cat. no. 501-077.
TIN METAL. Leco cat. no. 501-076.
SILICIC ACID A.R.
RED LEVELLING SOLUTION. see maker's manual.
CAUSTIC SOLUTION. see maker's manual.
MANGANESE DIOXIDE. Leco cat. no. 501-060.
PRECIPITATED SILVER METAL. precipitate from silver nitrate (AgN0 3 )

solution with sodium dithionite solution. Filter, wash precipitate with l
distilled water, and dry.
A3.3
PROCEDURE
Use finely ground (< 0.25 mm) air-dry soil and take sample weights
according to the following table:
Carbon Expected Sample Weight

% g
0.0 - 1.5 1.00

1.5 - 6 0.25
6 - 15 0.10
15 - 60 0.025
For loading the crucible use a scoop which delivers about 1 g iron
chips and charge the crucible in the following order:
1 g Sample less than 1 g Sample

1 scoop iron chips 1 scoop iron chips
c soil sample
~ scoop tin metal
soil sample
1 scoop silicic acid
2 scoops iron chips ~ scoop tin metal
2 scoops iron chips
Prepare blank crucibles, loaded as for samples, and run these until a
zero reading is obtained (usually-after 2 or 3 blanks), before proceeding
with samples.
Place the loaded crucible on the pedestal and adjust the rate of
oxygen flow from a cylinder to 0.8 litres/minute.
Raise the pedestal into the induction field. This simultaneously

closes the system and initiates induction, the combustion gases being
passed through the dust and chlorine traps, the carbon monoxide converter
furnace, and the sulphur trap before they reach the gasometric carbon
analyser (Fig. A3.1).
When the gases have displaced most of the H 2 SO~ in the burette, stop
the reaction and oxygen flow by lowering the pedestal.
Measure the percent carbon directly from the appropriate scale on the
calibrated burette applying the appropriate corrections for sample weight,
temperature and barometric pressure (see following table).
(
A3.4
Factor Chart for Leco Carbon Furnace
Atmospheric Pressure (mm) (

740 745 750 755 760 765 770 775 780
21 0.950 0.957 0 .963 0.970 0.976 0.983 0 .990 0.996 l.OOJ

22 0.945 0.952 0.958 0.965 0.972 0.978 0.985 0.991 0.998
,.......,. 2J 0.941 0.947 0.954 0. 960 0.967 0.973 o .980 0.986 0.993
0
o 24 0.936 0.942 0.949 0.955 0.962 0.968 0.975 0.981 o.9sa
'-.-'
Q) 25 0.931 0.937 0.944 0.950 0.957 0.963 0 .970 0.976 0.983

i-i
E al
26 0.926 0.932 0.939 0.945 0.952 0.958 0 .965 0.971 0.978
~P; 27 0.921 o. 927 0.934 0.940 0.946 0.953 0.959 0.966 0.972
~ 28 0.916 0.922 0 .928 0.935 0.941 0.948 0.954 0.961 0.967
E-i
29 0.910 0.917 0.923 0.930 0.936 0.942 0.949 0.955 0.962
JO 0.905 0 .911 0.918 0.924 0.931 0.937 0.943 0.950 0.956
"Degrees C" is temperature of gas as read from thermometer in

measuring burette.
c
"Atmospheric Pressure (mm)" is station pressure as read from a mercurial
or aneroid barometer. As mercury and steel expand with temperature, it is
necessary to correct the mm reading for surrounding air temperature. In
an aneroid barometer, this is accomplished by using an instrument with a
temperature compensated movement. With a mercurial barometer the
correction is made simply by reference to the following chart, which
brings the pressure to what it would be at 0 degrees C:
Room Subtract from

Temperature Uncorrected
(Degrees C) Reading
5 - 12 1 mm
13 - 20 2 mm
21 - 28 3 mm
29 - 35 4 mm
36 - 40 5 mm
A3.5
_.,. To gasometric
---- carbon analyser
Sulphur trap
Manganese dioxide
Carbon monoxide
1:~ converter furnace
lo~
lo·°""..._+-Copper oxide chips
lo
c I~~
0
Chlorine trap
Precipitated
silver metal
Dust trap
02 + C02 ...~......- ...
etc. from Calico filter
combustion tube
(
Fig. AJ.1. Flow diagram for carbon determination

using Leco induction furnace.
A3.6
NOTES:
(
(1) Use of silicic acid in mixture. One effect of the silicic acid
is to increase the viscosity of the molten material, thus decreasing crucible
failures caused by the permeation of the melt through the crucible walls.
While there is usually sufficient silica in soils to prevent this cause of
failure, there is not sufficient in blanks or organic samples (e.g., litters,
peats), and it is advisable always to include silicic acid in the crucible
charge when less than 1 g of sample is used.
(2) Constant temperature. A supply of temperature-controlled water to

the outer jacket of the carbon dioxide analyser is recommended, especially
when the temperature of the water from the mains supply is variable or when
it differs appreciably from room temperature.
(3) Cleaning of dust trap and gas delivery tube. The calico filter and
delivery tube leading to the dust trap must be cleaned and dried regularly
to prevent absorption of carbon dioxide by moisture and dust.
(4) Sulphur trap. Moist manganese dioxide has a tendency to absorb

carbon dioxide and cause low results. The effect of moisture on the
manganese dioxide can be minimised by placing the sulphur trap immediately
after the carbon monoxide converter furnace. It has been found that fresh
manganese dioxide also absorbs carbon dioxide and it as necessary to counter-
act this effect by passing copious amounts of carbon dioxide through the
trap and then flushing with oxygen to remove any excess carbon dioxide. (_
Experience has shown that as long as the sulphur trap is kept moisture-
free, renewal of the manganese dioxide and subsequent carbon dioxide
treatment are not frequently required.
(5) Use of variable transformer. Most furnaces are fitted with an auto-
matic cut-out device which operates if the safe current for the induction
coil is exceeded. To prevent this happening during an analysis it has
been found necessary to use a variable transformer to limit the induction
current to a safe level.
(_
A3. 7
( A3.B COLORIMETRIC DETERMINATION OF ORGANIC CARBON
INTRODUCTION
In 1934, Walkley and Black published a colorimetric method for carbon

determination. This was modified by Walkley in 1947, and the method given
in Metson (1956) is derived from the two papers.
The following method is essentially that of Metson with several minor

changes.
PREPARATION OF REAGENTS
CHROMIUM TRIOXIDE, about 3 M. 332.5 g chromium trioxide per litre.

Dissolve in water, make to volume and filter through sintered glass before
storing (the solution must be quite clear). The exact strength is unim-
portant.
SULPHURIC ACID, A.R., 98% w/w. This should be used fresh from the
bottle, and not left standing in a burette or beaker as it rapidly picks
up moisture from the air.
c SUCROSE, A.R., powdered. If necessary grind, using a clean mortar
and pestle, until particles are about 0.25 mm.
PREPARATION OF STANDARDS
FOR SOILS EXPECTED TO CONTAIN LESS THAN 10% C. Weigh out sucrose
standards which are equivalent to 0, 20, 40, 60, 80 and 100 mg soil carbon
according to the following table:
For 1 g Soil Samples
Soil Soil Sucrose Carbon Sucrose

Carbon Carbon Equivalent
(mg) (g)
(%) (mg)
0 0 0 0
2 20 19.6 0.0465
4 40 39.0 0.0926
6 60 58.4 0.1386
8 80 77.9 0.1849
10 100 97.4 0.2312
A3.8
FOR SOILS EXPECTED TO CONTAIN MORE THAN 10% C. Weigh out sucrose
standards which are equivalent to 0, 20, 40, 60, 80 and 100 mg soil carbon
according to the following table: c
For 0.2 g Soil Samples
Soil Soil Sucrose Carbon

Carbon Carbon Equivalent Sucrose
(g)
(%) (mg) (mg)
0 0 0 0
10 20 20.8 0.0494
20 40 41.6 0.0988
30 60 62.4 0.1481
40 80 83.2 0.1974
so 100 104.0 0.2469
PROCEDURE
FOR SOILS EXPECTED TO CONTAIN LESS THAN 10% C. Weigh out 1.00 g
finely ground soil (air-dry, < 0.25 mm) into a 200-ml Taylor type flask
which is calibrated to show the 200-ml level.
c
FOR SOILS EXPECTED TO CONTAIN MORE THAN 10% C. Weigh out 0.200 g
finely ground soil (air-dry, < 0.25 mm) into a 200-ml Taylor type flask
calibrated to show the 200-ml level.
To all soil samples and sucrose standards, add 12 ml cone. H2 S0 4 (from

a 250-ml rapid-flow dispensing burette) and swirl gently.
Stand for 10 minutes with occasional swirling.
Add 6 ml 3 M chromium trioxide solution (from a rapid automatic pipette)

and mix well by swirling, washing down any particles that have lodged on the
sides of the flask.
Stand for exactly 10 minutes and then dilute with water nearly to the
200-ml mark. It has been found that the addition of chromium trioxide
and the subsequent dilution can be conveniently carried out at 30 second
intervals.
Let the diluted solution stand overnight, preferably at a room

temperature of about 20°c.
After 18 to 24 hours, make up to the 200-ml mark with distilled water

and stir well.
Centrifuge for about 10 to 15 minutes at about 2000 rpm in a 40-ml

centrifuge tube.
Read absorption at 600 nm using 10-mm cells and with the absorptiometer
set to zero on water.
A3.9
Construct standard curves from the readings for the appropriate

standards and calculate the % carbon.
For 1 g sample, (~~) = C in soil (%)
For 0.2 g sample, (~) = C in soil (%)

2
REFERENCES
ALLISON, L.E. 1935:

Organic soil carbon by reduction of chromic acid.
Soil Science 40: 311-20
METSON, A.J. 1956:

Methods of chemical analysis for Soil Survey Samples.
N.Z. Soil Bureau Bulletin 12: 208 p.
METSON, A.J.; BLAKEMORE, L.C.; RHOADES, D.A. 1979:
c Methods for the determination of soil organic carbon

application to New Zealand so~ls.
New Zealand Journal of Science 22: 205-28.
a review, and
SCHOLLENBERGER, C.J. 1927a:

A rapid approximate method for determining soil organic matter.
Soil Science 24: 65-8.
1927b:
Exchangeable hydrogen and soil reaction.
Science 65: 552-3.
1931:
Determination of soil organic matter.
1945:
Determination of soil organic matter.
WALKLEY, A. 1947:
A critical examination of a rapid method for determining organic carbon
in soils - effect of variations in digestion conditions and of inorganic
soil constituents.
( WALKLEY, A.; BLACK, I.A. 1934:

An examination of the Degtjareff method for determining soil organic
matter, and a proposed modification of the chromic acid titration
method.
c
(
A4.l
A4. NITROGEN
c
INTRODUCTION
Method A4.A is a semi-micro method which employs a digestion to convert

nitrogen present in the sample to ammonium sulphate. Aminonium-nitrogen is
subsequently determined either by distillation and titration or by a colori-
metric Autoanalyzer method.
For samples likely to have greater than 20 ppm N0 3 (e.g. litters,

composts, plant materials, bioturbic soils) Method A4.B should be used as
it incorporates a modified digestion mixture to reduce nitrates to
ammonium sulphate.
A4.A : TOTAL NITROGEN DETERMINATION WHERE

NITRATE IS PRESENT IN TRACE AMOUNTS
(<20 PPM (0.002%) N03)
c INTRODUCTION
The method described is a modified semi-micro Kjeldahl method in

which the digestion is carried out in 50 ml calibrated test tubes inserted
in a drilled aluminium block on a hotplate. Two alternative determination
steps are described, I, the traditional steam distillation and titration
procedure and II, A colorimetric Autoanalyzer method described by Searle
(1975).
The colorimetric determination is based on the rea~tion of ammonia.

with a phenol (sodium salicylate) in alkaline oxidising conditions to
form an indophenol which absorbs strongly at 660 nm. The reaction is
catalysed by sodium nitroprusside, and a citrate-tartrate mixture is
employed to chelate metals that would otherwise form insoluble hydroxides.
DIGESTION
APPARATUS
DIGESTION TUBES. 'Exelo' 50 ml calibrated test tubes cat. no. T2/30.

l
ALUMINIUM HEATING BLOCK. Aluminium block (30 cm x 30 cm x 5 cm)
drilled with seven rows of six holes (2.7 cm diameter, 3.5 cm depth).
A4.2
HOT PLATE. Domestic single radiant element hotplate (element should

be at least 20 cm diameter and have an output of about 2 kW).
c
SULPHURIC ACID, CONC., A.R. (Special N-free or M.A.R. grades are

not required for routine work).
KJELDAHL CATALYST TABLETS. B.D.H. Cat. No. 33064. Each tablet

contains 1 g sodium sulphate and 0.1 g copper sulphate.
PROCEDURE
Weigh accurately 0.50 g finely ground (air-dry, < 0.25 mm) soil
into a dry 50 ml calibrated test tube. A dry tube is desirable to
prevent soil from sticking to the sides. For peaty soils use a smaller
sample - 0.10 to 0.20 g - to avoid excessive frothing.
A reagent blank should be carried throughout the following procedure:

Moisten the soil with a few drops of distilled water and allow the moisture
to penetrate the soil. Lower results have been reported for nitrogen
determinations on certain heavy clay soils where this slight wetting was
omitted (Bal 1925, Walkley 1935, Alper 1938). Add a Kjeldahl catalyst
tablet and 3.25 ml of cone. H2S04. (_
Significant errors will occur in the colorimetric Autoanalyzer method
(II) if the final acid content of the digest falls outside the range 2.75 -
3.25 ml of cone. H2S0 4 . Some soils (particularly Pacific Island soils
derived from andesitic ash) have been found to neutralise up to 0.5 ml
cone. H2 S04 per 0.5 g sample, and consequently, the higher amount of acid
(3.25 ml instead of 3.0 ml) has been adopted to eliminate this source of
eTror.
Place the tubes in a preheated aluminium digestion block on a radiant-

element hotplate. Boil the digestion mixture until it decolorises (usually
20-30 min.). Soils high in organic matter need careful watching as frothing
occurs. The digestion is then carried on for another 20-30 min. to ensure
conversion of all nitrogen to ammonium sulphate.
Remove tubes from block. For determination method I the complete

sample may be transferred to the distillation apparatus. This procedure
however may be difficult as the digest solidifies when cold and can be
a problem to redissolve. It is preferable, therefore, to prepare the
digests as for Method II and take an aliquot (usually 25 ml) for the
distillation.
For determination method II, before the digests are completely cold
(5-6 min. after removal) add carefully 10-15 ml of distilled water and
swirl to hasten the solution of salts. When cool make to 50 ml mark with (_
distilled water, stopper and shake vigorously. Allow solids to settle
(usually overnight) before the colorimetric determination is carried out.
A4.3
l. DETERMINATION USING MANUAL METHOD
(
BORIC ACID, 1% SOLUTION. Dissolve 100 g H3 B0 3 , A.R., in 10 litres

of distilled water.
HYDROCHLORIC ACID (HCl), 0.02 M.
BROMOCRESOL GREEN - METHYL RED MIXED INDICATOR (Ma and Zuazaga 1942).
Mix 5 parts 0.1% bromocresol green in 95% EtOH with 1 part 0.1% methyl red
in 95% EtOH. · These proportions may have to be varied to obtain the neutral-
grey transition colour of the indicator.
SODIUM HYDROXIDE, 1+2. Dissolve 1 kg NaOH pellets, A.R., in 2 litres

distilled water, stirring constantly.
PROCEDURE
To transfer total sample digest to distillation apparatus,

add, when cool, about 5 ml distilled water. Heat if necessary to hasten
solution of the sodium sulphate, and transfer total content to the
distilling flask, washing with two or three small portions of distilled
water.
Add approximately 10 ml 1+2 NaOH (or more if extra H2S04 was added
during the digestion). A little pH indicator will show whether sufficient
NaOH has been added, but usually formation of a brown precipitate of ferric
hydroxide, when the liquids are mixed, indicates neutralisation of the acid.
Rinse the funnel with a little distilled water.
Add 8 to 10 ml 1% boric acid* and 5-6 drops indicator to a 100 ml

Erlenmeyer flask and place under the delivery tube of the condenser so
that the tip is below the surface of the liquid.
Close sample inlet and drainage outlet and pass steam into the dis-
tillation flask. The liquid will soon boil, and the indicator in the
boric acid solution will change colour as soon as ammonia begins to distil
over.
NOTE: * At least 500 µg of N can be fixed by 10 ml 1% boric acid, with

less than 0.5% error (Yuen &Pollard 1953). The more dilute the boric
( acid that can be used with complete retention of ammonia, the sharper is
the end-point of the titration. The A.R. grade of boric acid is much
superior to the 'pure' or L.R. grade.
A4.4
After a minute or two, lower the flask so that the tip of the delivery
tube is clear of the liquid. No ammonia will be lost if the condenser is
efficient. The temperature of the distillate should not rise above 40°c (
(Yuen &Pollard 1953).
When about 20 to 25 ml of distillate have collected, rinse the tip of

the tube with a little distilled water and remove the flask.
Stop the entry of steam. The distilling flask will empty automatically
and the vacuum can be used to rinse the apparatus by immersing the delivery
tube in distilled water.
Titrate the distillate against 0.02 M HCl, to the neutral grey colour
of the indicator.
Correct titration for re_age11t blank.
1 ml 0.02 M HCl = 280 µg N.
For total digests
0.5 g soil: 0.02 M HCl (ml) x 0.056 = N (%)

0.2 g soil: 0.02 M HCl (ml) x 0.140 = N (%)
For aliquot
(_
0.02 M HCl (ml) x 0.056 x 50
0.5 g soil: aliquot (ml) = N (%)
50
0.2 g soil: 0.02 M HCl (ml) x 0.140 x = N (%)
aliquot (ml)
C.
A4.5
II. DETERMINATION USING AUTOANALYZER
c PREPARATION OF REAGENTS
DICHLORO-S-TRIAZINE - 2,4,6, TRIONE, SODIUM SALT (NaDTT),(Koch light

Cat. No. 1615h). Dissolve 10 g NaOH in 400 ml distilled water, add 0.25 g
NaDTT and make to 500 ml.
SODIUM SALICYLATE. Dissolve 15 g sodium salicylate A.R. in distilled

water and make to 1 litre.
SODIUM NITROPRUSSIDE. Dissolve 1.2 g sodium nitroprusside A.R. in

distilled water and make to 500 ml.
CITRATE-TARTRATE REAGENT. Dissolve 25 g NaOH in 800 ml distilled

water, add 6 g sodium citrate, A.R. and 18 g sodium tartrate A.R., dissolve
and make to 1 litre with distilled water.
WASH SOLUTION. Carefully add 120 ml cone. H2S0 4 , A.R. to 1500 ml

distilled water, add 40 g Na2S04, A.R. and 4 g CtiS04.5H20, A.R., dissolve
and make to 2 litres with distilled water.
c- PREPARATION OF STANDARDS
STOCK SOLUTION (1 ml= 500 µg N). Dissolve 2.3585 g ammonium

sulphate (M.A.R. or Aristar quality dried at 110°C) in approximately
800 ml distilled water. Carefully add 60 ml cone. H2S04, A.R.,20 g of
Na2S0 4, A.R.,2 g CuS0 4 .5H20,A.R.,dissolve and make to 1 litre with
distilled water in a volumetric flask.
WORKING STANDARDS. Pipette 2.5, 5.0, 10.0, 15.0, 20.0, 25.0, 40.0,
and 50.0 ml of stock solution into 250 ml volumetric flasks, and make each
to volume with wash solution (see preparation of reagents). These standards
contain 5, 10, 20, 30, 40, 50, 80, and 100 µg/ml N respectively.
PROCEDURE
Set ug Autoanalyzer as shown in flow diagram (Fig. A4.l) with heating

bath at 45 C and 660 nm filters in the colorimeter.
Pump reagents and wash solution through system for about 10 min. to
ensure complete flushing of the analytical system and wash receptacle.
Pour standard and sample solutions into cups on the sample tray, set
the recorder baseline with the colorimeter baseline control. Sample top
standard and when it reaches the colorimeter flow cell set recorder to
read 100% absorption using the standard calibration control on colorimeter
(a standard calibration of about 1 is usual). Reset baseline if necessary.
Sample standards and unknowns at a rate of 60/hr with a 5:1 sample:wash

ratio.
A4.6
Digests containing more than 50 µg/ml N can be diluted using the wash
solution as diluent. Soils with extremely high nitrogen contents should
be redigested using a smaller weight of soil. c
Prepare a standard curve of µg/ml N against % absorption.
For 0.5 g of soil made to 50 ml
µg/ml N =
N (%)
100
FLOW RATE TUBE COLOUR

AlO CONNECTORS HUHIN
REAGENT CODE
0.32 AIR BLACK
3 ML HEATING RED
(~
0.8 COMPLEXING AGENT
BATH COIL
4S0 c 0.1 SAMPLE ORANGE/GREEN
0.6 NAllTI WHITE

COLORIMETER
660 NM 0.23 NITROPRUSS !DE ORANGE/WHl"i E
15 MM FLOW
CELL 1.2 SALICYLATE YELLOW
LO WASH GREY
WASTE 2.0 PULL FROM CO LOR IMETER GREEN
Fig A4.l Flow diagram of Autoanalyzer II manifold

for total nitrogen and CEC determinations.
A4.7
A4.B TOTAL NITROGEN DETERMINATION WHERE NITRATE

CONTENT IS HIGH (>20 PPM)
NOTE: The digestion used in this method is also suitable for the
determination of total potassium and phosphorus in plant material.
DIGESTION
KJELDAHL CATALYST TABLETS. See method A4.A.
SULPHURIC ACID-SALICYLIC ACID MIXTURE. Dissolve 20 g salicylic acid,

A.R. in 600 ml cone. H2S04, A.R.
SODIUM THIOSULPHATE, A.R. crystals.
PROCEDURE
c
Weigh a 0.1 g sample into a 50 ml calibrated tube (plant material needs
to be dried for 2 hours at 105°C before weighing). Add 4.·o ml sulphuric
acid-salicylic acid mixture and allow to stand with occasional shaking for
1 hour. Stopper tubes and leave overnight.
Add 0.25 g sodium thiosulphate through a long-necked funnel and heat

gently for about 5 min.
Remove from heat, and when cool, add a Kjeldahl catalyst tablet and
carry out the digestion as described in method A4.A.
A reagent blank should be carried throughout the procedure.
I, DETERMINATION USING MANUAL METHOD
Carry out digestion, distillation, and titration according to method

A4.A, but use approximately 20 ml 1+2 NaOH for the distillation.
(_'
For total digest: 0.1 g sample: 0.02 M HCl (ml) x 0.280 N (%)
=
50
For aliquot: 0.1 g sample: 0.02 M HCl (ml) x 0.280 x aliquot = N (%)
A4.8

c_-
See method A4.AII.
STOCK SOLUTION(l ml= 500 µg N, 500 µg Kand 50 µg P). Dissolve

2.3585 g anunonium sulphate (M.A.R. or Aristar quality, dried at llOOC),
0.9533 g potassium chloride(A.R.,dried at 110°c), and 0.2292 g disodium
hydrogen orthophosphate(A.R.,dried at 110°c) in distilled water. Add
0.5 ml toluene as a preservative and make to 1 litre.
WORKING STANDARDS. Prepare 6 blank digests as described above but

add approximately 20 ml distilled water instead of making to 50 ml.
Pipette O, 1.0, 2.5, S.O, 7.5 and 10.0 ml of stock solution into
the blank digests. Make to 50 ml with distilled water.
These standards contain O, 10, 2S, SO, 75 and 100 µg/ml N and K; and
0, 1.0, 2.5, 5.0, 7.S and 10.0 µg/ml P.
c
PROCEDURE
As for A4.A.
Prepare a standard curve of µg/ml N against % absorption.
For 0.1 g sample made to SO ml

µg/ml N
= N (%)
20
NOTE: Determination of potassium in digest.
Compare potassium concentration in samples with standards using flame

emission spectrometry at 766.5 nm.
µg/ml K =
20 K (%)
A4.9
. Determination of phosphorus in digest.
c Prepare 1+1 dilutions of samples and standards with distilled water

and determine P as for AS.All.
µg/ml P p (%)
=
20
REFERENCES
ALPER, Pauline 1938:

An accurate wet-combustion method for the determination of carbon in
soils.
Journal of Agricultural Science 75: 173-80.
BAL, D.V. 1925:

The determination of nitrogen in heavy clay soils.
MA, T.S.; ZUAZAGA, G. 1942:

Micro-Kjeldahl determination of nitrogen. A new indicator and an
improved rapid method.
Industrial and Engineering Chemistry. Analytical edition 14: 280-2.
c SEARLE, P.L. 1975:

Automated colorimetric determination of ammonium ions in soil extracts
with 'TechniconAutoanalyzer II equipment".
N.Z. Journal of Agricultural Research 18: 183-7.
WALKLEY, A. 1935:
An examination of methods for determining organic carbon and nitrogen
in soils.
YUEN, S.H.; POLLARD, A.G. 1953:

Determination of nitrogen in soil and plant materials: use of boric
acid in the micro-Kjeldahl method.
Journal of the Science of Food and Agriculture 4: 490-6.
c
(__
AS.l
A5. PHOSPHORUS
(
INTRODUCTION
At the present time (1977) the main phosphorus values determined by

the New Zealand Soil Bureau Soil Analysis Section are:
AS.A TRUOG-SOLUBLE PHOSPHORUS. Determinations are normally carried

out on topsoil samples only. The values measure readily soluble phosphorus
and may be used, with some limitations, as a guide to soil fertility.
AS.B 0.5 M H2S04-SOLUBLE PHOSPHORUS. Determinations are carried out

on the separate horizons of selected whole profile samples and are used
to assess the amount of inorganic phosphorus which is present but not
fixed. The values so obtained are useful in pedological studies as they
provide an indication of the state of weathering and leaching.
AS.C PHOSPHATE RETENTION. An empirical measure of the ability of the

soil to rapidly remove phosphorus from solution, a process which is considered
to be a precursor to the much slower process of phosphorus fixation which
renders phosphorus unavailable to plants. In acid soils of pH <6.5,
compounds of iron and aluminium are considered to play an increasingly
important role (Saunders 1968) . The method has been devised so that the
concentration of phosphate used gives a high degree of differentiation between
c soils of high and low phosphorus-retention ability, and the pH used (4.6)
is close to the point of maximum phosphate retention in many soils.
AS.D ORGANIC PHOSPHORUS. Determinations are normally carried out on

all soil horizons and, when considered as a proportion of the total phos-
phorus present (particularly for B horizons), are useful in the study of
soil-forming processes.
AS.E TOTAL PHOSPHORUS. Determinations are used in conjunction with

other phosphorus fractions to elucidate the state of weathering and
leaching of a soil.
DETERMINATION
Two colorimetric methods are given for the determination of phosphorus

in the extracts. I - a manual procedure and I I - an Autoanalyzer procedure.
These methods are applicable for all the phosphorus values determined
except phosphate retention, for which a separate method is used.
A5.2
AS.A TRUOG-SOLUBLE PHOSPHORUS DETERMINATION
EXTRACTION
EXTRACTING REAGENT. 0.001 M H2 S0 4 buffered to pH 3. Dissolve 15 g

ammonium sulphate (NH 4 ) 2 S0 4 , A.R., in 10 ml 0.5 M H2 S0 4 , and dilute to 5
litres.
PROCEDURE
The amount of phosphorus extracted depends on the extraction time

which is relatively short (30 min.). Therefore it is necessary to arrange
the work so that shaking time is kept as close to the 30 min. as possible,
with minimum time spent in adding the extracting reagent to the soils,
placing flasks on shaker and filtering extracts after shaking.
Place 1 g soil (air-dry, < 2 mm) into a shaking bottle, add 200 ml
extracting reagent and shake for 30 min. on an end-over-end shaker. Filter
as soon as possible through No. 1 (Whatman) paper until at least 100 ml have
been collected, if using determination method I. If using method II filter (_
about 18 ml into a sampler test tube. (Fill to about 1 cm from top).
A reagent blank should be carried throughout the determination.
INTRODUCTION
This colorimetric procedure is based on the method of Murphy and

Riley (1962) as adapted by Watanabe and Olsen (1965). The procedure
involves reduction of the phospho-molybdate complex by ascorbic acid in
a reaction catalysed by antimony.
MURPHY AND RILEY REAGENT A. 1.2% solution of ammonium molybdate

((NH 4 ) 6 Mo 7 0 24 .4H 2 0) with 0.1 mg/ml antimony in 2.5 M H2 S0 4 •
To prepare 5 litres of solution:
Dissolve 60 g ammonium molybdate A.R., in 1 litre distilled water. The (-

rate of solution may be increased by warming, but do not warm above 60°C. -
Cool the solution.
In 250 ml distilled water dissolve 1.3343 g antimony potassium tartrate.

Add both of the dissolved reagents to 2.5 litres of 5 M H2 S0 4 (705 ml cone.
A5.3
H 2 SO~, A.R., made to 2.5 litres with distilled water). Mix thoroughly,
make to 5 litres and store in dark bottles.
(
MURPHY AND RILEY REAGENT B. In each 100 ml of reagent A dissolve
1.056 g ascorbic acid and mix. This reagent must be prepared as required
as it does not keep for more than 24 hours.
STOCK SOLUTION (100 µg/ml P). Dissolve 0.220 g potassium dihydrogen

phosphate (KH 2 PO~), A.R., in distilled water, add 0.5 ml toluene as a pre-
servative, and make up to 500 ml.
WORKING STOCK (1 µg/ml P). Pipette out 5 ml stock solution and

dilute to 500 ml in a volumetric flask.
WORKING STANDARDS. Pipette O, 5, 10, 15, 20 and 25 ml of the 1 µg/ml P

solution into 100 ml volumetric flasks (preferably of the mixing variety) and
dilute to approximately 80 ml with distilled water. These standards
contain O, 5, 10, 15, 20 and 25 µg P respectively. Treat these standards
as for samples.
PROCEDURE
c Pipette out a 50 ml aliquot of the Truog extract into a 100 ml volu-

metric flask (mixing variety if available) and dilute to approximately 80
ml with distilled water.
To standards and unknowns add 8 ml of Reagent B, make to 100 ml, and

mix well. The colour produced is stable for 24 hours and maximum intensity
is reached in 10 min.
Maximum absorption occurs at 880-885 nm. However an absorptionmeter

(e.g. Spekker) may be used, using 4 cm cells and 608 filter (660 nm).
When values of greater than 8 mg % P are encountered, smaller aliquots
should be taken and the same procedure followed.
Construct a standard curve. This should be near-linear. For a

50 ml aliquot (= 0.25 g soil) of the extract (from 2 g of soil and 400 ml
extracting reagent) made up to 100 ml:
P concentration in final solution (µg) x 0.40 =
Truog-soluble P (mg %)
c
A5.4
INTRODUCTION
The Autoanalyzer method is a modification of that proposed by Colwell

(1965) who utilised the ascorbic acid reduction of the phosphomolybdate
complex.
ACID AMMONIUM MOLYBDATE. 0.5% aIIDnonium molybdate (NH 4) 6 Mo 7 0 24 .4H 20

in 1.0 M H2S0 4 . Dissolve 5 g ammonium molybdate in 800 ml distilled
water; add carefully 56 ml cone. H2S0 4 A.R., cool and make up to 1 litre.
Add about 2 ml Wetting Agent A when cool.
ASCORBIC ACID. Dissolve 2.25 g ascorbic acid A.R. in distilled water
to make to 250 ml. This solution will keep for about a week if kept in
a refrigerator.
WASH SOLUTION. 0.5 M H2S04.
c
STOCK SOLUTION (100 µg/ml P). Dissolve 0.220 g potassium dihydrogen
phosphate (KH 2P0 4), A.R. in distilled water, add 14 ml cone. H2 S0 4 and make
to 500 ml.
WORKING STANDARDS. Pipette 1.0 and 2.0 ml aliquots of stock solution
(100 µg/ml P) into 200 ml volumetric flasks and make to volume with 0.5 M
H2S0 4 • These standards contain 0.5 and 1.0 µg/ml P.
PROCEDURE
To 18 ml of filtered extract add 0.5 ml of cone. H2S0 4 with a dispenser,

stopper and shake. Treat 18 ml of extracting solution in the same manner
to use as a blank. Cone. H2S0 4 is added to make the final solution 0.5 M
H2S0 4 and this enables the Truog solutions to be analysed with the same
manifold and reagents as for the other phosphate measurements. The error
introduced by the addition of the small volume of acid is insignificant.
Set up Autoanalyzer as shown in manifold diagram (Fig. A5.1), with

heating bath at 9o0 c and 880 nm filters in the colorimeter. Pump reagents (_
and wash solution for about 10 min. to ensure complete flushing of the
analytical system and wash receptacle. Pour standard and sample solutions
into tubes on the sample tray. Set recorder baseline with baseline control
on colorimeter.
A5.5
Sample top standard and when it reaches the colorimeter flowcell

adjust recorder to read 100% transmission with the standard calibration
( control on the colorimeter. Reset baseline if necessary, and repeat
this process to check calibration. Sample standards followed by unknowns,
at a rate of 60/hr with a 5:1 sample:wash ratio.
Prepare a standard curve of µg/ml P against % absorption.

Using a 1:200 soil:solution ratio:
µg/ml P x 20 = mg % P
FLOW RATE TUBE COLOUR
c 10 TURN
AlO CONNECTOR
MIXING COIL
5 TURN
MIXING COIL
MVMIN
0.23 AIR
REAGENT CODE
ORANGE/WH lTE
3 ML HEATING 0.6 MOLYBDATE WHITE
BATH COIL
9o c
0
0.23 SAMPLE ORANGE/WH lTE
0.6 ASCORBIC WHITE

COLORIMETER
880 NM
15 MM FLOW-
CELL
0.8 WASH RED
WASTE 1.0 PULL FROM GREY

COLORIMETER
Fig A5.l Flow diagram of autoanalyzer II manifold for phosphorus

detennination.
AS.6
AS.B 0.5 MH2 S0 4 - SOLUBLE PHOSPHORUS DETERMINATIOI~

c
EXTRACTION
SULPHURIC ACID, O.S M. Make up 280 ml cone. H2S04 A.R.,to 10 litres

(add the acid carefully and cool). Standardise to O.S M with standard
alkali.
PROCEDURE
Place O.S g of finely ground soil (air-dry, < 0.2S mm) into a 2SO ml
shaking jar and add 100 ml O.S M H2S0 4 . Shake on an end-over-end shaker for
16 hr (overnight) under temperature-controlled conditions (200 C). Filter
through a No. 42 (Whatman) 12.S cm filter paper and collect from 40 to SO ml
clear extract for determination method I (Manual). If using method II (auto-
mated), collect about 18 ml in a sampler tube. Include a reagent blank.

c
p-NITROPHENOL INDICATOR. Dissolve 0.S g p-nitrophenol in 2S ml

distilled water.
AMMONIUM HYDROXIDE, 1 + 1. One part of cone. NH 40H, A.R., (sp.gr.

0.88 -· 0.90) plus one part distilled water.
MURPHY AND RILEY REAGENT A, see Method AS.AI.
MURPHY AND RILEY REAGENT B, see Method AS.AI.
WORKING STOCK SOLUTION (1 µg/ml P) . See Method AS.AI.
WORKING STANDARDS. Prepare standards by pipetting 0, S, 10, lS, 20,

and 2S ml aliquots of working stock phosphate solution (1 µg/ml P) into
100 ml volumetric mixing flasks and make to about 80 ml with distilled
water. These solutions contain 0, S, 10, lS, 20 and 2S µg P respectively.
Treat these standards as for samples. c
A5.7
PROCEDURE
Pipette an aliquot of the filtrate containing not more than 25 µg P

into a 100 ml volumetric (mixing) flask; a 10 ml aliquot will be suitable
for most soils.
Dilute with water to about 80 ml and then adjust the pH to about 4.5
to 5.5 as follows: add 1 drop of p-nitrophenol indicator and then add 1 + 1
NH 40H drop by drop until the solution just turns yellow. For a 10 ml
aliquot, this should take from 1.5 to 2 ml (depending on the strength of
the NH40H).
Add 0.5 M H2 S0 4 drop by drop until the solution just loses its yellow
colour. When organic matter causes a yellow tinge in the solution, it
is advisable to add 2 drops of p-nitrophenol indicator and to make the pH
adjustment according to the change in indicator colour only.
Some soils give a precipitate of iron and aluminium hydroxide, but

this can be disregarded as it redissolves when the acid molybdate is added
during colour development.
Develop and measure the molybdenum blue colour using Murphy and Riley
molybdate reagent according to the procedure described under Method AS.AI.
c Construct a standard curve. This should be near-linear.
For 0.5 g sample:
(µg P in final 100 ml) x 20

Aliquot (ml) = 0. 5 M HiS0 4 - soluble P (mg %)
ACID AMMONIUM MOLYBDATE. As for Method A5.AII.
ASCORBIC ACID. As for Method A5.AII.
WASH SOLUTION. 0.5 M H2 S0 4 extraction solution.
( STOCK SOLUTION (100 µg/ml P). See Method A5.AII.

AS.8
WORKING STANDARDS. Pipette 2.0, 4.0, 6.0, 8.0, 10.0, 12.0, 16.0, and
20.0 aliquots of stock solution (100 µg/ml P) into 200 ml volumetric flasks
and make to 200 ml with 0.5 M H 2 SO~. These standards then correspond to 1,
c··
2, 3, 4, 5, 6, 8, and 10 µg/ml P.
PROCEDURE
Set up the Autoanalyzer as described in Method AS.All. Sample unknowns
at a rate of 60/hr with a 5:1 sample:wash ratio, using the appropriate range
of standards (1-5 µg/ml or 2-10 µg/ml).
For a 1:200 soil:solution ratio:
µg/ml P x 20 = mg % P.
l
A5.9
AS.C PHOSPHATE RETENTION DETERMINATION

c
EXTRACTION
P-RETENTION SOLUTION (1 mg P/ml). Dissolve 8.80 g potassium dihydrogen

phosphate (KH 2 P0 4 ) , A.R., and 32.8 g anhydrous sodium acetate (CH 3COONa), A.R.,
in distilled water, add 23 ml glacial acetic acid, A.R., and dilute to 2 litres
in a volumetric flask. The pH of this solution should be 4.6 ± 0.05.
PROCEDURE
Weigh 5 g soil (air dry, < 2 mm) into a stoppered 50 ml polypropylene

centrifuge tube, and add 25 ml P-retention solution. Shake for 24 hr
at about 20°c.
Centrifuge at 2000 rpm for 15 min.
c DETERMINATION
NITRIC VANADOMOLYBDATE ACID REAGENT. Vanadate solution - dissolve

0.8 g ammonium vanadate, A.R., in 500 ml boiling distilled water, cool
the solution, add 6 ml cone. HN03, A.R. and dilute to 1000 ml with
distilled water. Mo16bdate solution - dissolve 16 g ammonium molybdate
in distilled water at 50 C, cool and dilute to 1000 ml. Prepare dilute
HN03 by diluting 100 ml cone. HN03 , A.R., to 1000 ml with distilled water.
To this add first the vanadate solution and then the molybdate solution.
Mix well.
WORKING STOCK SOLUTIONS. Pipette 0, 10, 20, 30, 40, and 50 ml

aliquots of P-retention solution (1 mg P/ml) into 50 ml flasks and make
to volume with distilled water. These solutions contain O, 0.2, 0.4,
0.6, 0.8, and 1.0 mg P/ml and correspond to 100, 80, 60, 40, 20 and 0
percent retention respectively.
AS.10
PROCEDURE
Take 1 ml aliquots with an automatic dilutor from the samples in the

centrifuge tubes, and from the working standards, and dispense into
labelled 30 ml tubes with 19 ml of the nitric vanadomolybdate acid reagent.
Shake well.
Wipe the delivery tip of the dilutor after each step, and carry out
a complete step with distilled water between standards to avoid possible
contamination of working stock solutions.
Read the absorbance, after at least 30 min., at 466 nm, setting the
instrument to read zero on distilled water.
Prepare a standard curve of % phosphate retention against absorbance.

Read off unknowns.
l_
AS.11
A5.D ORGANIC PHOSPHORUS DETERMINATION

IGNITION METHOD
INTRODUCTION
This phosphorus fraction is determined from the increase in 0.5 M

H2S0 4 -soluble phosphorus caused by ignition of the soil, which converts
organic phosphorus to inorganic phosphate. It has been found that in
some soils with very low base status, phosphorus may be lost during
ignition. To prevent this, calcium acetate is added prior to ignition.
In strongly weathered soils ignition causes positive errors due to

solubilisation of some forms of inorganic phosphorus (which were previously
insoluble in 0.5 M H2S0 4). In some tropical soils (e.g. Cook Island
soils) these errors are sufficient to render the results for organic
phosphorus invalid.
EXTRACTION
c CALCIUM ACETATE, 20%. Dissolve 100 g anhydrous salt, A.R., by

heating in 400 ml distilled water. Add about 5 ml glacial acetic acid
to aid solution and make up to 500 ml with water.
0.5 M SULPHURIC ACID. See Method AS . B.
PROCEDURE
Weigh 0.5 g finely ground soil (air-dry, < 0.25 mm) into a 5 ml
silica crucible, wet with 0.5 ml calcium acetate solution (20%) and dry
in an oven (110°C). Ignite for 60 minutes at SS0°C, cool, and drop
crucible into a 250 ml shaking jar containing 100 ml 0.5 M H2S0 4 .
Carry out extractions as for Method AS.B.
I DETERMINATION BY MANUAL METHOD
Carry out colour development and calculation as described in Method

AS.BI. This calculation gives the amount of ignited 0.5 M H2S0 4 soluble
phosphorus.
( II DETERMINATION USING AUTOANALYZER
Carry out determination and calculation described in Method AS.BII.

This calculation gives the amount of ignited 0.5 M H2S04 soluble phosphorus.
AS.12
[Ignited o. s M H2SOa. -soluble P (mg%)l-Co. 5 M H2SOa. -soluble P (mg%)]=

c
Organic P (mg%)
A5.13
AS.E TOTAL PHOSPHORUS DETERMINATION

(
INTRODUCTION
The following method is based on the method recommended by Syers

et al. (1968) who compared several extraction procedures for determining
total phosphorus in soils and parent materials. They found that the
sodium carbonate procedure of Muir (1952) modified by Jackson (1958)
gave the most reliable results.
FUSION
SULPHURIC ACID, 1 + 3. Carefully add 250 ml cone. H2S0 4 , A.R., to

750 ml distilled water. Cool in running water.
SODIUM CARBONATE anhydrous Na 2C0 3 , A.R.
PROCEDURE
(
Weigh 0.25 g finely ground soil (air-dry, < 0.25 mm) into a 60 ml
platinum crucible. Add approximately half of a weighed 2 g
amount of anhydrous Na2C03,A.R., and stir thoroughly with a platinum
wire or glass rod. Cover the mixture with the rest of the Na 2C0 3 •
Place the covered crucible at a slight angle on a silica triangle over
a small diameter head Meker-type burner. Heat gently for about 5 min,
until sample is molten, carefully lifting the lid to allow air in through
a slit.
NOTE: In order to avoid reducing conditions during the fusion, it is most

impoT ant to ensure that the flame from the burner does not completely
envelope the crucible.
Increase the heat gradually until the full heat of the flame is being
used. The bottom of the· crucible should be a bright cherry red. Maintain
this heat for 4-5 min. The crucible lid should be about ~ removed to
allow the admission of air, and for the last 2 min. removed completely.
Remove the crucible and swirl until the melt has solidified around the
sides of the crucible. Cool, and transfer the crucible and lid to a 250 ml
beaker. Holding the crucible lid with platinum tipped tongs, wash any
residue from the underside, with approximately 2 ml 1 + 3 H2S04 from a
full 15 ml pipette, into the beaker and set the lid aside. Cover the
beaker with a watch-glass and carefully add the remainder of the 15 ml
1 + 3 H2S0 4 into the crucible through the gap between the beaker spout
and the watch-glass. After the effervescence has completely subsided,
tip the contents of the crucible into the beaker, and remove the crucible
after washing it thoroughly with hot distilled water. Digest for 1 hour
on a boiling water bath and filter through a No. 42 (Whatman) 12.5 cm
filter paper into a 100 ml volumetric flask. Wash beaker and filter paper
with hot distilled water, cool and make to volume. A Na 2C0 3 blank should
be treated in the same way as the samples.
AS.14
I DETERMINATION. BY MANUAL METHOD
PREPARATION OF REAGENTS c-
MURPHY AND RILEY REAGENTS A AND B. see Method AS.AI.
WORKING STOCK ( 1 ml =1 µg P. ) See Method AS. AI.
WORKING STANDARDS. Pipette O, S, 10, lS, 20 and 2S ml aliquots

of standard phosphate solution (1 ml = 1 µg P) into 100 ml volwnetric
flasks and dilute to approximately 30 ml with distilled water. These
solutions contain O, S, 10, lS, 20 and 2S µg P respectively. Treat
these solutions as for samples as regards pH adjustment and colour
development.
PROCEDURE
Pipette a suitable aliquot (usually 10 ml) of the sample solution

into a 100 ml yolwnetric flask. Adjust the pH, develop and read the
colour as described in Method AS.BI.
Prepare a standard curve from the readings for standards and read
off the phosphorus concentrations for the unknowns in µg p per 100 ml:
P in final 100 ml (µg) volume (ml)

10 x weight soil (g) x aliquot (ml) = Total phosphorus (mg %)
or, for a 0.2S g sample, making up to lOOml and taking a 10 ml aliquot:
P in final 100 ml (µg) x 4 ~ Total P (mg %)
II DETERMINATION USING AUTOANALYZER
Set up Autoanalyzer as described in Method AS.AII, using appropriate

standards for the range expected.
For 0.2S g made to 100 ml

µg/ml P x 40 = mg % P
Apply a blank correction.
AS.15
REFERENCES
COLWELL, J.D. 1965:

Determination of phosphorus in sodium hydrogen carbonate extracts
of soils.
Chemistry and Industry 21: 893-5.
JACKSON, M.L. 1958:

"Soil Chemical Analysis". Prentice-Hall. Englewood Cliffs, New
Jersey. 490 p.
MUIR, J.W. 1952:

The determination of total phosphorus in soil with particular reference
to the control of interference by soluble silica.
Analyst, London 77: 313-7.
MURPHY, J.; RILEY, J.P. 1962:

A modified single solution method for the determination of phosphate
in natural waters.
Analytica Chimica Acta, 27: 31-6.
SAUNDERS, W.M.H. 1968:

Phosphorus. Chapter 7.7 pp. 95-102 in "Soils of New Zealand, Part 2".
New Zealand Soil Bureau Bulletin 26(2): 221 p.
SYERS, J.K.; WILLIAMS, J.D.H.; WALKER, T.W. 1968:

The determination of total phosphorus in soils and parent materials.
c N.Z. Journal of Agricultural Research 11: 757-62.
WATANABE, F.S.; OLSEN, S.R. 1965:
Test of an ascorbic acid method for determing phosphorus in water
and NaHC0 3 extracts from soil.
Soil Science Society of America Proceedings 29: 677-8.
(
(
A6.l
A6. CATION EXCHANGE PROPERTIES

c
INTRODUCTION
Cation exchange properties in:lude cation exchange capacity (CEC),

total exchangeable bases by titration (TEB), exchangeable bases, i.e., Ca,
Mg, K, Na, and percentage base saturation(% BS).
The methods described here are suitable only for the usual soils of
humid regions, that is, for soils in which calcium carbonate and soluble
salts are both virtually absent. Where appreciable amounts of such
substances are present, other more complex methods of analysis must be
used for the determination of the cation exchange properties (e.g. Metson
1956).
The following methods enable the levels of individual exchangeable

bases to be determined by atomic absorption spectrometry (AAS) or by
flame emission spectrometry (FES). They also permit determination of
CEC and of TEBt. on the same sample.
1tn
The exchangeable bases are leached from the soil with 1 M _
ammonium acetate, pH 7.0, the excess removed by washing with alcohol,
leaving the exchange sites saturated with ammonium ions. These are
removed by leaching with M sodium chloride and the CEC determined from
c the amount of ammonium ions in the extract (distillation or Autoanalyzer

colorimetric determination of annnonia). Although this procedure involves
an extra leaching step for the determination of CEC, it is preferable to
the method in which the ammonia is replaced directly from the soil by
distillation ( using magnesium oxide) because the results have been found
to be more reliable and more convenient (Metson &Blakemore 1964).
TEB measurements are carried out on aliquots of the leachates.

Although summation of exchangeable Ca, Mg, K, and Na (i.e., I bases, or
TEBsum) should be used to calculate% BS (Blakemore 1964), the TEBt.t1
value is useful as a check on the individual base determinations n
and also gives a useful indication of the presence of adsorbed sulphate
when compared with I bases.
Choice between AAS and FES will depend partly on the availability of
instruments and partly on individual preferences. At Soil Bureau FES is
preferred for Ca, K, and Na. It is essential that the instrument is of
sufficiently good resolution to avoid spectral interferences such as
those caused by calcium during sodium determination and strontium during
calcium determination. Advantages of FES over AAS for these elements
include greater sensitivity for K and Na, steadier base line and sample
readings, and elimination of the recurring trouble and expense of failing
hollow cathode lamps. However, FES is not sufficiently sensitive for
the determination of exchangeable Mg, and AAS is more suitable.
For AAS analysis, strontium is added to the test solutions to overcome

the depression of calcium absorption by phosphorus and suppression of
magnesium absorption by aluminium and silicate. It is also necessary to
A6.2
add strontium during FES analysis to overcome phosphate interference on

calcium emission. Hydrochloric acid is added to ensure that there is
adequate chloride present for optimum atomic absorption, especially for
calcium determinations by AAS. Caesium is added to test solutions for
both AAS and FES to eliminate ionization of the analyte in the flame.
PREPARATION OF REAGENTS see Method A6.E.II. for reagents for

Autoanalyzer determination of CEC)
ACID-WASHED SILICA SAND. Silica sand to be treated should be

relatively pure (white) and should be sieved so that it is in the 0.25 -
0.5 mm size range (to pass through a 30-60 mesh sieve). Place about 10
litres of this material into a suitable container (e.g. lixiviating
beaker, chromatography tank), wash with tap water to disperse organic
matter, silt, and clay, and after vigorous stirring, remove these
impurities by decanting. This process should be.repeated until the
supernatant water is clear. Add 2.5 litres cone. HCl (commercial grade)
to sand and leave overnight. Stirring vigorously, wash out the acid from
the sand with copious quantities of tap water. Using a large Buchner
funnel (with a Whatman No. 542 filter paper) connected to a vacuum pump,
wash portions of the sand with distilled water until the filtrate is
chloride-free. Dry in an oven.
MACERATED FILTER PAPER. Macerate by means of a suitable machine

(e.g. food blender), a quantity of fast-filtering acid-washed filter
paper (e.g. Whatman No. 31 or 41) in distilled water.
closed jar.
Keep moist in a
c
AMMONIUM ACETATE (CH3COONH 4 ), M,pH 7.0. This is best prepared from
glacial acetic acid and strong ammonia solution as it is cheaper, and
the results for blank solutions are usually lower than when it is
prepared from the solid salt, even of A.R. grade .
. Prepare as follows: Add 1150 ml acetic acid (CH::iCOOH) (about 99%,A.R.)
to about 15 litres distilled water, shake, and add 1500 ml ammonium hydroxide
(NH 4 0H) solution (A.R. sp. gr. 0.91). Make up to ·20 litres and mix by
shaking. Che.ck pH and adjust to pH 7.0 ± 0.05 with 2 M NH1tOH and 2 M CH 3COOH.
Allow to cool before using.
WASH ETHANOL (WASH ALCOHOL). Dilute ethanol (L.R. or commercial

grade) to 90% w/w with distilled wate.r, using a hydrometer to check
strength. (N.B. water required= 9.7 ml water/litre alcohol/percentage
change. e.g. 20 litres of 95% alcohol requires 970 ml water.) Add
0.25 ml of 2 M NH 4 0H per litre. Determine the ammonium content by
distillation of a 10 ml aliquot with NaOH (steam distillation as for
nitrogen determination), and titrate the distillate with 0.0200 M HCl.
The titration should take between 0.18 and 0.33 ml, using bromocresol
green - methyl red indicator.
SODIUM CHLORIDE, approximately lM. Dissolve 1170 g NaCl, A.R., in

20 litres distilled water.
SODIUM HYDROXIDE 1 + 2. Dissolve 1 kg NaOH pellets, A.R., in 2

litres distilled water stirring constantly.
BORIC ACID, 1% solution, A.R.

A6.3
HYDROCHLORIC ACID, 0.020 M.
HYDROCHLORIC ACID, 1 M.
SODIUM HYDROXIDE, 0.020 M.
BROMOCRESOL GREEN-METHYL RED MIXED INDICATOR (Ma and Zuazaga 1942).

Mix 5 parts of 0.1% bromocresol green in 95% ethanol with 1 part of 0.1%
methyl red in 95% ethanol. These proportions may have to be varied to
obtain the neutral-grey transition colour of the indicator.
METHYL RED INDICATOR, 0 .1%. Weigh 1. 0 g finely ground methyl red

powder into a 1500 ml beaker. Add 964 ml 95% ethyl alcohol and 36 ml
0.1 M. NaOH. Stir until all the methyl red has dissolved.
STRONTIUM CHLORIDE - CAESIUM CHLORIDE SOLUTION. (7500 ppm Sr, 25000

ppm Cs). Weigh 46 g SrCh.6H20 A.R., and 6:1.6 g CsCl A.R., into a beaker,
dissolve and make to 2· litres with distilled water. This solution
contains strontium to eliminate possible phosphate interference during
the flame emission determination of calcium. Caesium is added to
eliminate ionisation of all exchangeable cations in the air/acetylene
flam.e.
1 + 3 DILUENT SOLUTION. Carefully add 54 ml cone. HCl, A.R., to

about 200 ml distilled water, add 213 ml SrC1 2 /CsCl solution and make to
2 litres with distilled water.
( l + 9 DILUENT SOLUTION. Carefully add 45 ml cone. HCl, A.R., to

233 ml 1 M ammonium acetate, add 180 ml SrCl/CsCl solution and make to
(
A6.4
A6.A LEACHING PROCEDURES
Mix 5 g soil (air-dry, < 2 mm) with 10 g acid-washed silica sand

and pack into a leaching tube (see Fig. A6.1) which has a macerated
filter paper plug.
Percolate the soil with 230 ml 1 M ammonium acetate, pH 7.0 into~

250 ml volumetric flask and make to volume (250 ml) with distilled water.
Leaching time should be at least one hour, or low results may be obtained.
Carry out a blank determination with each set on 10 g acid washed

silica sand.
NOTE: It is essential that formation of channels and air-locks in

the colum.i1 of soil and sand are avoided during leaching. This may be
ensured by application of suction to the outlet of the leaching tube when
the ammonium acetate is first added. The suction must be gentle, and
may be generated by attaching a short length of rubber tube to the outlet,
squeezing the whole tube and,while blocking off the end, releasing the
squeezed portion. The suction so obtained is applied until the ammonium
acetate just reaches the filter paper plug, at which time the end of the
rubber tube is released and the rubber tube quickly removed. The outlet
of the leaching tube is then placed into the neck of the receiving
volumetric flask during leaching.
Rinse the top of the leaching tube and the soil several times with
smc-_ll ai-nounts of wash ethanol, allowing to drain between each washing.
Percolate 200 ml ethanol through the tube and discard the percolate.
Place a 250 ml volumetric flask under the leaching tube, and leach
the soil column with 230 ml 1 M NaCl solution. Make the solution to
250 ml with distilled water.
,NOTE:
--
1. In order to avoid contamination with sodium, it is advised that·
a separate set of glassware be used for the sodium chloride
leaching.
2. A further leaching of the sample may be made to extract oxalate

soluble iron, aluminium, manganese and silicon (see Method AS).
I
1•.
A6.5
MACRO
( E
(.)-
\~~. '!/
.
CN
' vI
24mm o.d. light wall

(Jobling 5500/24)
SEMI-MICRO
E ~
0
~ \ I
v
E
0
<O
( 15mm o.d. light wall

(Jobling 5500/15 )
7mm o.d. light wall

8mm o.d. light wall (Jobling 5500/07)
(Jobling 5500/08)
E
0
<O
Fig.A6.1. Leaching tubes (actual size).

A6.6
A6.B DETERMINATION OF INDIVIDUAL (

EXCHANGEABLE BASES
CONCENTRATED STOCK SOLUTIONS:
CALCIUM, 2.000 N solution: carefull6 dissolve 50.045 g calcium

carbonate (CaC03) A.R. (dried at 110 C), in enough 1 + 1 HCl
to just dissolve it (about 200 ml), and make up to 500 ml with
0.2 M HCl.
MAGNESIUM, 0.2000 N solution: carefully dissolve 1.216 g

magnesium ribbon, A.R., in 1 + 1 HCl, as for calcium, and make
to 500 ml with 0.2 M HCl.
POTASSIUM, 0.2000 N solution: dissolve 7.455 g potassium

chloride (KCl) A.R. (dried at 110°C), in 0.2 M HCl, and make
to 500 ml with 0.2 M HCl.
SODIUM 0.2000 N solution: dissolve 5.845 g NaCl A.R. (dried

at 1100C), in 0.2 M HCl, and make to 500 ml with 0.2 M HCl.
MULTIPLE WORKING STOCK SOLUTION. Pipette 25 ml of each concentrated

c
stock solution into a 1000 ml volumetric flask, and make to mark with
deionised water. Store in a plastic (preferably teflon) bottle.
WORKING STANDARDS. Pipette out aliquots of the multiple working stock

solution to 500 ml volumetric flasks according to the following table:
Working Volume of Multiple Concentration of Working

Standard Working Stock Standards (10- 4 N)
(ml per 500 ml) Ca Mg K Na
1 0.0 0.0 0.0 0.0 0.0

2 2.5 2.5 0.25 0.25 0.25
3 5.0 5.0 0.50 0.50 0.50
4 10.0 10.0 1.00 1.00 1.00
5 15.0 15.0 1.50 1.50 1.50
6 25.0 25.0 2.50 2.50 2.50
7 50.0 50.0 5.00 5.00 5.00
(
A6.7
To each flask add 10 ml cone. HCl, 40 ml strontium-caesium solution

( (7500 ppm Sr, 25000 ppm Cs) and 125 ml 1 M ammonium acetate. Make up to
500 ml with deionised water and mix well. Store in plastic bottles.
PROCEDURE
Dilute sample solutions using the 1 + 3 diluent solution.
Determine exchangeable bases by flame spectrometry using the working

standards (previously prepared as above) for comparison. Normally standard
number 5 is used as the top standard, however if sample concentrations
exceed this standard, standards 6 and 7 may be used to avoid further
dilution of the sample. If further sample dilution is necessary, perform
a 1 + 9 dilution using the appropriate diluting solution.
Prepare a standard curve from the readings for the standards in each
case (i.e. Ca*, Mg, Na and K) and read off concentrations as N x 10- 4 •
For a 1 + 3 dilution; N x 10- 4 x 2 = me.%

For a 1 + 9 dilution; N x 10- 4 x 5 = me.%
Apply blank corrections in terms of me.%.
* See Section AlO (p. Al0.4) for correction needed when free CaC0 3 present.
(
A6.8
A6.C DETERMINATION OF TOTAL EXCHANGEABLE

(
BASES BY TITRATION <TEBtitn)
PROCEDURE
Pipette a 100 ml aliquot of the ammonium acetate leachate into a

silica basin, evaporate to dryness, and muffle for 30 min. at 50o0 c.
Take up in a known amount of 0.050 M HCl, (usually 10 ml), digest
on a waterbath for 30 min., and back titrate with 0.020 M NaOH, while
still hot, using methyl red as indicator.
This procedure is basically that described by Metson (1956) except
that the reagents are weaker and therefore NaOH is preferable to NH 4 0H.
0.0200 M HCl used (ml) = TEB (me.%)

or
(0.0500 M HCl added (ml) x 2.5) - (0.0200 M NaOH required (ml)) = c
TEB (me.%).
Apply a blank correction in terms of me.%.
c
A6.9
A6.D : CALCULATION OF TOTAL EXCHANGEABLE

( BASES BY SUMMATION <TEB sum. or E Bases)
CALCULATION
This valUe represents the sum of the individual exchangeable bases

(i.e., Ca, Mg, K, Na) when each is expressed as me.%. For the usual
soils of humid regions, TEB .t closely corresponds to TEB However,
ti n sum.
when soluble salts are present and are not removed prior to determination,
TEBsum. will exceed TEBtitn by approximately the equivalent of the metal
cations present as neutral salts. When calcium carbonate is present some
is dissolved by the ammonium acetate leaching solution, but this is titratable
by the TEBtitn procedure, .so that both the apparent TEBtitn and the apparent
TEB are increased by an amount equivalent to the amount of calcium
sum.
carbonate dissolved.
In very acid soils much aluminium, replaceable by aIIUllonium acetate,

may be present. As this aluminium is associated with the sulphate ion,
an acid reaction is developed on ignition of the aluminium sulphate formed
on evaporation, reducing the apparent TEBtitn figure and, in extreme cases,
a negative value for TEBtitn may even be obtained (Blakemore 1964) .
. Disregarding such exceptions, a comparison of TEBt.t

1 n
with TEB sum.
provides a useful guide to the accuracy of the analysis as a whole.
A6.10
A6.E : DETERMINATION OF CATION

EXCHANGE CAPACITY <CEC)
c
I DETERMINATION BY DISTILLATION
PROCEDURE
Transfer a 20 ml aliquot of the 1 M NaCl leachate to a suitable

ammonia distillation apparatus, using about 5 ml 1 + 2 NaOH to drive off
the ammonia. See Section A4.Al (p. A4.3 ) for details.
Collect the ammonia in about 10 ml 1% boric acid and titrate with

0.0200 M HCl using bromocresol green-methyl red indicator.
For a 5 g sample and 20 ml aliquot:
0.0200 M HCl used (ml) x 5 = CEC (me.%)
II DETERMINATION USING AUTOANALYZER
INTRODUCTION
The colorimetric determination of ammonium-nitrogen as described

in Method A4.A is used to determine the ammonia present in the 1 M NaCl
leachates obtained by Method A6.A. This procedure is an alternative to
the distillation method.
NaDTT, see Method A4.A.
SODIUM NITROPRUSSIDE, see Method A4.A.
SODIUM SALICYLATE, see Method A4.A.
WASH SOLUTION distilled water plus a few drops Brij 35 Wetting Agent.
CITRATE-TARTRATE, see Method A4.A.
STOCK SOLUTION (1 ml= 700 µg N). Dissolve 3.3011 g (NH4)zS04
(M.A.R. or Aristar quality dried at ll0°C) in 1 M NaCl and make to 1 litre
with 1 M NaCL
A6.ll
WORKING STANDARDS. Pipette 5.0, 10.0, 20.0, 30.0, and 40.0 ml

aliquots of stock solution into 250 ml volumetric flasks and make to mark
( with 1 M NaCl. These solutions then correspond to 14.0, 28.0, 56.0, 84.0
and 112.0 µg/ml N respectively.
PROCEDURE
Prepare sample solutions as in Method A6.A.
Set up manifold as in Method A4.A (see figure A4.1 but use 1 M NaCl
as wash solution). Set the recorder baseline using the colorimeter
baseline control.
Sample 112.0 µg/ml N standard and when it reaches the colorimeter flow-
cell, set the recorder to read 100%_absorption using the standard calibration
control on colorimeter. Reset baseline if necessary. Sample standards
and unknowns at 60/hr with a 5:1 sample:wash ratio. Samples containing
more than 112 µg/ml N can be diluted using 1 M NaCl as diluent.
With 5 g soil made to 250 ml the standards are equivalent to the

following CEC (me.%) values.
(~
Standard CEC
µg/ml N me. %.
112.0 40.0
84.0 30.0
56.0 20.0
28.0 10.0
14.0 5.0
Construct a standard curve of CEC (me.%) against % absorption for .

the standards (this should be near-linear).
Read off unknowns directly as me.%.
l
A6.12
A6.F : CALCULATION OF PERCENTAGE

BASE SATURATION C%BS)
CALCULATION
This value is derived from the CEC and TEB (or sometimes TEBtitn)
figures, when both are expressed as me.%, thus, sum.
TEB sum. (me.%) x 100

CEC (me.%) = %BS
(__
c
A6.13
A6.G SEMI-MICRO LEACHING
PROCEDURE
Mix 1 g of soil (air-dry, < 2 mm) with 2 g of acid-washed silica

sand and pack into a semi-micro leaching tube (see Fig. A6.l) which has
a macerated filter paper plug. Percolate the soil with SO ml 1 M ammonium
acetate, pH 7.0 into a SO ml flask. Make to volume with distilled water.
Dilute 1 + 3 as for Method A6.B.
The solution is then equivalent to the diluted macro-leachate and

ready for flame determination of exchangeable bases. Cation exchange
capacity is determined by washing the soil with SO ml of 90% ethanol,
leaching with 4S ml of 1 M NaCl, and making to volume in a SO ml flask.
The NaCl leachate is equivalent in concentration to that obtained in the
macro determination of CEC.
Leachings may be carried out on smaller amounts of soil with suitable

adjustment of reagent volumes and glassware.
A6.14
A6.H KCL-EXTRACTABLE ALUMINIUM ( '
INTRODUCTION
This property is sometimes referred to as "exchangeable" aluminium and
is used together with the sum of exchangeable bases to estimate the Effective
Cation Exchange Capacity (ECEC).
i.e., KCl extractable Al (me.%) + ~bases (me.%) = ECEC (me.%)
POTASSIUM CHLORIDE 1 M. Dissolve 373 g potassium chloride, A.R. in

S litres of distilled water.
STOCK SOLUTION (200 µg/ml Al). Dissolve 0.200 g pure aluminium wire
in about S ml cone. HCl with the addition of a trace (one single crystal)
of a mercury salt to catalyse the reaction. Make to 1 litre with distilled
water.
WORKING STANDARDS. Pipette 0, S, 10, 2S and SO ml of stock solution

c
(200 µg/ml Al) into 200 ml vol~etric flasks, add SO ml of 1 M KCl, 1 ml cone.
H2 S0 4 , and then make to 200 ml with distilled water. These solutions then
contain 0, S, 10, 2S and SO µg/ml Al respectively.
PROCEDURE
Weigh S.O g of soil (air-dried, < 2 mm) into a 12S ml conical flask.
Add 2S ml of 1 M KCl and swirl gently to saturate soil. Allow to stand
for about 16 h. (overnight). Filter through a No. 42 (Whatman) filter
paper into a 200 ml volumetric flask. Wash the remaining soil in the conical
flask and filter paper with a further 2S ml of 1 M KCl. Wash soil and filter
paper twice with distilled water. When filtered add 1 ml cone. H2 S0 4 and
make volumetric flask to volume with distilled water. Include a reagent
blank in the procedure.
Determine aluminium in extracts directly by high-temperature flame

spectrometry.
N.B. H2 S0 4 is added to extracts to prevent biological growths.
Prepare a standard curve of µg/ml Al against % transmission or absorbance.
µg/ml Al x 0.444 =Al (me.%).

A6.15
A6.I EXCHANGE ACIDITY
INTRODUCTION
This property refers to the acidity measured by releasing aluminium and
displaced hydrogen at pH 8.2, neutralising the resulting acidity with
triethanolamine (TEA) and titrating the excess TEA with standard acid. The
value is an indicator of pH dependent charge, and when added to total
exchangeable bases, gives a value for CEC at pH 8.2
There are a number of methods available for the determination of this

property, including leaching and shaking methods. The method described
here has been found to offer advantages in reproducibility and convenience.
Main features are the use of overnight shaking rather than leaching and the
titration of an aliquot of the equiliberated buffer solution rather than the
whole solution. This avoids the need to recover the remaining triethanolamine
completely by leaching with replacement solution, or with further portions
of buffer solution.
BUFFER SOLUTION. To 61.07 g BaC1 2 .2H 2 0 add 28 ml triethanolamine and
make to 1 litre with distilled water. Adjust the pH of the solution to
8.2 with 1 + 1 HCl (usually about 10 ml per litre). Protect from C0 2 by
attaching a drying tube containing a C0 2 absorbant (e.g. soda lime) to the
air intake.
HYDROCHLORIC ACID. 0.10 M
BROMOCRESOL GREEN. 0.1% aqueous solution.
MIXED INDICATOR. Dissolve 1.250 g methyl red and 0.825 g methylene

blue in 1 litre 90% ethanol.
PROCEDURE
Weigh 2.5 g soil (air-dry, < 2 mm) (1.0 g for soils high in organic
matter or amorphous oxides) into so ml, screw-cap, polypropylene centrifuge
tubes. Add 25 ml of buffer solution and shake overnight (16 h.) on an end-
over-end shaker. Centrifuge at 2000 r.p.m. for 15 min. Also shake at
least two blanks (i.e. 25 ml buffer solution).
Transfer 10 ml aliquot to 125 ml conical flask and add about 20 ml

distilled water. Add 1 drop bromocresol green and 5 drops mixed indicator.
Titrate with 0.10 M HCl until solution reaches first full purple colour.
Titrations on blanks should be carried out first and unknowns titrated to
same point of colour change.
A6.16
Using 2.5 g soil and 25 ml buffer solution,
[ml 0.10 M HCl, (Blank) - ml 0.10 M HCl (Sample)] x 10 = Exchange

Acidity (me.%).
Using 1.0 g soil and 25 ml buffer solution,
[ml 0.10 M HCl, (Blank) - ml 0.10 M HCl (Sample)] x 25 = Exchange

Acidity (me.%).
REFERENCES
BLAKEMORE, L.C. 1964:

Effect of adsorbed sulphate on the determination of total exchangeable
bases in soils.
MA, T.S.; ZUAZAGA, G. 1942:

Micro-Kjeldahl determination of nitrogen. A new indicator and an
improved rapid method.
Industrial and Engineering Chemistry. Analytical Edition 14: 280-2.
METSON, A.J. 1956:

METSON, A.J.; BLAKEMORE, L.C. 1964:

Determination of cation-exchange capacity of soils by ammonium absorption:
comparison of methods for determination of absorbed ammonium ion.
N.Z. Soil Bureau Report 6/1964: 12 p.
A7.l
A7. RESERVE POTASSIUM <Kc)

AND MAGNESIUM (MGR)
Al.A DETERMINATION OF Kc VALUE
INTRODUCTION
This value, which was proposed by Metson et al. (1956), represents

the long-term potassium-supplying power of the soil. The method disregards
the more readily extractable fraction of the non-exchangeable potassium
(which would be obtained in a single extraction or a small number of 1 M
HN03 extractions) and represents the nearly constant rate of release
after several extractions. This rate of release is a function of the
mineral reserves present in the soil (Metson 1968) and is not affected by
organic matter return, fertiliser applications, urine patches, etc.
In order to determine this value, the more readily soluble potassium

is removed by a single extraction with 1 M HN03 at a wide acid:soil ratio.
This fraction is discarded. Two or three successive extractions with 1 M
HN03 at a narrower acid:soil ratio are then made and K concentration in
these extracts is determined. The results of these two or three extractions,
( which should be fairly similar, are averaged to give the K value.
c
·
NITRIC ACID, approximately 1 M. Dilute 318 ml cone. HN0 3, A.R.,

sp. gr. 1.42, to 5 litres with distilled water.
CAESIUM CHLORIDE (20000 ppm Cs). Weigh 25.4 g CsCl A.R., into a
beaker, dissolve and make to 1 litre with distilled water. This solution
is added to samples and standards to suppress potassium ionisation in the
air/acetylene flame.
STOCK SOLUTION 0.200N K, see Method A6.B.
WORKING STOCK SOLUTION 0.002 N K. Pipette 10.0 ml of stock solution

(0.200 N K) into a 1 litre flask and make to volume with distilled water.
WORKING STANDARDS. Pipette O, 5, 10, 15, 20, 30 and 50 ml aliquots

of the working stock solution (0.002 N K ) into 200 ml volumetric flasks add
c 20 ml caesium chloride solution (20000 ppm Cs) 100 ml of 1 M HN0 3 and make
to volume. These solutions then correspond to 0, 0.5, 1.0, 1.5, 2.0, 3.0
and 5.0 N x 10~ 4 with respect to potassium.
A7.2
PROCEDURE
Weigh out 2.00 g soil (air-dry, < 2 mm) into a 400 ml extraction flask,
or wide-mouth conical flask.
Add 200 ml 1 M HN03 and boil for 20 min. with a smaller conical
flask inverted in the neck to act as a reflux condenser.
Allow solution to stand until supernatant is clear (about 30 min.).

Remove the bulk of the supernatant with a suitable suction device taking
care not to remove any soil. Alternatively if solution does not clear on
standing, transfer to a 250 ml centrifuge bottle using distilled water
and centrifuge for 15 min. at about 2000 rpm. Paur off and discard the
liquid. With approximately 25 ml 1 M HN0 3, transfer soil to a 40 ml
centrifuge tube, centrifuge, and discard liquid.
Transfer soil to a 100 ml conical flask with 819/26 Socket, using

exactly 25 ml 1 M HN03 in approximately five portions (dispensed from
a 25 ml burette).
Fit a 819/26 cone joint (about 110 mm in length) in the neck of the
flask to act as an air condenser, and gently boil on a hot plate for
10 min. (actual boiling time).
Transfer liquid to the 40 ml heavy-duty centrifuge tube (coarse sand

etc. may be left in flask) with a very small amount of distilled water,
centrifuge, and pour liquid into a 50 ml volumetric flask. Add 5 ml
of caesium chloride solution and make to volume with distilled water. c
Transfer soil to original 100 ml conical flask with a further 25 ml
of 1 M HN03 and repeat this boiling and centrifuging process.
Repeat, again, with a further 25 ml 1 M HN03, if a third extraction

is to be made (normally two extractions give a sufficiently accurate
result).
Determine potassium concentrations in the separate extractions by

flame emission spectrometry (FES) (cf. p. A6.l). Include a blank
determination throughout the procedure.
Prepare a standard curve of N x 10""4 K against % transmission.
For 2 g made to 50 ml
mean N x 10- 4 K
4
= Kc (me.%)
(
A7.3
c A7.B DETERMINATION OF MGR VALUE
INTRODUCTION
This value represents the acid soluble 'reserve' magnesium of the soil
(Metson &Brooks 1975) and is calculated by determining the magnesium
soluble in boiling 1 M HCl (Mg ) and subtracting the exchangeable magnesium
(Mg) obtained by leaching witRs 1 M ammonium acetate (see method A6.B).
e
HYDROCHLORIC ACID 1 M. Carefully add 430 ml of cone. HCl A.R.,to

2 litres of distilled water and make to 5 litres. Standardise with
standard alkali of comparable strength.
1 + 9 DILUENT SOLUTION. Add 175 ml SrC1 2 /CsCl solution (see method

A6) and 16 ml cone. HCl A.R.,to 1100 ml 1 M ammonium acetate and make to
(
WORKING STANDARDS. As for method A6.B.
PROCEDURE
Weigh 2.5 g of soil (air dry, < 2 mm) into a 400 ml extraction flask,
add 100 ml 1 M HCl and place an inverted 50 ml conical flask in the neck
of the extraction flask to act as a condenser. Place the extraction
flasks on a preheated hotplate (the liquid should boil after approximately
10 min and then the hotplate heat should be reduced). Boil for 15 min
(use timer) with occasional swirling. Cool for 10 min after removing
from hotplate and rinse the condenser flask into the extraction flask.
Filter extract into a 250 ml volumetric flask through a No. 42 (Whatman)
filter paper and wash four times with hot distilled water. Allow the
filtrate to cool before making to volume with distilled water. Include
a reagent blank throughout the procedure.
Dilute the sample solutions 1 + 9 with the diluent solution and

determine magnesium by atomic absorption spectrometry (AAS) at 285.2 nm
(_ using the exchangeable base standards.
A7.4
Prepare a standard curve of N x 10- 4 Mg against absorbance. c

For 1 + 9 dilution
Mg (N x 10- 4 ) x 10 = Mgas (me.%)
Mg (moisture factored)(me.%)- Mg (moisture factored)(me.%)= Mg (me.%)

as e r
REFERENCES
METSON, A.J.; ARBUCKLE, R.H.; SAUNDERS, M.L. 1956:

The potassium-supplying power of New Zealand soils as determined by
a modified normal-nitric-acid method.
Transactions of the 6th International Congress of Soil Science B: 619-27.
METSON, A.J. 1968:
The long-term potassium-supplying power of New Zealand soils.
Transactions of the 9th International Congress of Soil Science 2: 621-9.
METSON, A.J.; BROOKS, Jean M. 1975:

Magnesium in New Zealand soils. II. Distribution of exchangeable
and reserve magnesium in the main soil groups.
(
l
A8.l
c: A8. EXTRACTABLE IRON, ALUMINIUM AND SILICON
A8.A ACID OXALATE-EXTRACTABLE IRON,

ALUMINIUM AND SILICON
INTRODUCTION
The acid oxalate extraction method (Tamm 1922) depends mainly on the
complexing affinity of acid oxalate to extract colloid complexes. The
reagent dissolves amorphous oxides and hydrous oxides (its attack on crystalline
oxides and crystalline clay minerals is very limited (Tamm 1932) and, because
the forms which it dissolves play a major part in cation and anion retention
and other surface phenomena, extraction with this reagent is useful in soil
studies (Saunders 1965).
Two extraction procedures are used:
c (1)
(2)
A shaking method.
A leaching method (Daly &Binnie 1974), following the leachings

for cation exchange properties in the soil, thus avoiding ..
weighings, shakings and filterings.
Historically at Soil Bureau the extraction solution proposed by Tamm

(1922) has been used. This was a 0.175 M solution of ammonium oxalate
buffered to pH 3.25 with oxalic acid, giving a total oxalate strength of
0.275 M. To be consistent with what most workers in soil science use, and
perhaps to avoid extracting more Al, Fe and Si than they would, it has been
decided to change to the weaker extracting solution described by McKeague
and Day (1966). This is a 0.2 M solution of ammonium oxalate buffered to
pH 3 with 0.2 M oxalic acid giving a total oxalate strength of 0.2 M. It
has been found that the stronger reagent (0.275 M) used at a 1:40 soil reagent
ratio for extraction by leaching gives very similar values to a 1:100 ratio
extraction by shaking, for a wide range of Al, Fe and Si values. However,
when using the weaker reagent (0.2 M) for samples with relatively large amounts
of amorphous (> about 2% Al) materials, it has been found that neither a 1:40
leaching nor a 1:40 shaking extract as much as the stronger reagent or a
1:100 shaking.
Therefore it is recommended that if high values (> about 2% Al) are

obtained or expected, the extraction be carried out by shaking at a 1:100
ratio. For lower values, the 1:40 ratio leaching is preferred for analytical
convenience.
(
· One of the main factors which has enabled greater use to be made of the
acid oxalate method is the development of atomic absorption and flame emission
techniques by which iron, aluminium and silicon·determinations may be carried
out directly on the extracts much more easily and quickly than previously.
A8.2
Choice of the flame technique to be used and of the conditions under

which this technique is employed will be governed by the types of instruments
available. However, there are some considerations which should be taken
into account and the following notes are based on experience at Soil Bureau
c
using both absorption and emission techniques (Searle &Daly 1977).
Iron concentration may be determined by either atomic absorption

spectrometry (AAS) or flame emission spectrometry (FES). The use of the
nitrous oxide-acetylene flame for both techniques is recommended.
Aluminium concentrations may be determined either by AAS or by FES with

a nitrous oxide-acetylene flame. The FES method is more sensitive and
convenient and should be used whenever there is available a good quality
instrument equipped for the nitrous oxide-acetylene flame.
Silicon concentrations are determined only-by AAS with a nitrous oxide-

acetylene flame because FES is insufficiently sensitive. The AAS method
is not highly sensitive and a good quality instrument with scale expansion
capabilities is required for successful determinations.
NOTE: For maximum sensitivity, in both AAS and FES it is necessary to

suppress-ionisation of the species being determined, and this can be achieved
by adding an excess of a readily ionisable salt, e.g., caesium chloride.
ACID OXALATE REAGENT. A.

0.2 M Ammonium Oxalate. Dissolve 284 g
c
(NH~) 2 C 2 0~.H 2 0 in 10 litres distilled water.
B. 0.2 M Oxalic Acid. Dissolve 252 g H 2 C 2 0~.2H 2 0
in 10 litres distilled water.
Mix 1 part solution A with 0.75 parts solution B, (e.g., 5700 ml A and 4300 ml
B to give 10 litres). Check and adjust pH to 3 by adding either A or B.
CAESIUM CHLORIDE, 20 OOO µg/ml Cs. Dissolve 12.65 g CsCl A.R., in

500 ml distilled water.
1 + 4 DILUENT SOLUTION. Make 1.6 g CsCl A.R., and 25 ml cone. HCl to

1 litre with distilled water.
1 + 19 DILUENT SOLUTION. Make 1.35 g CsCl A.R., 190 ml acid oxalate

reagent and 21 ml cone. HCl to 1 litre with distilled water.
1 SUPERFLOC 1 SOLUTION, 0.4%.
STOCK SOLUTION (1000 µg/ml Fe, Al, Si). Dissolve 1.000 g pure
aluminium wire in 20 ml cone. HCl with the addition of a trace (one small
crystal) of a mercury salt to catalyse the reaction.
l
Dissolve 1.000 g pure iron wire in 40 ml 1:1 HCl. The dissolution is
hastened if the wire is cut up into small pieces and the solution heated on
a water bath.
A8.3
C-. NOTE: It may be necessary to clean the iron before weighing. This can be
done by immersing 1.5-2.0 g in cone. HCl until clean, washing with distilled
water and drying quickly.
Weigh 2.139 g pure silica sand (finely ground in an agate motar and
pestle and dried at 450°C) into a platinum crucible and add 12 g Na 2 C0 3 A.R.
Heat over a burner till molten and transfer to a muffle furnace at 1000°C
for half an hour. Cool, and dissolve the melt in about 200 ml of distilled
water. If the melt solution is cloudy, discard and refuse with finer ground
sand.
Add Al and Fe solutions to a 1000 ml volumetric flask, add approximately

500 ml H2 0, then add Si solution slowly, while stirring and make to volume
with distilled water. Add about 1 ml of toluene as a preservative.
WORKING STANDARDS (Fe, Al and Si). Pipette 0, l, 2, 6, 10, 15 and 20 ml

stock solution (1000 µg/ml Fe, Al and Si) into 200 ml flasks, add 10 ml CsCl
solution (20 OOO µg/ml), 40 ml acid oxalate reagent, 4 ml cone. HCl, and make
to volume with distilled water.
EXTRACTION
SHAKING METHOD. Shake 1.0 g soil (air-dry, < 2 mm) with 100 ml acid
c oxalate reagent in a 250 ml centrifuge bottle on an end-over-end shaker for
4 h. (The extraction should be carried out in the dark.) Add 5 drops 0.4%
superfloc and shake vigorously.
Centrifuge for 5 min at about 2000 r.p.m., filter through a No. 42

(Whatman) filter paper and collect about 50 ml. Include a reagent blank
throughout the procedure.
LEACHING METHOD. Leach 190 ml acid oxalate reagent through the soil
retained in leaching tube following the various leachings for cation exchange
properties (Method A6.A), into a 200 ml volumetric flask.
NOTE: If cation exchange properties are not required on the samples, the
same results are obtained by leaching acid oxalate reagent through the soil
without any pre-treatment by the cation exchange leachings (Daly &Binnie
1974) .
Make to volume with acid oxalate reagent.
PROCEDURE
Dilute samples 1 + 4 using the 1 + 4 diluent. Using the 0-100 µg/ml

standards this dilution ratio gives a range of 0-2% (Fe, Al and Si) in the
soil for the leaching method, and 0-5% for the shaking method. Samples
containing higher amounts should either be diluted with the 1 + 19 diluent
or read with higher standards (up to 300 µg/ml).
Measure Al and Fe by AAS or FES using a lean nitrous oxide-acetylene

flame and Si by AAS using a moderately rich nitrous oxide-acetylene flame.
A8.4
NOTE: A fuel-rich nitrous oxide-acetylene flame has a strong emission band r-

near the Fe and Al wavelengths (370.0 nm to 390.0 nm) so that it is necessary \_
to use a lean flame to obtain a suitable signal:noise ratio for FES. However,
a very lean flame is relatively cool and will cause a decrease in sensitivity.
The ideal flame has a "red feather" zone 1 to 2 cm high.
Prepare standard curves for µg/ml (Fe, Al or Si) against % transmission

or absorbance.
(1) Shaking method (1:100)
µg/ml in final solution x dilution factor (5 or 20)

100
= % (Fe, Al or Si)
µg/ml
i.e., for 5 x dilution (1 + 4) = % (Fe, Al or Si)
20
µg/ml
and for 20 x dilution (1 + 19) = % (Fe, Al or Si)
5
(2) Leaching method (1:40)
µg/ml in final solution x dilution factor (5 or 20)

c
250 = % (Fe, Al or Si)
i.e.' for 5 x dilution (1 + 4) µg/ml

50
= % (Fe, Al or Si)
and for 20 x dilution (1 + 19) µg/ml = % (Fe, Al or Si)

12.5
c
A8.5
A8.B PYROPHOSPHATE EXTRACTABLE IRON AND ALUMINIUM
INTRODUCTION
This method extracts Fe and Al complexed to organic matter. The

pyrophosphate has only a slight attack on amorphous inorganic forms (McKeague
1967). Results are used in a number of soil classification systems to separate
podzolised soils.
In other published methods, a choice is offered for ways of cleaning the

extracts prior to measurement. Some use high speed tabout 20 OOO r.p.m.)
centrifugation while others use 'superfloc' followed by low speed centrifugation
(up to 2 OOO r.p.m.). It has been found that the latter method, when used
on soils which have large amounts of amorphous material or finely divided
secondary iron oxides, does not provide suitably clear extracts. This causes
erroneously high values to be obtained by flame spectrometry. This problem
has also been noted in Canada (Ballantyne et al. 1980). The procedure used
at Soil Bureau combines high speed centrifugation (20 OOO r.p.m.) and the
addition of 'superfloc'. The presence of 'superfloc' helps avoid the re-
(_ suspension of the solid material after centrifuging.
Na~P 2 0 7 .lOH 0
SODIUM PYROPHOSPHATE, 0.1 M. Dissolve 223 g 2 in distilled
water and make to 5 litres.
1
SUPERFLOC 1 SOLUTION, 0.4%.
STOCK SOLUTION (1000 µg/ml Fe, Al and Si) (see method AS.A).
WORKING STANDARDS. Pipette 0, 2, 5, 10, 15 and 20 ml stock solution

into 200 ml volumetric flasks, add 40 ml 0.1 M sodium pyrophosphate solution
and make to volume with distilled water. These solutions contain O, 10, 25,
SO, 75 and 100 µg/ml Fe and Al (and Si).
PROCEDURE
(_
Shake 1 g soil (air-dry, < 2 mm) with 100 ml 0.1 M sodium pyrophosphate
reagent in a 250 ml centrifuge bottle on an end-over-end shaker overnight
(16 h).
A8.6
Add 5 drops 0.4% superfloc and shake vigorously. Centrifuge at 20 OOO

r.p.m. for 30 min.
(
Dilute cleaned extracts 1 + 4 with distilled water and read concentration
of Fe and Al by high temperature FES or AAS. Include a reagent blank through-
out the procedure.
Prepare standard curves for µg/ml (Fe or Al) against % transmission or

absorbance.
µg/ml (Fe or Al) = % Fe or Al
20
l
A8.7
c
A8.C DITHIONITE-CITRATE EXTRACTABLE IRON AND ALUMINIUM
INTRODUCTION
Dithionite-citrate reagent extracts 'free' (non-silicate)iron, which

includes some inorganic crystalline forms, plus the fractions extracted by
pyrophosphate and acid-oxalate (organic complexes and amorphous inorganic
forms).
The amounts of aluminium extracted by this reagent are not easy to inter-
pret however, and usually approximate the amount removed by acid-oxalate.
In s9me podzols and volcanic ash derived soils, acid-oxalate extracts larger
amounts of aluminium than does dithionite-citrate.
The method described is an adaption of that of Holmgren (1967) and

involves an overnight shaking at room temperature. This is more convenient
than the traditional methods in which the sample is extracted a number of
(' times, with heating.
SODIUM CITRATE, 22%. Dissolve 1100 g sodium citrate (Na 3 C6 H5 0 7 .2H 2 0)

in distilled water and make to 5 litres. This solution should be made on
the day required.
SODIUM DITHIONITE, Na 2 S2 0 4 , A.R.
SUPERFLOC SOLUTION, 0.4%
STOCK SOLUTION (1000 µg/ml Fe, Al and Si). See method AS.A.
DITHIONITE-CITRATE SOLUTION. Dissolve 55 g sodium citrate and 5 g

sodium dithionite in distilled water and make to 250 ml.
WORKING STANDARDS
Pipette 0, 2, 5, 10, 15 and 20 ml of stock solution in 200 ml volumetric

flasks; add 20 ml dithionite-citrate solution and make to volume with
distilled water. These solutions contain 0, 10, 25, 50, 75 and 100 µg/ml
Fe and Al (and Si).
A8.8
PROCEDURE
Weigh 1 g soil (air-dry, < 0.25 nun) into a 250 ml centrifuge bottle.
c
Add 1 g sodium dithionite and 50 ml 22% sodium citrate solution.
Shake overnight (16 h) on an end-over-end shaker. Add 50 ml distilled

water and 5 drops 0.4% superloc. Shake vigorously for a few seconds.
Centrifuge and filter through a No. 42 (Whatman) filter paper. Dilute 1 + 9
with distilled water and leave loosely stoppered for at least 2 days. Include
a reagent blank throughout the procedure.
Read Fe and Al concentration by AAS.
NOTE: It has been found necessary to use AAS rather than FES for measuring
Fe and Al levels in these extracts because a significant background interference
occurs. This presumably is caused by dissolved S0 2 and the amount will vary
from sample to sample and also between samples and standards. Severe inter-
ference has also been noted when determining iron by AAS. This would probably
be overcome by digesting samples on a water bath, but it has been found that
leaving the samples loosely stoppered for at least 2 days is a convenient and
effective means of avoiding the interference.
Prepare standard curves for µg/ml (Fe or Al) against absorbance. (~

Then, µg/ml (i~ or Al) = % Fe or Al
REFERENCES
BALLANTYNE, A.K.; ANDERSON, D.W.; STONEHOUSE, H.B. 1980:

Problems associated with extracting Fe and Al from Saskatchewan soils
by pyrophosphate and low speed centrifugation.
Canadian Journal of Soil Science 60: 141-3.
DALY, B.K.; BINNIE, H.J. 1974:

A leaching method for the extraction of acid oxalate soluble aluminium
and iron from soil in conjunction with cation exchange leachings.
Communications in Soil Science and Plant Analysis 5: 507-14.
HOLMGREN, G.G.S. 1967:

A rapid citrate-dithionite extractable iron procedure.
McKEAGUE, J.A. 1967:

An evaluation of 0.1 M pyrophosphate and pyrophosphate-dithionite in (_
comparison with oxalate as extractants of the accumulation products of
podzols and some other soils.
A8.9
c· McKEAGUE, J.A.; DAY, J.H. 1966:

Dithionite- and oxalate-extractable Fe and Al as aids in differentiating
various classes of soils.
SAUNDERS, W.M.H. 1965:

Phosphate retention by New Zealand soils and its relationship to free
sesquioxides, organic matter, and other soil properties.
SEARLE, P.L.; DALY, B.K. 1977:

The determination of aluminium, iron, manganese and silicon in acid
oxalate soil extracts by flame emission and atomic absorption spectrometry.
Geoderma 19: 1-10.
TAMM, 0. 1922:
Eine Methode Zur Bestimmung de anorganischen Komponente des Gelkomplexes
im Boden.
0
Meddelanden fran Statens skogsforsoksanstalt Stockholm 19: 387~404.
TAMM, .0. 1932:

Uber die Oxalatmethode
0
in der chemischen Bodenanalyse.
Meddelanden fran Statens skogsforsoksanstalt Stockholm 27: 1-20.
(
(
(_
A9.1
( A9. SOLUBLE SALTS
INTRODUCTION
For chemical analyses of soils from humid regions, determinations of

amounts of soluble salts present is seldom required and is usually confined
to soils from areas affected by sea water or by abnormally high amounts of
cyclic salts, and to soils which have received large dressings of fertilisers
or have been affected by animal excretion. Usually, the presence of salts
will be suspected from knowledge of the nature of the sample, but the
unexpected presence of salts is usually noted when results for total exchange-
able bases by titration are compared with results for total exchangeable
bases by swnmation. If significant amounts of salts are present, the
result for TEBt.t will be lower than TEB because there is incomplete
conversion of 1 n these cations to basicsum.oxides during ignition. Low
TEBt.t values are also obtained when ammonium acetate displaces adsorbed
sulpfia¥e from strongly acid soils during leaching (Blakemore 1964), and
it is necessary to differentiate between the effects of soluble salts and
of displaceable (adsorbed) sulphate. This is usually done by carrying
out a conductivity test on a water extract, the result of which will not
only confirm or disprove the presence or absence of soluble salts but will
also give an approximate measure of the amount present.
c Methods for extraction of soluble salts, measurement of conductivity

of the extracts and determination of the anions and cations present are
described in detail by Metson (1956). The only significant changes
which have been made to these methods are the use of atomic absorption
spectrometry (AAS) or flame emission spectrometry (FES) for the determination
of concentrations of calcium, magnesium, potassium, and sodium, and the use
of the method of Johnson and Nishita (1952) for the determination of the
amounts of sulphate ions. However, for the sake of completeness the
conductivity method, determination of cations, and determination of the
common anions (chloride and sulphate) are all described here.
PREPARATION OF EXTRACT
Shake 20 g soil (air-dry, < 2 mm) with 100 ml distilled water

for 30 minutes at about 20vC, and centrifuge. Alternative weights may
be taken provided a 1:5 soil:water ratio is retained. For soils high in
salts, centrifuging will suffice to provide an acceptable separation of
extract (owing to flocculation of clay), but for less salty soils it may
be necessary to filter through a retentive paper, a membrane filter, or a
Pasteur-Chamberland filter candle.
Conductivity measurements should be made on the extract whatever its

state of clarity, as soon as possible, because of possible changes in
(_ ionic content due to microbiological activity (Piper 1942).
A9.2
A9.A MEASUREMENT OF CONDUCTIVITY

c·
PROCEDURE
Measure the specific conductivity of the water extract in millimhos

after first rinsing the cell with de-ionised water.
Note the temperature.
Correct the reading for cell constant and temperature (see table
below) to obtain conductivity at 25°C (K 25 o).
Table A9 Temperature Factors, for Correcting

Conductivity Data on Soil Extracts to 25°c
From data of Whitney and Means, as given in L.A. Richards (1947)
Temperature Correction Temperature Correction

(oC) Factor, ft (oC) Factor, f
t
(
8 1.499 21 1.092
10 1.421 22 1.067
12 1.350 23 1.044
14 1.284 24 1.021
15 1.254 25 1. OOO
16 1.224 26 0.979
17 1.196 28 0.941
18 1.168 30 0.906
19 1.142 32 0.873
20 1.118 34 0.843
The following equations give approximate values for total soluble salts
in soil using 1:5 soil:water ratio:
C.
K o (millimho/cm) x 0.350
25
= Total Soluble Salts (%)
and K o (millimho/cm) x 5
25
= Total Soluble Salts (me.%)
A9.3
(
A9.B DETERMINATION OF WATER-SOLUBLE CATIONS
INTRODUCTION
As with exchangeable base analysis, either AAS or FES is suitable

for determination of Ca, K, and Na, but AAS is used for Mg. The standards
used for exchangeable base determinations are suitable for soluble salt
analysis, providing the extracts contain approximately the same amounts
of CsCl, HCl, ammonium acetate (CH3COONH4) and SrC1 2 as the exchangeable
base standards.
1 + 9 DILUENT SOLUTION. See Method A6.
( Although the proportions of cations present in soil/water extracts

are usually different from the proportions in the standards used for
exchangeable base analysis (sodium and magnesium usually predominate in
soil/water extracts), it has been found convenient and sufficiently
accurate to use the exchangeable base standards for determining
concentrations of soluble salts.
PROCEDURE
Dilute sample solutions 1 + 9 with diluent solution. Determine Ca,

Mg, Na and K concentrations as for Method A6.B.
Prepare standard curves of N x 10- 4 against % transmission or % absorbance.
For 1:5 soil:solution ratio and 1 + 9 dilution
= me.%
(
A9.4
A9.C DETERMINATION OF WATER-SOLUBLE ANIONS
INTRODUCTION
The-only change in the methods for determination.of water-soluble

anions described by Metson (1956) is in the method for.sulphate (described
below) which is now (1977) carried out by the colorimetric method of
Johnson and Nishita (1952).
SULPHATE (JOHNSON AND NISHITA 1952)
This method employs a special distillation apparatus in which a

suitable aliquot of the unknown solution is taken to dryness and then
heated with a strong reduction mixture (hydriodic, hypophosphorus, and
formic acids) in a stream of nitrogen. The hydrogen sulphide evolved
is trapped in zinc acetate and the resulting zinc sulphide is then used
to form methylene blue from the "amino reagent", (NN'-dimethyl-p-pheny-
lenediamine sulphate, Eastman Cat. No. 1333). The method is suitable
for the range 0 to 100 µg S (0 to 300 µg S0 4 ) in a 2 ml aliquot and it
is often necessary to dilute the soil/water extract fo.r this determination.
Sulphur standards for calibration are treated similarly to the samples.
c
Details of the method and apparatus are given under "Phosphate extractable
Sulphur", Section All.
Construct a standard curve.
For a 1:5 soil:water extract and 2 ml aliquot:
µg/ml (final solution) x 1.56 = so4 2-cme.%)
(
A9.5
CHLORIDE (SCHALES AND SCHALES 1941)
The extract is titrated with mercuric nitrate (Hg(N0 3) 2 ) and forms

the very slightly dissociated mercuric chloride (HgC1 2). The end point
is recognised by the formation of a blue complex of the excess mercuric
ions and the indicator, s-diphenylcarbazone.
MERCURIC NITRATE SOLUTION (approximately 0.02 N). Add 20 ml 2 M

HN0 3 , A.R.,to approximately 700 ml distilled water and then about 3.0 g
of mercuric nitrate, A.R. Stir to dissolve, and make to 1 litre.
DIPHENYLCARBAZONE INDICATOR, 0.1%. Dissolve 0.1 g s-diphenylcarbazone

in 100 ml 95% ethyl alcohol, store in a refrigerator.
CHLORIDE STANDARD, 0.02 N. Dry NaCl, A.R., at 120°c for 4 hr,

dissolve 1.169 g in distilled water, and make to 1 litre.
c PROCEDURE
Standardise the mercuric nitrate solution by titrating against 10 ml

0.02 N NaCl solution using 10 drops of s-diphenylcarbazone indicator.
The end point is recognised by the firs~ appearance of a faint violet-blue
colour.
Transfer a suitable aliquot of the extract to a conical flask and add

10 drops of indicator. If a faint colour appears before the addition of
mercuric nitrate, add a few drops of dilute HN0 3.
on the 1:5 soil:water extract
Hg(N03)2 (ml)x normality x 500 Cl- (me.%)

· aliquot taken (ml) =
l
A9.6
REFERENCES
BLAKEMORE, L.C. 1964:

Effect of adsorbed sulphate on the determination of total exchangeable
bases in soils.
JOHNSON, C.M.; NISHITA, H. 1952:

Microestimation of sulfur in plant material, soils, and irrigation
waters.
Analytical Chemistry 24: 736-42.
1
METSON,A.J. 1956:
Methods of chemical analysis for Soil Survey Samples.
PIPER, C.S. 1942:

"Soils and Plant Analysis". University of Adelaide, Adelaide. 368 p.
RICHARDS, L.A. (Ed.) 1947:

Diagnosis and Improvement of Saline and Alkali Soi.ls.
U.S. Department of Agriculture Regional Salinity Lalx>ratory, Riverside,
California. 149 p.
SCHALES, O.; SCHALES, SELMA S. 1941:
A Simple and Accurate Method for the Determination of Chloride in
Biological Fluids.
Journal of Biological Chemistry 140: 879-84.
Al0.1
(_ AlO. CALCIUM CARBONATE
INTRODUCTION
If a pH of 7.0 or more is obtained the soil should be analysed for

carbonate because the presence of calcium carbonate (CaC03) must be
allowed for in determinations of exchangeable cations. It occurs in
soils from arid regions, soils derived from limestone, soils affected by
lime-bearing ground waters and heavily limed soils.
AlO.A GASOMETRIC CARBON DIOXIDE METHOD
INTRODUCTION
The method described below involves treating a known weight of soil

with 20% perchloric ac1d and measuring the C02 evolved. The procedure
is similar to that of Tinsley et al. (1951); as described in Metson (1956).
c However, the acid treatment is not carried out under vacuum and the C0 2
evolved is measured volumetrically instead of by titration.
PERCHLORIC ACID, 20% w/w. Dilute 1 part of 60% HC10 4 , A.R., with
2 parts of distilled water.
PROCEDURE
Weigh an appropriate amount of finely ground soil (air-dry, < 0.25 mm)
into a 125 ml conical flask. (5 g covers the range 0-2.5% CaC0 3 and 1 g,
0-12.5% CaC03).
Fit the special rubber stopper containing oxygen inlet, acid inlet,
and gas outlet to the conical flask (Fig.Al0.1 ).
Flush the flask with oxygen to remove atmospheric C02 and then close
the gas inlet.
Add enough perchloric acid through the acid inlet to cover the soil
and gently shake the flask to ensure adequate mixing.
After about a minute, flush the flask with oxygen, transferring the
gases (C0 2 + 02 ) into the gasometric analyser where the percentage carbon
value is read as in method A3.A using the 1 g scale. Because of the
possibility of inefficient flushing or prolonged evolution of C02 from the
sample, it is advisable to repeat the flushing and gasometric determination
step (about three times) until a zero reading is obtained.
Al0.2
The total of the individual readings is then corrected for temperature

and pressure (see Method A3.A).
c
Total reading (corrected for temperature and pressure) x lOO =

12 x weight of
sample
CaC03%
20% w/w PERCHLORIC ACID

RESERVOIR
~STOPCOCK
CONTROLLED BY
NEEDLE VALVE
--· TO GASOMETRIC
CARBON AN~LYSER
(02 + C02) (
-tt----RUBBER STOPPER
f "--r---GAS OUTLET
OXYGEN _ _ _--+---+
INLET ..,__--CONICAL FLASK
---+--ACID INLET
- .
SAMPLE
l_
Fig Al0.1 Apparatus for Gasometric CaC03 determination.
Al0.3
( AlO.B DIFFERENTIAL METHOD
INTRODUCTION
Although lack of sensitivity limits the accuracy of this method,

especially when CaC0 3 contents are low (<5%), speed and simplicity makes
it useful in assessing the CaC0 3 content of soils.
CaC0 3 is determined from the difference between total carbon %

(Method A3.A) and the carbon content of the sample after pretreatment
with acid to remove carbonate carbon as carbon dioxide (Wimberly 1969).
HYDROCHLORIC ACID, A.R.,1 + 4.
IRON CHIPS. See Method A3.A.
SILICIC ACID. See Method A3.A.
( . PROCEDURE
Weigh into art empty Leco combustion crucible the same weight of sample
as used for total carbon method A3.A.
Add 1 + 4 HCl drop-wise until all visible C0 2 evolution ceases. Samples

with high carbonate content may require several additions.
Dry the crucible at loo 0 c for 30 min.
Remove from oven, add one scoop of silicic acid (if weight of soil <1 g)
followed by 2 scoops of iron chips.
Determine carbon content of the sample as for Method A3.A.
Total C% - Acid treated C% = carbonate carbon %
Assuming all carbonate to be CaC03, then:
( Carbonate carbon x ~~O = CaC03%

Al0.4
CORRECTING EXCHANGEABLE CALCIUM FOR CALCIUM CARBONATE - CALCIUM

c
WHEN %CAC0 3 IS GREATER THAN 1
CaC03 at this level is not extracted quantitatively by 1 M ammonium
acetate in the leaching process 'and values obtained for exchangeable Ca,
TEB(titn)' ~bases and% BS are incorrect and therefore are not quoted.
The words 'free lime' are inserted under these headings on the analysis
card.
WHEN %CAC03 IS LESS THAN 1

Where less than 1% CaC03 occurs in New Zealand soils it is usually
completely extracted by 1 M ammonium acetate during the leaching process
and, for these soils, extractable calcium should be corrected using the
relationship:
1% CaC03 = 20 me.% Ca
However, this relationship may not be valid for soils containing hard
CaC0 3 fragments, such as shells, where complete solubility of the CaCOa .is
not obtained for levels of less than 1%.
WHEN % CAC0 3 IS LESS THAN 0.1

Exchangeable Ca should not be corrected because the accuracy of the
CaC03 determination at this level is inadequate for useful correction and
the figures '<0.1%' are entered under 'CaC0 3 ' on the analysis card.
REFERENCES
METSON, A.J. 1956:

TINSLEY, J.; TAYLOR, T.G.; MOORE, J.H. 1951:

The determination of carbon dioxide derived from carbonates in
agricultural and biological materials.
Analyst, London, 76: 300-10.
WIMBERLY, J.W. 1969:

A rapid method for the analysis of total and organic carbon in shale
with a high-frequency combustion furnace.
Analytica Chimica Acta 48: 419-23.
All.I
All. PHOSPHATE EXTRACTABLE SULPHUR

(
INTRODUCTION
In 1954 Ensminger showed the presence of soil sulphate which is insoluble
in water but replaceable by other strongly adsorbed anions such as hydroxyl,
acetate, phosphate and fluoride. This sulphate was termed "Adsorbed sulphate"
and accumulations of it were found particularly in subsoils containing clays
high in aluminium, iron oxides and 1:1 (kaolinitic) clay minerals. Ensminger
measured this sulphate turbidimetrically as BaSO • Since then it has generally
been accepted that although smaller amounts are ~sually found in topsails,
measurement of such sulphate affords a good guide to available sulphur status
and replacement by phosphate solutions is now widely used to measure available
sulphur status.
In 1952 Johnson and Nishita developed a very sensitive distillation method

for measurement of sulphate. This involves reduction of sulphate and measurement
of the H S produced, by conversion to methylene blue. These authors noted that
as well ~s sulphate, sulphides, sulphites and possibly some very labile forms
of organic sulphur, would be included. For several reasons (e.g., high sensi-
tivity) the Johnson and Nishita method became widely used to measure sulphur in
soil extracts and a looseness of terminology crept in. Both "adsorbed sulphate"
and "adsorbed sulphur" have been commonly used even though the Johnson and
Nishita method is known to include some organic forms of sulphur.
c Other measurement techniques available include Johnson and Nishita
distillation with charcoal pre-treatment, turbidimetry with various pre-treatments
including dialysis, oxidation and charcoal. Some of these techniques will
measure varying amounts of extracted organic sulphur while others will measure
only extracted inorganic sulphate. For this reason the following nomenclature
is now used at Soil Bureau:
Phosphate-extractable sulphur: as determined by Johnson and Nishita

distillation or by turbidimetry on pre-oxidised extracts.
Phosphate-extractable sulphate: as determined by Johnson and Nishita

distillation of charcoal treated extracts.
Adsorbed sulphate: calculated by subtracting H2 0-soluble sulphate from

phosphate-extractable sulphate.
The distillation apparatus used at Soil Bureau (Fig. All.l) is a modifi-

cation of that described by Johnson and Nishita (1952). A bank of 6 individual
distillation units forms a convenient group for simultaneous operation.
Differences in the method from that described in the previous edition

(1977) include a narrower extraction ratio (1:5 instead of 1:20) and a more
concentrated extraction solution (0.04 ~instead of 0.01 ~(Searle 1979).
( PREPARATION OF REAGENTS
EXTRACTING SOLUTION 0.04 M Ca(H 2 P0 4 ) 2 • Add 44.6 g H3 P0 4 , cone., A.R.,
(88%) to about 2.5 litres distilled water in a 5 litre flask. Slowly add
with stirring a suspension containing 20 g CaC0 3 , A.R., in about a litre of
All .2
814 joint
t-tt----- Splash head
111&+----- Rubber joining tube

r-----HH------Gas washer
Condenser---------'•
>---100ml volumetric
...__.;:..._, flask
814 j o i n t - - - - - - - - - '
- - - - - - - - - - N i t r o g e n inlet
Nitrogen carrier
gas attachment - - - - - - - - - - l
814 joint-------~
Electric heating mantle or

gas - heated graphite block
Fig. All.l. Modified Johnson and Nishita apparatus.

Single distillation unit.
All.3
distilled water. Dilute to S litres with distilled water. Adjust to pH 4

(_ (pH will usually be slightly lower than this) with calcium hydroxide (made by
shaking Cao with distilled water and filtering).
CHARCOAL. Boil 2SO g decolourizing charcoal (e.g., Norit NK) with

2SO ml 1 + 1 HCl for 10 to lS min. Allow charcoal to settle and decant off
clear liquid. Wash charcoal thoroughly in a Buchner funnel with distilled water
and dry at lOS°C.
REDUCTION MIXTURE. Mix together:

either SOO ml hydriodic acid, A.R., sp. gr. 1.7,
125 ml hypophosphorous acid, SO% w/w, and
200 ml formic acid, A.R., 90%.
or SOO ml hydriodic acid, A.R., sp. gr. 1.94,

171 ml hypophosphorous acid, SO% w/w,
274 ml formic acid, A.R., 90%, and
18S ml distilled water.
Heat this mixture to llS to 117°C for 10 min and bubble nitrogen through it
to remove any hydrogen sulphide evolved, and to prevent bumping.
The reduction mixture may be re-used after regeneration as follows:

to 200 ml used mixture, add: 20 ml hydriodic acid (sp. gr. 1.7 or 1.94)
4 ml hypophosphorous acid, SO% w/w, and
36 ml formic acid, A.R., 90%.
( Heat, with nitrogen bubbling through to remove water, until the temperature
reaches llS to 117°C, and then reflux (with nitrogen bubbling through) for l~
to 2 h. Johnson and Nishita (19S2) report that the mixture may be regenerated
as many as four times provided excessive amounts of perchloric acid have not
been introduced with the samples.
SULPHIDE-ABSORBING SOLUTION (zinc acetate-sodium acetate). Weigh out

SO g zinc acetate, A.R., and 12.S g sodium acetate, A.R., hydrated, and dissolve
in distilled water. Filter through a No. S31 (Whatman) filter paper and make
up to 1 litre with distilled water.
COLOUR REAGENT ("amino reagent", Gustafsson 1960). This reagent is

prepared by acidifying the amino compound, NN'-dimethyl-p-phenylenediamine
sulphate (Eastman Cat. No. 1333) with H2 S0 4 as follows:
Dissolve 2.0 g of the amino compound in lSOO ml distilled water,

add 400 ml H2 S0 4 , cone., A.R., and dilute to 2 litres with distilled
water.
AMMONIUM FERRIC SULPHATE SOLUTION. To SO g ammonium ferric sulphate,

A.R., ((NH 4 ) 2 S0 4 .Fe 2 (S0 4 ) 3 .24H 2 0), add 10 ml H2 S0 4 , cone., A.R., and 390 ml
distilled water. Filter through a No. 42 (Whatman) filter paper.
NOTE: The methylene blue molecule contains an atom of S and the colour
reaction depends on the formation of the dye methylene blue from the
solution containing sulphide ions (equivalent in amount to the sulphate
present in the original extract), amino reagent, and ferric iron.
The reaction is very sensitive and entirely specific for sulphide
(Gustafsson 1960). It is particularly suitable for the determination
of the trace amounts of sulphate present in many soils.
All.4
STOCK SULPHATE SOLUTION (100 µg/ml S). Weigh 0.5436 g K2 S0 4 A.R.
(dried at 105°C) and dissolve in 0.04 M Ca (H 2 P0 4 ) 2 extracting solution.
c
Make to 1 litre with the extracting solution. Add a few drops of chloroform
as preservative.
WORKING STANDARDS. Pipette 0, 2.5, 5, 10, 20, 30, 40 and 50 ml

aliquots of stock solution (100 µg/ml S) into 100 ml volumetric flasks and
make to volume with extracting solution. Add 2 or 3 drops of chloroform
as a preservative. These solutions contain 0, 2.5, 5, 10, 20, 30, 40 and
50 µg/ml S. 2 ml aliquots will then contain 0, 5, 10, 20, 40, 60, 80 and
100 µg s.
PROCEDURE
PREPARATION OF EXTRACTS. Weigh 5 g soil (air-dried, < 2 mm) into
stoppered 50 ml polypropylene centrifuge tubes and add 25 ml of extracting
solution. Shake on an end-over-end shaker for 16 h (overnight) at 20°C
and then centrifuge at 2000 r.p.m. for 15 min. Include reagent blanks.
PRETREATMENT OF EXTRACTS.
1. Phosphate-extractable sulphur: Transfer 2 ml aliquots of extract
to 50 ml flask (Fig. All.l).
2. Phosphate-extractable sulphate: Transfer 10 ml of extract to
25 ml tube containing 0.1 g charcoal. Stopper and shake for a few seconds,
then allow to stand for 30 min. with occasional shaking. Filter through
No. 42 (Whatman) filter paper and transfer 2 ml aliquot to 50 ml flask for c
distillation.
STANDARDS. Pipette 2 ml of each standard into 50 ml flasks and treat

as for sample extracts.
DISTILLATION AND DETERMINATION. At the beginning of a set of

determinations, flush out the apparatus with copious quantities of distilled
water (using a vacuum to suck the water through) and suck air through the
apparatus to remove the water. With a filter paper, remove any water adhering
to the inner surface of the Bl4 cone. Turn on nitrogen supply. Wash
carrier gas attachment and dry thoroughly with filter paper. Connect to
apparatus. Add deioniseq water to the gas washer (about 1/3 full) and connect
this to the apparatus. Fit a washed glass delivery tube to the rubber on the
side arm of the gas washer.
Prepare collecting solution by measuring out 70 ml distilled water into

a 100 ml volumetric flask and pipetting into this 10 ml zinc acetate-sodium
acetate reagent. Fit the collecting flask to the distillation apparatus so
that the glass delivery tube nearly reaches to the bottom. Add 6 ml reduction
mixture to the distillation flask containing the sample extract, connect the
flask to the apparatus. Turn on the water supply to the condensers and
adjust the nitrogen flow so that the rate through each unit is about 150 ml/min.
Turn on heat source and carry out the distillation for 20 min. Disconnect (
the delivery tubes and collecting flasks from the apparatus, leaving the -
delivery tube inside the flask. Stopper the collecting flask and set aside
for colour development. Turn off the heat source. Disconnect the digestion
flasks and retain the conents for regeneration of the reduction mixture.
All.5
Fit another delivery tube and the next rece1v1ng flask containing zinc
( acetate-sodium acetate reagent and distilled water. Carry out the
distillation on this artd subsequent runs as for the first run. Change the
water in the gas washer after 6 runs.
When all the distillations have been completed and the contents of the
receiving flasks have been equilibrated with room temperature, carry out
colour development and measurement as follows:
Add 10 ml colour reagent (using a rapid-delivery safety pipette, or an

automatic dispensing pipette), re-stopper and shake gently. Add 2 ml
ammonium ferric sulphate reagent, re-stopper flask and shake vigorously.
Rinse the glass delivery tube into the flask and remove. Make up the
contents of the flask to the 100 ml mark with distilled water. After at
least 30 min. read absorbance at 670 nm on a suitable spectrophotometer (the
colours are reported to be stable for several days if stored in the dark).
The absorbance maximum is rather sharp at 670 nm (Johnson and Nishita 1952)
and should be tested for the particular spectrophotometer in use.
Construct a graph of µg S against absorbance (670 nm) and read off
unknowns as µg S.
µg S x 2.5 = S(ppm) (in soil).

(
REFERENCES
ENSMINGER, L.E. 1954:
Some factors affecting the adsorption of sulphate by Alabama soils.
GUSTAFSSON, LILY 1960:

Determination of ultramicroamounts of sulphate as methylene blue.
Part II. The reduction. Talanta 4: 236-43.
JOHNSON, C.M.; NISHITA, H. 1952:

Microestimation of sulfur in plant material, soil, and irrigation
waters.
Analytical Chemistry 24: 736-42.
SEARLE, P.L. 1979:

Measurement of adsorbed sulphate in soils - effect of varying soil-
extractant ratios and methods of measurement.
New Zealand Journal of Agricultural Research 22: 287-90.
c
c
Al2.1
Al2. ANALYSES OF PLANT LITTERS, PEATS AND COMPOST
INTRODUCTION
In the analytical work associated with soil surveys a sample should

be treated as a litter when the loss on ignition exceeds 80%. Peat and
compost samples are treated in a similar way to litters. The sample
should be air-dried and pulverised in a Wiley mill, or similar apparatus,
in order to obtain a homogeneous sample. The methods described below
are basically those outlined by Metson (1956) but have been updated for
modern instrumentation.
MOISTURE
(a) Moisture on sample as received. Compost samples only.

Weigh out a sample of about 50 g and dry overnight in an
oven at about 105°c. Cool in a desiccator and reweigh.
( CALCULATION OF RESULTS
(weight, moist sample - weight; oven dry sample) x 100

weight, moist sample
= Moisture %
(b) Moisture factor. See Method A2.
LOSS ON IGNITION
Weigh 10.00 g of air-dry material into an ignited weighed silica

basin. Heat on a buns en burner until the material has c·ompletely
charred, but do not allow it to burst into flame (smother flames with
watch glass if necessary). Ignite at 50o 0 c in a muffle furnace until
stirring with a fine wire shows that all organic matter has disappeared
(i. e. no glowing particles remaining). Cool in a desiccator and
reweigh. Keep the ash for analysis.
Weight of ash = weight Qf basin + ash - weight of basin

( Weight 0£ ash x ·10 = ash %
100 - (% ash x moisture factor) = loss on ignition.
Carry out determinations of insoluble ash, total phosphorus and total
bases only if the loss on ignition exceeds 80%. If not, samples are
treated as soils and analysed in the normal manner.
Al2.2
pH See Method Al.
CARBON See Method A3.
NITROGEN See Method A4.B.
CALCIUM CARBONATE See Method AlO.
INSOLUBLE ASH
To the ash from the loss on ignition determination add 20 ml 1 + 4 HCl,

and about 20 ml distilled water. Cover with watch glass and digest for
30 min.on waterbath. Filter through No. 542 filter paper into a 250 ml
volumetric flask and wash residue with hot water. Make filtrate to 250
ml with distilled water for total phosphorus and total bases determination.
Place filter paper and residue in an ignited, weighed, silica crucible and
char slowly over a bunsen burner. After charring, heat in muffle at 5oo 0 c
for 30 min, cool in desiccator and re-weigh.
CALCULATION OF RESULTS (~
Weight of residue (g) x 10 = Insoluble ash %
TOTAL PHOSPHORUS
Dilute an aliquot from the insoluble ash filtrate 1 + 4 with 0.55 M

H2S04 (31 ml cone. H2S04/litre). Determine phosphorus (µg/ml in extract)
by the automated method described in Method A5.B.II.
µg/ml P x 12.5 = Total P mg.%
TOTAL BASES (Ca, Mg, K and Na)
Dilute an aliquot of the insoluble ash filtrate 1 + 9 (using the

1 + 9 bases diluent (see Method A6).· Carry out the determination of
individual bases, using the standards and procedure as outlined in (_.
Method A6.B.
N x 10- 4 x 2.5 =me.% (Ca, Mg, K and Na)
Al3.l
(
Al3. PRESENTATION AND RATING OF RESULTS
CONVERSION OF VALUES TO OVEN-DRY BASIS
As results are reported on an oven-dry basis, results of analyses of

air-dry soil must be corrected using an appropriate moisture factor (see
Method A2).
The moisture factor is to be applied to results of the following

determinations:
Carbon and Nitrogen (%)

Truog, 0.5 M H 2 SO~. Organic P, and Total P (mg%)
CEC, TEB, Exchangeable bases (Ca, Mg, K, Na) (me.%)
K , Mg (me.%)
c r
Acid oxalate-extractable. Al, Fe and Si (%)
Soluble salts (me.%) or
(%)
Phosphate extractable sulphur and sulphate (ppm)
(
Calcium carbonate (%)
Insoluble ash (%)
The moisture factor is not applied to:
pH (values are not expressed on basis of a weighed amount

of soil)
C/N (ratio of values that are already corrected)
% BS (calculated from corrected results)
Conductivity (property of an extract from soil)
P Retention (empirical method based on air""'..dry soil)
REPORTING OF RESULTS
Generally, results should be reported so that the uncertainty is

restricted to the last figure given and should be rounded off to the
recommended figure after the moisture factor has been applied. On this
basis the following should be used as a guide to the number of significant
decimal places reported.
(
Al3.2
Property Determined Recormnendation

pH 1 decimal place
(
c % >15 whole number
<15 1 decimal place
N% 2 decimal places
C/N whole number
Truog-soluble P (mg.%) >l whole number
<l 1 decimal place
0.5 M H2 S0 4 -Soluble P (mg.%) >l whole number
<l 1 decimal place
Organic P (mg.%) whole number
Total P (mg.%) whole number
P retention (%) whole number
CEC (me.%) 1 decimal place
TEB (titn) (me.%) 1 decimal place
L: bases (me.%) 1 decimal place
BS (%) whole number
Exchangeable Ca (me.%) >30 whole number
<30 1 decimal place
(
Exchangeable Mg (me.%) >10 1 decimal place
<10 2 decimal places
Exchangeable K As for Mg
Exchangeable Na As for Mg
KCl extractable Al 1 decimal place
Exchangeable Acidity 1 decimal place
Acid Oxalate Al, Fe &Si (%) >l 1 decimal place
<l 2 decimal places
Pyrophosphate Al &Fe As for acid oxalate
Citrate dithionite Al &·
Fe As for acid oxalate
Phosphate extractable
sulphur (ppm) whole number
Kc (me.%) >l 1 decimal place
<l 2 decimal places
Mgr (me.%) >10 whole number
<10 1 decimal place
Water-soluble cations as for exchangeable bases (
Conductivity K25 oC (millimhos/cm) 2 decimal places
Total Soluble Salts (%) (from conductivity) 2 decimal places
Calcium Carbonate (%) <0.1 quote as <0.1%
<l 1 decimal place
..... , who1 e number
.....,;,,;:--...
f' ,,..--'
RATINGS FOR CHEMICAL PROPERTIES

The following ratings of chemical properties are used by Soil Bureau for New Zealand soils:
Phosphorus
Organic C Total N 0.5M P retention
RATING pH (1:2.5 soil:water) C/N
(%) (%) Truog H2 S0 4 Inorg. Org. Total %
(mg %) (mg %) (mg %) (Mg %) (mg %)
Very high ) >9.0 (extremely alkaline) >20 >1.0 >24 >5 >40 >50 >70 >120 90-100 I
) 8.4-9.0 (strongly alkaline)

) 7.6-8.3 (moderately alkaline) -f;
High ) 7.1-7.5 (slightly alkaline) 10-20 o. 6-1. 0 16-24 3-5 20-40 30-50 50-70 80-120 60-90
) 6.6-7.0 (near neutral) 00
Medium ) 6.0-6.5 (slightly acid) 4-10 0.3-0.6 12-16 2-3 10-20 20-30 20-50 40-80 30-60
) 5.3-5.9 (moderately acid) 7'()
/
Low 4.5-5.2 (strongly acid) 2-4 0.1-0.3 10-12 1-2 5-10 10-20 10-20 20-40 10-30
,r:;
Very low <4.5 (extremely acid) <2 <0.1 <10 <l <5 <10 <10 <20 0-10
Cation-Exchange Properties
RATING Exchangeable
CEC (me.%) TEB (me.%) BS (%) Ca (me.%) Mg (me.%) K (me.%) Na (me.%)
Very high >40 >25 80-100 >20 >7 >1.2 >2

High 25-40 15-25 60-80 10-20 3-7 o. 8-1.2 0.7-2
Medium 12-25 7-15 40-60 5-10 1-3 0.5-0.8 0.3-0.7
Low 6-12 3-7 20-40 2-5 0.5-1 0.3-0.5 0.1-0. 3
Very low <6 <3 <20 <2 <0.5 <0.3 <0.1
;i:..
~
VI
VI
RATINGS FOR CHEMICAL PROPERTIES
(cont)
Acid oxalate-extractable Phosphate-

Soluble Salts
C d t. . t * K Mg
RATING Al Fe Si sextractable
1 h on UC 1V1 y % salt
c r
(%) (%) (%) (~p~ ~~ (millirnhos/cm) (me.%) (me.%)
Very high >3.0 >2.0 >150 >2 >0.7 >0.5 >30

High 1.0-3.0 1.0-2.0 0.5 50-150 0.8 -2 0.3 -0.7 0.35-0.5 15-30
Medium 0.5-1.0 0.5-1.0 0.15-0.5 15-50 0.4 -0.8 0.15-0.3 0.20-0.35 7-15
Low 0.2-0.5 0.2-0.5 0.05-0.15 5-15 0.15-0.4 0.05-0.15 0.10-0.20 3-7
Very low <0.2 <0.2 <0.05 < 5 <0.15 <0.05 <0.10 < 3
;i:..
~
VI
.j::.
I ,r---, ~
"

Methods For Chemical Analysis of Soils

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Methods For Chemical Analysis of Soils

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A.

METHODS FOR CHEMICAL ANALYSIS OF SOILS

Bv L.C. BLAKEMOREJ P.L. SEARLEJ B.K. DALY

Soil Bureau, Department of Scientific

N-EW ZEALAND SoIL BUREAU Sc1ENTIF1c REPORT lOA

BLAKEMORE, L.C.; SEARLE, P.L.; DALY, B.K. 1981:

P.D. HASSELBERG, GOVERNMENT PRINTER, WELLINGTON, NEW ZEALAND - 1981 ( ....

A2 Moisture factor A2.l

A6 Cation exchange properties A6.l

AS Extractable iron, aluminium and silicon AS.l

A9 Soluble salts A9.l

AlO Calcium carbonate AlO.l

All Phosphate extractable sulphur All. l

Al2 Analyses of plant litters, peats and compost Al2.l

Al3 Presentation and rating of results Al3. l

In 1956, "Methods of Chemical Analysis for Soil Survey Samples" by

In common with all scientific disciplines, soil chemistry has made

These methods have been written with a minimum amount of explanatory

METSON, A.J. 1956:

This 1977 revised edition incorporates recent developments in instrumental

c 1 mg% = 1 mg per 100 g oven dry (10S°C) soil

The use of 'Soil Taxonomy' for classification of soils by Soil Bureau,

The measurement of soil pH is usually regarded as one of the simplest

Choice of conditions for measurement of pH in soils involves the

Moistness of soil to be tested,

MOISTNESS OF SOIL TO BE TESTED. The choice is between air-dry soil

SUSPENSION MEDIUM. Ideally, measurement of soil pH should be made in

In New Zealand laboratories water has usually been the suspension

When 1 M KCl is used, extensive ion exchange takes place, including

Peech (1965) advocated use of 0.01 M CaC1 2 as the suspension medium

The overall effect of using salts is to lower the measured pH values.

RATIO OF SOIL TO SUSPENSION MEDIUM. Because soil pH values decrease

DEGREE OF STIRRING. Because it has been found that pH levels for

POSITIONING OF ELECTRODES. Electr0des can be positioned to be in

Although the positioning of the glass electrode is not of such

pH 6.5 BUFFER: CONCENTRATED BUFFER. Dissolve 89.7 g disodium hydrogen

WORKING BUFFER. Pipette 20 ml concentrated buffer

pH 4.0 .BUFFER: 0.05 M ~OTASSIUM HYDROGEN PHTHALATp. Dissolve 5.106 g

1 M POTASSIUM CHLORIDE. Dissolve 74.56 g KCl, A.R., in one litre of

0.01 M CALCIUM CHLORIDE. Dry CaCh (anhydrous) at 110°C and dissolve

PREPARATION OF SAMPLE. Weigh 10 g of air-dry soil into a 100-ml

Leave to stand overnight.

MEASUREMENT OF pH. Position the electrodes so that the contact point (

~---...... Liquid level

Al.B PH IN NAF SOLUTION

BATES, R.G. 1964:

FIELDES, M.; PERROTT, K.W. 1966:

INTERNATIONAL SOCIETY OF SOIL SCIENCE COMMITTEE ON SOIL REACTION MEASUREMENTS,

A2. MOISTURE FACTOR

Most results should be reported on an oven-dry basis (see Section

Weigh 10 g to 20 g soil (air-dry, < 2 mm) into a weighed dish with

1. weight air-dry soil (g) =Moisture Factor (M.F.)

At Soil Bureau, two methods for determination of carbon in soils are

The alternative is a colorimetric method which has the advantage that

A3.A : DETERMINATION OF TOTAL CARBON USING

The following method refers particularly to the equipment produced by

There are many details of operation of the induction furnace and

TIN METAL. Leco cat. no. 501-076.

SILICIC ACID A.R.

RED LEVELLING SOLUTION. see maker's manual.

CAUSTIC SOLUTION. see maker's manual.

MANGANESE DIOXIDE. Leco cat. no. 501-060.

PRECIPITATED SILVER METAL. precipitate from silver nitrate (AgN0 3 )