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Methods of Analysis for Soils Salines

Methods of Analysis for Soils Salines

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METHODS OF ANALYSIS FOR SOILS

OF ARID AND SEMI-ARID REGIONS
by
Issam I. Bashour
and
Antoine H. Sayegh
American University of Beirut
Beirut, Lebanon
Food and Agriculture Organization of the United Nations
Rome, 2007
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proouct oo not imply tLe expression ol any opinion vLatsoever on tLe part
ol tLe !ooo ano Agriculture Crganization ol tLe Lniteo Þations concerning tLe
legal or oevelopment status ol any country, territory, city or area or ol its autLorities,
or concerning tLe oelimitation ol its lrontiers or lounoaries.
¡SBÞ 978-92-5-105661-5
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commercial purposes is proLiliteo vitLout vritten permission ol tLe copyrigLt Loloers.
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© !AC 2007
i
TABLE OF CONTENTS
PREFACE........................................................................................................................... 1
ACKNOWLEDGEMENTS................................................................................................... 2
INTRODUCTION................................................................................................................. 3
GENERAL LABORATORY GUIDELINES.......................................................................... 5
1. SOILS OF ARID AND SEMI-ARID REGIONS.......................................................... 13
1.1. Calcareous Soils ................................................................................................. 13
1.2. Gypsiferous Soils ................................................................................................ 13
1.3. Salt Affected Soils............................................................................................... 13
2. SOIL SAMPLING AND PREPARATION.................................................................. 15
2.1. Soil Sampling Tools ............................................................................................ 15
2.2. Sampling for Soil Fertility Tests........................................................................... 16
2.2.1. Time of Sampling......................................................................................... 16
2.2.2. Depth of Sampling ....................................................................................... 17
2.2.3. Methods of Sampling ................................................................................... 17
2.3. Soil Sampling for Soil Survey and Classification Studies.................................... 19
2.4. Preparation of Soil Samples................................................................................ 19
2.5. Grinding and Sieving of Soil Samples................................................................. 21
2.6. Reduction of Sample Size................................................................................... 22
3. SOIL MOISTURE...................................................................................................... 23
4. SOIL TEXTURE – PARTICLE SIZE DISTRIBUTION............................................... 25
4.1. Introduction ......................................................................................................... 25
4.2. Dispersion........................................................................................................... 26
4.3. Sedimentation..................................................................................................... 27
4.4. Bouyoucos Method ............................................................................................. 27
4.5. Gypsum Removal from Soil ................................................................................ 31
4.5.1. Gypsum Removal by Ammonium Oxalate ................................................... 31
4.5.2. Gypsum Removal by Hydrochloric Acid ...................................................... 31
4.5.3. Pretreatment of Soil with BaCl
2
to Coat Gypsum with BaSO
4
...................... 32
4.5.4. Pretreatment of Soil with BaCl
2
Solution followed by Ethanol ..................... 32
4.5.5. Pretreatment with BaCl
2
Solution (Modified Method) ................................... 33
5. SOIL DENSITY AND TOTAL PORE SPACE ........................................................... 34
5.1. Introduction ......................................................................................................... 34
5.2. Measurement of Bulk Density ............................................................................. 35
5.2.1. Bulk Density of a Disturbed Soil Sample...................................................... 35
5.2.2. Bulk Density of an Undisturbed Soil Sample................................................ 35
5.3. Measurement of Particle Density ........................................................................ 37
5.3.1. The Graduated Cylinder Method.................................................................. 37
5.3.2. The Volumetric Flask Method ...................................................................... 38
5.4. Calculation of Percent Pore Space ..................................................................... 39
6. ANALYSIS OF SATURATION PASTE EXTRACT................................................... 40
6.1. Introduction ......................................................................................................... 40
6.2. Preparation of Saturation Paste.......................................................................... 40
6.2.1. Calculation of Saturation Percentage........................................................... 41
6.2.2. Determination of Soil pH.............................................................................. 41
ii
6.3. Preparation of Saturation Extract ........................................................................ 42
6.3.1. Determination of Soil Salinity (Electric Conductivity).................................... 43
6.3.2. Determination of Soluble Sodium and Potassium........................................ 44
6.3.3. Determination of Soluble Calcium and Magnesium..................................... 44
6.3.4. Determination of Carbonate and Bicarbonate.............................................. 46
6.3.5. Determination of Chloride ............................................................................ 48
7. CALCIUM CARBONATE.......................................................................................... 49
7.1. Determination of Total Calcium Carbonate ......................................................... 50
7.2. Determination of Active Calcium Carbonate ...................................................... 50
8. CATION EXCHANGE CAPACITY (CEC) ................................................................. 53
8.1. Determination of Cation Exchange Capacity (CEC)............................................ 54
8.2. Determination of CEC in Gypsiferous and Calcareous Soils............................... 55
8.3. Exchangeable Sodium Percentage..................................................................... 56
9. SOIL GYPSUM......................................................................................................... 58
10. SOIL ORGANIC MATTER........................................................................................ 61
10.1. Walkley – Black Wet Combustion Method .......................................................... 61
11. SOIL NITROGEN...................................................................................................... 64
11.1. Total Nitrogen (Kjeldahl method) ........................................................................ 64
11.2. Determination of Mineral Nitrogen ...................................................................... 65
11.2.1. Determination of Nitrate by the Phenoldisulfonic Acid Method .................... 66
11.2.2. Determination of Nitrate by the Specific Ion Electrode................................. 68
11.3. Extraction of Exchangeable Ammonium............................................................. 69
11.3.1. Determination of Ammonium by Indophenol Blue Method........................... 69
11.3.2. Determination of Ammonium by Specific Ion Electrode ............................... 71
12. SOIL PHOSPHOROUS............................................................................................. 73
12.1. Fractionation of Soil Phosphorous ...................................................................... 73
12.2. Fate of Applied Phosphatic Fertilizer .................................................................. 73
12.3. Influence of Soil Parent Materials on the Distribution of the Inorganic P-
fractions .............................................................................................................. 74
12.4. Phosphorous Retention....................................................................................... 74
12.5. Iron and Aluminium Amorphous Phosphate in Calcareous Soils ........................ 74
12.6. Determination of Available Phosphorous (Olsen’s method) ................................ 75
13. SOIL POTASSIUM.................................................................................................... 77
13.1. Determination of Available Potassium................................................................. 77
13.2. Determination of Fixed Potassium...................................................................... 78
14. SOIL SULPHUR........................................................................................................ 80
15. GYPSUM REQUIREMENT ....................................................................................... 82
16. SOIL MICRONUTRIENTS......................................................................................... 84
16.1. Iron, Zinc, Manganese and Copper..................................................................... 84
16.1.1. Iron............................................................................................................... 84
16.1.2. Zinc.............................................................................................................. 84
16.1.3. Manganese.................................................................................................. 85
16.1.4. Copper ......................................................................................................... 86
16.2. Determination of Available Micronutrients........................................................... 87
16.2.1. DTPA Extraction Method ............................................................................. 87
iii
16.2.2. Measurement of Element Concentration Using Atomic Absorption
Spectroscopy ............................................................................................... 87
16.3. DTPA Extractability and Availability for Plant Uptake.......................................... 89
17. SOIL BORON............................................................................................................ 90
17.1. Total Boron by Na
2
CO
3
Fusion ........................................................................... 90
17.2. Available Boron by Hot Water Extraction ............................................................ 92
17.3. Measurement of Concentration by Colourimetric Methods ................................. 93
17.3.1. Colour Development – Carmine Method...................................................... 93
17.3.2. Colour Development – Azomethine-H Method............................................. 94
18. SOIL MOLYBDENUM............................................................................................... 96
19. SOIL SELENIUM ...................................................................................................... 98
20. POTENTIALLY TOXIC ELEMENTS - CD, CR, NI AND PB ..................................... 99
21. IDENTIFICATION OF CLAY MINERALS BY X-RAY DIFFRACTION (XRD) ......... 102
References..................................................................................................................... 106
List of Tables
Table 1. Chemical characteristics of saline, non-saline sodic and saline sodic soils......... 14
Table 2. Electrical conductivity values for different CaSO
4
concentrations in water .......... 59
Table 3. Effect of pretreatments on the d-spacing of selected clay minerals................... 103
List of Figures
Figure 1. Sampling pattern for fertility test in a non-uniform land ...................................... 18
Figure 2. Sampling-sites selection methods for fertility test............................................... 18
Figure 3. Field data sheet.................................................................................................. 20
Figure 4. Reduction of sample size by quartering ............................................................. 22
Figure 5. Data sheet for recording of hydrometer readings ............................................... 29
Figure 6. Texture triangle showing the percentages of sand, silt and clay in the
textural classes .................................................................................................. 30
Figure 7. Modified textural triangle for determining soil texture by the feel method .......... 30
Figure 8. Effect of soil:water ratio and particle size on total gypsum extraction................. 58
Figure 9. Identification of kaolinite using its characteristic XRD patterns ....................... 104
Figure 10. Identification of smectite using its characteristic XRD patterns ..................... 105
List of Appendices
Appendix A. List of the atomic weights of the elements .................................................. 112
Appendix B. pH indicators ............................................................................................... 113
Appendix C. Properties of laboratory materials ............................................................... 114
Appendix D. Grades of chemicals ................................................................................... 115
Appendix E. Nutrient range in soils, mg/kg (Bashour, 2001) ........................................... 116
Appendix F. Temperature factors (f
t
) for correcting resistance and conductivity data
on soil extracts to the standard temperature of 25°C....................................... 117
iv
Appendix G. Conversion factors for SI and non-SI units (Soil Science Society of
America Journal) .............................................................................................. 118
1
PREFACE
About one fourth of the land surface is in arid and semi-arid regions. Soils of
these regions are generally characterized by their slightly alkaline reaction (pH
7.8 – 8.6), and elevated accumulation of calcium- and magnesium-carbonates,
and sulphates. Because of low rainfall, high evaporation, and restricted leaching,
soluble salts accumulate to some high levels in certain areas, which lead to
saline conditions. Abundance of lime and gypsum, and the accumulation of
soluble salts, markedly influence the physical and chemical properties and the
fertility status of these soils. The surface layers of most of these soils, which
contain various kinds of deposits, are coarse textured and low in organic matters.
These factors make the management of these soils difficult, and demand studies
based on rightly adapted methods of soil analysis. The saying "test and don't
guess" is appropriate for the management of these soils, and the determination
of the problems related to irrigation and drainage, salinity, sodicity, and gypsum
content.
A number of books are available describing numerous alternative
procedures for soil analysis, and users are often confused in selecting the
appropriate methods. This publication aims to establish a middle ground between
the so-called “cook-book” and the detailed comprehensive type of manual. In
doing so, analytical methods, which have been developed and adapted specially
to the particular conditions of these soils, are described.
It is believed that this publication will be of particular interest to students,
teachers, researchers and chemists working in laboratories for providing soil
testing and analytical services to farmers in arid and semi-arid regions. It is also
hoped that this manual will be a valuable reference to organizations helping in
agricultural development projects in these regions.
2
ACKNOWLEDGEMENTS
The contributions of G. Hamdallah, for conceptualization and initiation, and M.
Bazza, for further following up of this publication, are duly acknowledged. Special
thanks are due to R.N. Roy, C. LiconaManzur, M.R. Motsara and A. Shammas
for their technical contributions in revising, editing and finalizing this document.
3
INTRODUCTION
With growing dependence on agriculture production in arid and semi-arid
regions, use of fertilizers has increased tremendously. Ironically, more fertilizers
are being applied than before, but agriculture production problems are, in
general, getting worse. An important reason, yet little understood, is the improper
use of fertilizers when it comes to kind and application rate. The problem arises
partly from the lack of proper methods of soil analysis that reflects the actual soil
status, and partly from the misunderstanding of what a fertilizer really is, how it
should be used, and for what purpose. Soils of the semi-arid and arid regions
vary widely in their condition and texture that range from sandy to loamy to
clayey. The sandy soils vary in their chemical composition, such as content of
silica, calcium carbonate and gypsum. The soil clay fraction varies in its
mineralogical composition, which is a range of combinations of kaolonite,
montmorillonite, micas, chlorite and attapulgite (Aba-Husayn and Sayegh, 1974).
In addition, the proportionate occurrence of calcium carbonate, gypsum and
soluble salts vary from one soil to another. Thus, fertilizer requirements of crops
differ from one soil to another. Yet, fertilizer practices, as followed today in the
Middle East, are carried-out on a trial and error basis without regard to soil
properties and its fertilizer needs.
A sound soil management programme should provide crops with an
adequate amount and in balanced proportion of all essential nutrients for
optimum production. Diagnosis of deficiency can be checked by analysis of plant
tissues and by soil analysis that reflect the actual condition of the soil. However,
it should be recognized that fertility is only one of the major factors affecting crop
production. Crop yield, both quantity and quality, is a function of several factors,
like the soil, water, crop variety, management practices, climate, etc.
It is difficult to successfully manage salt affected calcareous and
gypsiferous soils due to their poor physical conditions. Because of poor structure,
aeration is seriously hindered. So is water infiltration and movement because of
poor porosity. The outcome would be water logging and poor aeration.
In addition to their poor physical conditions, soils of arid and semi-arid regions
possess chemical properties that would set off certain nutritional problems, like:
ƒ Nitrogen volatilisation losses of surface applied ammonium or
ammonium-forming fertilizers due to alkaline soil reaction and high
Ca
2+
activity.
ƒ Phosphorus retention/fixation (precipitation of available fertilizer-P into
less available forms) due to alkaline soil reaction and high Ca
2+
activity.
ƒ Reduction in plant uptake of potassium due to poor aeration resulting
from excessive soil moisture content.
ƒ Micronutrient deficiencies due to reduced solubility of Fe, Zn, Mn and
Cu under alkaline soil reaction.
4
ƒ Restricted root development due to poor structure and hard pan.
Consequently, the need and motivation for this publication grew out of the
need to establish the use of soil and plant analyses as a guide to fertilizer
recommendations. The scope of this publication has been kept limited to soil
testing methods. Similar publication on methods of plant analysis will be
considered at a future date.
5
GENERAL LABORATORY GUIDELINES
In chemical laboratories, the use of acids, alkalis and some hazardous and
explosive chemicals is inescapable. Apart from this, some chemical reactions
during the process of analysis may release toxic gases and if not handled well,
may cause explosion. Inflammable gases are also used as a fuel/heating source.
Thus safe working in a chemical laboratory needs special care, both in terms of
design and construction of the laboratory building, and handling and use of
chemicals. For chemical operations special chambers also need to be provided.
Air temperature of the laboratory and working rooms should be maintained
at a constant level between 20-25
0
C. Humidity should be kept at about 50%. Soil
samples are often affected by the temperature and humidity. The temperature
influences even some chemical operations. Hence, maintenance of temperature
and humidity as specified is critical.
Proper air circulation is also important so as hazardous and toxic fumes
and gases do not stay in the laboratory for long. The release of gases and fumes
in some specific analytical operation are controlled through fume hood, trapped
in acidic/alkaline solutions and washed through flowing water. Maintenance of
clean and hygienic environment in the laboratory is essential for the good health
of the workers.
Care is needed to be taken to store acids and hazardous chemicals in
separate and safe racks. An inventory of all the equipment, chemicals, glassware
and miscellaneous items in a laboratory should be maintained. A safe laboratory
building should have suitable separate rooms for different purposes and for
performing different operations.
Laboratory Safety Measures
Special Care is required while operating equipment, handling the chemicals and
in waste disposal.
Equipment
Electrical cables, plugs and tubing need proper check to avoid accident. Various
types of gas cylinders needed in the laboratory like acetylene, nitrous oxide and
LPG may be kept under watch and properly sealed/capped and may be stored in
ventilated cupboards.
6
Chemical Reagents
Hazardous chemicals may be stored in plastic bottles. While working with
chemicals such as perchloric acid, fume hood may be used. Chemicals may be
properly labelled indicating their hazardous nature.
Bottles with inflammable substances need to be stored in stainless steel
containers.
Waste Disposal
Each country has special rules and methods for disposal of hazardous waste.
Cyanides, chromates, arsenic, selenium, cobalt and molybdate are very
commonly used but hazardous chemicals and should never be disposed off in
the laboratory sink but collected in a metal container for proper disposal at the
specified places and in the manner as described in the country’s law for waste
disposal.
General Rules and Required Care
- Learn safety rules and use of first aid kits. Keep the first aid kit handy at a
conspicuous working place in the laboratory.
- Personal safety aids such as laboratory coat, hand protection gloves,
safety glasses, face shield and proper footwear should be used while
working in the laboratory.
- Observe normal laboratory safety practice in connecting equipment with
power supply, in handling chemicals and preparing solutions of reagents.
All electrical work must be done by qualified personnel.
- Maintain instrument manual and logbook for each equipment to avoid
mishandling, accident and damage to equipment.
- Keep the working tables/space clean. Clean up spillage immediately.
- Wash hands after handling toxic / hazardous chemical.
- Never suck the chemicals with mouth but use automatic pipetting device.
- Use forceps / tongs to remove containers from the hot
plates/ovens/furnaces.
- Do not use laboratory glassware for eating/drinking.
- Use fume hood while handling concentrated acids, bases and hazardous
chemicals.
- Never open a centrifuge cover until the machine has stopped.
- Add acid to water and not water to acid while diluting the acid.
- Always put labels on bottles, vessels and wash bottles containing
reagents, solutions, samples and water.
- Handle perchloric acid in fume hoods. Avoid direct contact with organic
matter/rubber. In wet oxidation method of sample digestion, destroy
organic matter first with nitric acid.
- Read the labels of the bottles before opening them.
7
Laboratory Quality Control
Quality control is an important part of quality assurance, which is defined by ISO
as “the operational techniques and activities that are used to satisfy quality
requirements”. Quality assessment or evaluation is necessary to see if the
activities performed to verify the quality are effective. Thus, an effective check on
all the activities and processes in a laboratory can only ensure that the results
pronounced on a product quality are within the acceptable parameters of
accuracy.
In quality control system, the following steps are involved, which when
implemented properly, ensure that the results delivered are acceptable and
verifiable by another laboratory.
- Check on the performance of the instruments.
- Calibration or standardization of instruments and chemicals.
- Adoption of sample-check system as a batch control within the laboratory.
- External check – inter-laboratory exchange programme.
To ensure obtaining accurate and acceptable results of analysis on a
sample, the laboratory has to run in a well regulated manner where the
equipment are properly calibrated and the methods and techniques employed
are scientifically sound which will give reproducible results. For ensuring the high
standards of quality, Good Laboratory Practice (GLP) has to be followed. The
GLP can be defined as “the organizational process and the conditions under
which laboratory studies are planned, performed, monitored, recorded and
reported”. Thus, the GLP expects a laboratory to work according to a system of
procedures and protocols whereas the procedures are also specified as the
Standard Operating Procedure (SOP).
Standard Operating Procedure
A Standard Operating Procedure (SOP) is a document, which describes the
regularly recurring operations relevant to the quality of the investigation. The
purpose of a SOP is to carry out the operation correctly and always in the same
manner. A SOP should be available at the place where the work is done. If, for
justifiable reasons, any deviation is allowed from SOP, the deviated procedure
may be fully documented.
In a laboratory, SOP may be prepared for:
- Safety precaution.
- Procedure for operating instruments.
- Analytical methods and preparation of reagents.
- Registration of samples.
8
To sum up, all the operations have to be properly documented so as no
chance is left for adhocism in any manner.
Error, Precision, Accuracy and Detection Limit
Error
Error is an important component of the analysis. In any analysis, when the
quantity is measured with the greatest exactness that the instrument, method
and observer are capable of, it is found that the results of successive
determination differ among themselves to a greater or lesser extent. The average
value is accepted as most probable. This may not always be true value. In some
cases, the difference in the successive values may be small, in some cases it
may be large, and the reliability of the result depends upon the magnitude of this
difference. There could be a number of factors responsible for this difference
which is also referred as ‘error’. The error in absolute terms is the difference
between the observed or measured value and the true or most probable value of
the quantity measured. The absolute-error is a measure of the accuracy of the
measurement. The accuracy of a determination may, therefore, be defined as the
concordance between it and the true or most probable value. The relative error is
the absolute error divided by the true or most probable value.
The error may be caused due to any deviation from the prescribed steps
required to be taken in analysis. The purity of chemicals, their
concentration/strength and the accuracy of the instruments and the skill of the
technician are important factors.
Precision and Accuracy
In analysis, other important terms to be understood are precision and accuracy.
Precision is defined as the concordance of a series of measurements of the
same quantity. The mean deviation or the relative mean deviation is a measure
of precision. In quantitative analysis, the precision of a measurement rarely
exceeds 1 to 2 parts per thousand.
Accuracy expresses the correctness of a measurement, while precision
expresses the reproducibility of a measurement. Precision always accompanies
accuracy, but a high degree of precision does not imply accuracy. In ensuring
high accuracy in analysis, accurate preparation of reagents including their perfect
standardization is critical. Not only this, even the purity of chemicals is important.
For all estimation, where actual measurement of a constituent of the sample in
terms of the “precipitate formation” or formation of “coloured compound” or
“concentration in the solvent” is a part of steps in estimation, chemical reagents
involved in such aspects must always be of high purity which is referred as AR-
grade (Analytical Reagent).
9
Detection Limit
In the analysis for trace elements in soils, plants and fertilizers and for
environmental monitoring, need arises to measure very low contents of analytes.
Modern equipment is capable of such estimation. However, while selecting
equipment and the testing method for such purpose, it is important to have
information about the lowest limits up to which analytes can be detected or
determined with sufficient confidence. Such limits are called as detection limits or
lower limits of detection.
The capacity of the equipment and the method may be such that it can
detect the traces of analyte in the sample. In quantitative terms, the lowest
contents of such analyte may be decided through appropriate research as the
values of interpretable significance. The service laboratories are generally
provided with such limits.
Quality Control of Analytical Procedures
Independent Standards
The ultimate aim of the quality control measures is to ensure the production of
analytical data with a minimum of error and with consistency. Once, an
appropriate method is selected, its execution has to be done with utmost care. To
check and verify the accuracy of analysis, independent standards are used in the
system. The extent of deviation of analytical value on a standard sample
indicates the accuracy of the analysis. Independent standard can be prepared in
the laboratory from pure chemicals. When new standard is prepared, the
remainder of the old ones always has to be measured as a mutual check. If the
results are not within the acceptable levels of accuracy, the process of
calibration, preparation of standard curve and the preparation of reagents may be
repeated till acceptable results are obtained on the standard sample. After
assuring this, analysis on unknown sample has to be started.
Apart from independent standard, certified reference samples can also be
used as ‘standard’. Such samples are obtained from other selected laboratories
where the analysis on a prepared standard is carried out by more than one
laboratory and such samples along with the accompanied analytical values are
used as a check to ensure the accuracy of analysis.
Use of blank
A blank determination is an analysis without the analyte or attribute or in other
words, an analysis without a sample by going through all steps of the procedure
with the reagents only. Use of blank accounts for any contamination in the
chemicals used in actual analysis. The ‘estimate’ of the blank is subtracted from
the estimates of the samples. The use of ‘sequence control’ samples is made in
10
long batches in automated analysis. Generally two samples, one with a low
content of analyte and another with very high content of known analyte (but the
contents falling within the working range of the method) are used as standards to
monitor the accuracy of analysis.
Blind sample
A sample with known content of analyte. This sample is inserted by the head of
the laboratory in batches and times unknown to the analyst. Various types of
sample material may serve as blind samples such as control samples or
sufficiently large leftover of test samples (analysed several times). It is essential
that analyst is aware of the possible presence of a blind sample but is not able to
recognize the material as such.
Validation of procedures of analysis
Validation is the process of determining the performance characteristics of a
method / procedure. It is a pre-requisite for judgement of the suitability of
produced analytical data for the intended use. This implies that a method may be
valid in one situation and invalid in another. If a method is very precise and
accurate but expensive for adoption, it may be used only when the data with that
order of precision are needed. The data may be inadequate, if the method is less
accurate than required. Two types of validation are followed.
Validation of own procedure
In-house validation of method or procedure by individual user laboratory is a
common practice. Many laboratories use their own version of even well
established method for reasons of efficiency, cost and convenience. A change in
liquid solid ratio in extraction procedures for available soil nutrients and shaking
time etc. result in changed value, hence needs validation. Such changes are
often introduced to consider local conditions, cost of analysis, required accuracy
and efficiency.
Validation of such changes is the part of quality control in the laboratory. It
is also a kind of research project, hence all types of the laboratories may not be
in a position to modify the standard method. They should follow the given method
as accepted and practised by most other laboratories.
Internal quality control
Apart from validation of methods, a system of internal quality control is required
to be followed by the laboratories to ensure that they are capable of producing
reliable analytical data with minimum of error. This requires continuous
monitoring of the operation and systematic day to day checking of the produced
data to decide whether these are reliable enough to be released.
11
Following steps need to be taken for internal quality control:
- Use a blank and a control (standard) sample of known composition along
with the samples under analysis.
- Round off the analytical values to the 2
nd
decimal place. The value of 3
rd
decimal place may be omitted if less than 5. If it is more than 5, the value
of second decimal may be raised by 1.
Since the quality control systems rely heavily on control samples, the
sample preparation may be done with great care to ensure that the:
- Sample is homogenous.
- Sample material is stable.
- Material has uniform and correct particle size as sieved through a
standard sieve.
- Relevant information such as properties of the sample and the
concentration of the analyte are available.
The samples under analysis may also be processed/prepared in such a
way that it has similar particle size and homogeneity as that of the standard
(control) sample.
As and when an error is noticed in the analysis through internal check,
corrective measures should be taken. The error can be due to calculation or
typing. If not, it requires thorough check on sample identification, standards,
chemicals, pipettes, dispensers, glassware, calibration procedure and
equipment. Standard may be old or wrongly prepared. Pipette may indicate
wrong volume, glassware may not be properly cleaned and the equipment may
be defective or the sample intake tube may be clogged in case of flame
photometer or Atomic Absorption Spectrophotometer. Source of error may be
detected and samples be analysed again.
Validation of the Standard Procedure
This refers to the validation of new or existing method and procedures intended
to be used in many laboratories including procedures accepted by national
system or ISO. This involves an inter-laboratory programme of testing the
method by a member of selected renowned laboratories according to a protocol
issued to all participants. Validation is not only relevant when non-standard
procedures are used but also when standard procedures are used, and even
more when variants of standard procedures are introduced. The results of
validation tests should be recorded in a validation report from which the suitability
of a method for a certain purpose can be deduced.
Inter-Laboratory sample and data exchange programme:
12
If an error is suspected in the procedure and uncertainty cannot readily be
solved, it is not uncommon to have the sample analysed in another laboratory of
the same system/organisation. The results of the other laboratory may or may
not be biased, hence doubt may persist. The sample checks by another
accredited laboratory may be necessary and useful to resolve the problem.
An accredited laboratory should participate at least in one inter laboratory
exchange programme. Such programmes do exist locally, regionally, nationally
and internationally. The laboratory exchange programme exists for method
performance studies and laboratory performance studies.
In such exchange programme, some laboratories or the organizations
have devised the system where periodically samples of known composition are
sent to the participating laboratory without disclosing the results. The
participating laboratory will analyse the sample by a given method and find out
the results. It provides a possibility for assessing the accuracy of the method
being used by a laboratory and also about the adoption of the method suggested
by the lead laboratory. Some of Such Programmes are:
- International Plant Analytical Exchange (IPE) Programme, and
- International Soil Analytical Exchange (ISE) Program.
They come under the Wageningen Evaluating Programme for Analytical
Laboratories (WEPAL) of the Wageningen Agricultural University, the
Netherlands. Other programmes run by the Wageningen Agricultural University
are:
- International Sediment Exchange for Tests on Organic Contaminants
(SETOC).
- International Manure and Refuse Sample Exchange Programme
(MARSEP).
Another International Organization operating such laboratory and method
evaluation programme is Association of Official Analytical Chemists (AOAC) of
USA. One of the most popular programme of AOAC is for Fertilizer Quality
Control Laboratories and the analytical methods for fertilizer testing.
For quality check, each laboratory will benefit if it becomes part of some
sample/method check and evaluation programme. The system of self-check
within the laboratory also has to be regularly followed.
13
1. SOILS OF ARID AND SEMI-ARID REGIONS
The soils of arid and semi-arid regions are the products of several factors, mainly
climate, parent materials and topography. The dominant rocks are limestone,
sandstone and metamorphic rocks. Wind-blown sand constitutes a major part of
the soil material. Gypsum is encountered in variable depths and salts accumulate
because leaching is not active. Predominantly, the following types of soils are
found in arid and semi-arid regions
1.1. Calcareous Soils
Most soils of the arid and semi-arid regions in the Near East are high in calcium
because they were developed from limestone and sandstone of various
hardness. The amount and form of CaCO
3
(total versus active) and its
distribution down the soil profile affect soil physical and chemical characteristics.
According to the research done in Lebanon by the authors, with the same
amount of CaCO
3
, soils derived from hard limestone, have less active CaCO
3
than the soils derived from soft limestone (marl). The CaCO
3
rich soils are widely
spread in the Near East region due to year-round warm dry climatic conditions
and insufficient annual rainfall (less than 400 mm) to dissolve the lime and leach
it off the soil profile. Though, the soils have a potential for agricultural
development under rainfed as well as irrigated conditions, the productivity is
limited due to low fertility, low water holding capacity, shallow soil depth,
prevalence of hardpan and faulty irrigation practices.
1.2. Gypsiferous Soils
Gypsum is found in soils of the arid and semi-arid regions in amounts ranging
from traces to high level. In some soils, gypsum is present in sedimentary
deposits from which the soil was derived and in others it is formed by
precipitation of Ca
2+
and SO
4
2-
(during salinization) when the ground water is
brought upward by capillary action to replace water lost by evaporation.
Gypsiferous soils have different forms of gypsum in soils because of the varied
sources and conditions under which it forms (Boyadgiev and Sayegh, 1992).
Solubility of gypsum is low, like 2.6 g/litre of CaSO
4
.2H
2
O in distilled water at
25°C. Continued irrigation of gypsiferous soil lead to subsidence and collapse of
the irrigation and drainage systems.
Measurement of total gypsum in soils by conventional methods is
unreliable as was proven by Sayegh et al. (1978). Figures quoted in the literature
for gypsum contents are commonly much lower than the actual amount present.
1.3. Salt Affected Soils
Since ancient times man had noticed that there are soils that contain excessive
amounts of salts. Plant growth on these soils is sporadic, production is low and
14
farmers usually abandon such lands to let them eventually become a barren
desert.
The primary salinity usually spreads out in poorly drained lowlands in arid
and semi-arid regions.
In arid and semi-arid regions “P/ET” (the ratio of precipitation to
evapotranspiration) is 0.03 < P/ET < 0.2 and 0.2 < P/ET < 0.5, respectively
(Balba, 1995). Introduction of irrigation without providing efficient drainage
changes the natural water balance in the newly irrigated areas causing the
ground water level to rise up with water logging, salinization or sodification. The
chemical properties of salt affected soils are summarized in Table 1
Table 1. Chemical characteristics of saline, non-saline sodic and saline
sodic soils
Soil EC dS/m ESP pH
Saline >4.0 <15 <8.5
Sodic (nonsaline) <4.0 >15 >8.5
Saline Sodic >4.0 >15 <8.5
Source: Richards, 1954
15
2. SOIL SAMPLING AND PREPARATION
Soils are sampled for different purposes and, so, different methods are employed
to satisfy the purpose for which the sample is collected. Sampling errors are
often greater than analytical errors. If the collected soil samples are not truly
representative samples, results of the analyses will not reflect the properties of
the soil under investigation. Therefore, collecting a representative soil sample
from the field is the most important aspect of soil analysis. According to Cline
(1944), the analytical values can serve as an accurate description of the soil
property under investigation if:
- The gross (or bulk) sample accurately represents the whole soil from
which it was taken,
- No changes occur in the gross and sub-samples prior to analysis,
- The sub-sample analyzed represents the gross sample accurately,
- The analytical data produced are truly measuring the soil parameter
under investigation.
2.1. Soil Sampling Tools
Tarzi (1984) reported two important requirements of a soil sampling tool: first,
that the tool allows for a uniform slice to be taken from the surface to the depth of
insertion of the tool, and second, that the same volume of soil be taken from
each sampling point. Bucket auger, shovels or garden trowels have proven to be
useful tools in sampling arid and semi-arid soils.
In general, soil-sampling tools are divided into four major groups:
1. Various types of hand augers, such as:
- Bucket auger: This is a cylindrical auger with specially designed
cutting bits at the lower end. This type is the most suitable for
medium textured soils.
- Dutch auger: This auger is particularly effective on coherent moist
and rather wet soils of high clay content. It is not effective on sandy,
gravelly or stony soils or on dry soils of any texture.
- Jarret auger: This is an open bucket auger with side cutters of robust
design. It penetrates most soils and is particularly effective in gravelly
soils, but will not collect samples in dry non-coherent soils unless
they are wetted during boring.
- Screw auger: The screw auger is of limited value for soil observation
because of the severe disturbance of the sample during collection. It
can be useful in collecting samples for fertility evaluation and rapid
soil examination to check map boundaries. It is not effective on sandy
or gravelly soils.
16
- Tube sampler: This sampler is useful for rapid sampling of topsoil in
medium textured soils. It is not effective on non-coherent soils, hard
clays or gravelly soils.
- Blades, shovels, spades, knives, and core samplers.
2. Tubes and cylinders.
3. Hydraulic equipment.
2.2. Sampling for Soil Fertility Tests
Chemical analysis of soil samples is a prime source of information on the relative
availability of plant nutrients. When the soil test is calibrated with crop response
and soil samples are properly obtained, the test results can be a strong pivotal
point around which management decisions on fertilizer application and soil
fertility management can be taken. However, if soil test correlations are weak or
soil samples unrepresentative, then the soil test will not be very useful and it may
be misleading. This leads to the following questions:
1. Does the soil nutrient level indicated by the chemical analysis actually
have a relationship to the nutrient uptake and growth of plants? In
other words, does the soil test correlate with fertilizer requirements and
crop performance in the field?
2. How well does the soil sample represent the field in question? The
analytical aspect of soil testing may correlate perfectly with crop
response, but if the soil sample is unrepresentative, then the soil test
result cannot have much value.
2.2.1. Time of Sampling
The correct time of sampling cannot be decisively specified. However, sampling
after fertilization should be avoided. A key point is to collect samples in time to be
analyzed for deciding fertilizer application rates and their application. Samples
can be taken during crop growing period when soil content of nutrients is
stressed. For example, samples collected in spring, as soil starts warming up,
would give lower values of available-P than samples collected in autumn when
soil temperature is low. The reason for the lower values for available-P in spring
could be the increased soil microbiological activities, which use up part of the
soil-P. It is important to take this into consideration in the evaluation.
It is usually recommended that each field be tested once every three
years. In most instances this is often enough to determine whether the
fertilization programme is adequate, and whether there is need for an increase or
decrease in the rate of application.
17
2.2.2. Depth of Sampling
Samples are usually collected from soil surface layer down to a depth of 15-25
cm in cultivated fields. Some farmers plough to a depth of 30 cm, and then
samples should be collected up to this depth. When fertilizers are broadcast on
soil surface, still the samples must be collected all through the plough-depth of
15-25 cm. In vegetable fields, it is advisable to collect separate samples from the
0-15 and 15-30 cm layers. In fruit tree orchards, the depth of soil sampling should
be extended to the depth of root zone, 0-30, 30-60 and 60-100 cm, if the root
system reaches to about 100 cm of depth.
2.2.3. Methods of Sampling
A field can be sampled to estimate its fertility through soil analysis by several
methods. These include, among others:
1. A composite sample, i.e., a single sample consisting of the composite
of several randomly selected soil cores.
2. Multiple samples taken systematically on a grid pattern.
The multiple sampling method is the best because, in addition to providing
estimates of nutrient levels, it shows variation in fertility from one part of the field
to another.
Intensive soil sampling will not be practical unless the economic returns
justify the costs, or where the topographic conditions are such that high variability
is expected. Thus, the most commonly recommended sampling procedure is the
composite sample. A good composite sample is made up of a number of soil
cores taken at random from 15 – 20 sites in a 1 – 5 ha cultivated field. The
purpose of this procedure is to minimize the influence of any local variability in
the soil. For example, band-applied fertilizers are not uniformly applied over the
soil surface. In addition, there may be some spots in the field where fertilizers
were spilled or plant refuse was buried. A sample taken from such an area would
be completely misleading. Consequently, most recommendations call for taking
borings at 15-20 locations over the field for each composite sample.
Areas that vary in appearance, slope, drainage, soil type, and previous
treatments should be sampled separately, and areas that cannot be treated or
fertilized separately should be omitted. Figure 1 shows a sampling pattern in a
heterogeneous land. Many growers are directing attention to these small spots in
their fields and treating them as needed. Hence, it is advisable to take separate
samples from these localized areas of poor crop growth.
Sampling recently fertilized bands, dead furrows, areas adjacent to roads,
or where manure, compost or crop residues have been piled should be avoided.
A random distribution of individual sample sites would be ideal. However, equally
reliable information is obtainable with much less effort by reducing the sampling
area when the fields are relatively uniform. Sampling areas are often traversed in
18
a zigzag pattern to provide a uniform distribution of sampling sites. Some of
these methods are presented in Figure 2. In fruit tree orchards, particularly those
irrigated by a drip system, soil samples should be collected from the root zone of
trees, i.e., the zone moistened by irrigation, reaching to the depth of the root
system. Trees, around which soil is to be sampled, are selected in a random or
systematic pattern. A reasonable number of sites (trees) would range from 5-
20% of total number of trees.
Figure 1. Sampling pattern for fertility test in a non-uniform land
(Sample numbers refer to composite samples) (Source: Tarzi, 1984)
Figure 2. Sampling-sites selection methods for fertility test
19
2.3. Soil Sampling for Soil Survey and Classification Studies
Soil survey is a type of pedological study the purpose of which is to describe soil
characteristics for areas of a few to hundreds or thousands of hectares, and
delineate these areas on a map. Normally, these surveys are government
projects carried out to determine and develop land use and management.
In soils having distinguishable genetic horizons, pits are dug to about two
meters depth or to bed rock if it is shallower than 2 m. Soil profiles are studied
and samples are taken from each horizon. Where surface soil did not develop
from the underlying parent materials, as in depositional soils, samples are
collected from a sequence of depth intervals, e.g. 20-30 cm intervals.
Soil surveyors commence from a convenient point or landmark, and then
select fields or sites for boring or digging of pits. The methodology will vary in
details depending upon the type of terrain, geology, landforms and spatial
variability of the land. More important are the survey objectives, the mapping
scale, and the complexity of the soil pattern to be surveyed. Arial photos taken
for the terrain to be surveyed, and now images taken by remote sensing from
satellites, are first studied to collect some basic information about relief and other
physical feature of the terrain to be surveyed. The dependability of these images
serves in approaching and executing soil survey projects.
In areas with a relatively simple soil pattern, the average observation
density will be one pit per 15-20 hectares. In areas with complex soil patterns,
the density will be one per 10-15 hectares. The observation density will be lower
in areas of poor soils such as shallow soils, rocky soils, undulating and ridges.
Soil surveyors correlate soil series and mapping units with landform units and
land surface features.
2.4. Preparation of Soil Samples
Following the sampling process, soil cores are placed in a clean container and
clods are crushed. After mixing well the gross soil sample, about one kg is
transferred into a clean plastic or canvas lined with plastic bag. This is the
composite sample to be sent for analysis. Bags should be properly labelled.
Information such as sample number, depth, and date of sampling should be
written on the bag from outside, and on a sample card placed inside the bag.
Bags should be closed tightly, placed in wooden or cardboard box, and then
shipped or taken to the laboratory.
It is essential that a Field Data Sheet be filled and sent with the samples to
the laboratory (Figure 3). Information recorded on the data sheet must be
accurate. Questions for which reliable answers cannot be provided should be left
unanswered. In the laboratory, the collected sample is spread thinly on a plastic
sheet or tray for air-drying. Air-drying is the most accepted procedure of sample
preservation and may reduce the rate of possible reactions in the disturbed soil
sample. A soil sample should not be allowed to stay moist for extended periods
20
of time. Soil aggregates should be broken carefully to accelerate the drying
process. It is generally assumed that chemical and biochemical reactions in air-
dry soils are reduced to a minimum, although these reactions are still possible
sources of error.
FIELD DATA SHEET
Sample No. _____________
Collector _______________ Address______________________ Date ___________
Area _______________ Location_______________ Owner ___________________
Farm Size ____________________ Vegetative Cover_________________________
Source of Water ____________________ Water Quality ______________________
Sample Depth _____________________ Previous Crop ______________________
Site Selection Method: ¯ Random Sample Type: ¯ Individual
¯ Zig Zag ¯ Composite
¯ Two Way Diagonal ¯ No. of cores
¯ Two Way Cross-Strip
¯ Test Plot
Purpose of Analysis: ¯ Capability Assessment Slope: ¯ 1-2%
¯ Fertility Evaluation ¯ 2-5%
¯ Salinity Appraisal ¯ 5-10%
¯ Soil Classification ¯ 10-25%
¯ > 25%
Irrigation Method: ¯ Flood Years of Irrigation: ¯ Never Irrigated
¯ Furrow ¯ 1-5
¯ Sprinkler ¯ 5-15
¯ Center Pivot ¯ > 15
¯ Drip
¯ Rainfed
Years of Cultivation: ¯ Never Cultivated Drainage: ¯ Good
¯ 1-5 years ¯ Moderate
¯ 5-15 years ¯ Poor
¯ >15 years
Manure/Fertilizer Application History:
Manure (type) ________________________ Rate (kg/ha)_______________________
Fertilizers (mineral) ____________________ Rate (kg/ha)_______________________
Note: Questions for which accurate answers cannot be provided should be left
unanswered.
Figure 3. Field data sheet
21
To accelerate the drying process, samples may be placed in forced draft
of moving air, but not in heated air. The temperature must not exceed 35°C
because drying at elevated temperatures may cause drastic changes in the
physical and chemical characteristics of the soil sample (Hesse, 1972). Drying
may also result in increased cementation, which may particularly affect particle
size distribution analysis. Other possible results from drying at higher
temperatures are chemical changes in the oxidation status of elements, variation
in the content of available nutrients (Sayegh, 1986) and microbiological
reactions. The degree to which such changes occur varies with temperature and
time of drying.
For some quick soil analysis, like NO
3
-N and NH
4
-N, the measurements
are done on moist soil samples as collected from the field. A separate sample is
taken to determine soil moisture which is then used to convert results to oven-dry
basis.
2.5. Grinding and Sieving of Soil Samples
Thorough mixing requires that the sample be crushed and ground to particles of
uniform size. After drying the sample, clods and large aggregates are crushed
and mixed. Then the crushed material is further ground to pass 2 mm sieve. Care
should be taken not to break the individual soil particles during the grinding
process. The purpose of grinding is to reduce heterogeneity and to provide
maximum surface area for physical and chemical reactions. Various devices are
used for crushing and grinding soils. The choice of equipment depends on four
factors:
1. The amount of sample to be crushed or ground.
2. The degree of fineness to be attained.
3. The contamination that can be tolerated.
4. The analysis in question.
Soil aggregates can be crushed by using jaw crushers, hardened steel
mortars or rocking boards (Tan, 1996). Jaw crushers are used for crushing large
aggregates, steel mortars for smaller aggregates, and rocking boards for small
aggregates. The types of grinders used are plate grinders (friction mills), ball
mills, rod mills, agate mortars, and boron carbide mortars. For large amounts of
samples, plate grinders or ball mills or rod mills are used. The sample is mixed
with stainless steel rods or balls, in a container and the container is rolled over a
period of time. When properly operated, rod and ball mills are efficient grinders
(Coghill and Devaney, 1937). For least contamination and for small amounts of
samples, an agate or boron carbide mortar can be used.
After grinding, the soil is sieved through a 2 mm sieve and stored in air-
tight glass or clean plastic containers as soon as possible to avoid adsorption of
gases in the laboratory. This will serve as stock samples for analysis. Then,
22
samples should be stored in a cool and well-ventilated room. Analysis of samples
that are passed through sieves of unspecified sizes may produce results that
would not be comparable to internationally accepted data. Therefore, the sieve
size should be reported with the results of analysis.
2.6. Reduction of Sample Size
When a very large sample is collected, it is necessary to reduce the size of the
sample for ease of storage and handling. The bulk sample must be reduced in
size, and the sub-sample taken for analysis should represent the soil
characteristic of the field under investigation. In order to achieve this goal, a
random and unbiased method of sub-sampling is essential. Sample splitting can
be performed with a mechanical sample splitter, such as a riffle sampler, by
which the sample is divided in half by a series of chutes (Krumbein and Pettijohn,
1938; Willard and Dhiel, 1943; Hesse, 1972). This process can be repeated as
many times as necessary.
Another way for reduction of sample size is by quartering. The sample is
spread uniformly over a plastic sheet and divided into four equal portions (Figure
4). Portions 2 and 3 are collected and thoroughly mixed, whereas the remainder
is discarded. This process of quartering can be repeated as many times as
necessary until the proper size of sample is attained.


1 2
discard


keep
Á

À
Keep


3 4

discard
Figure 4. Reduction of sample size by quartering
23
3. SOIL MOISTURE
Water is held in soil by adhesive and cohesive forces. Adhesion is the force of
attraction between the solid soil particles and water molecules. Cohesion is the
mutual force of attraction between water molecules. Another force that affects
water retention and movement in soil is the capillary force, which is a function of
the size of micropores or capillaries.
The pF is the term mostly used to express soil moisture, although other
terms are also used, like atmosphere or bar. Water can exist in soil under a
tension varying from pF = 0 (no tension) to pF = 7.0 (high tension). The point at
which water is held in soil after excess water has drained out by gravity is called
field capacity (pF = 2.54). The point at which water is held in soil at a force that
plants cannot extract at a sufficient rate to maintain turgor, is known as wilting
point (pF = 4.2). At this point the plants start to wilt. The amount of water
between field capacity and wilting point is called available water. Water in air dry
soil is held with a tension of pF 6.0.
Apparatus
- Moisture determination cans
- Analytical balance
- Drying oven
- Desiccator
Procedure
1. Weigh accurately a metal can with lid (W
1
).
2. Place about 50 g of soil in the can and weigh accurately along with the lid
(W
2
).
3. Place the can with the lid under it in a drying oven at 105°C for 24 – 48
hours, or until constant weight is reached.
4. Remove the can from the oven, cover it tightly with the lid, and place in a
desiccator to cool.
5. After cooling, weigh the can accurately with the oven-dry soil in it. Record
the weight (W
3
).
6. Compute percent moisture content on oven-dry basis.
Calculation
3 2
W W water of Weight ÷ =
1 3
W W soil dry oven of Weight ÷ =
100
W W
W W
basis) dry (oven % Moisture
1 3
3 2
×
÷
÷
= ÷
24
The corresponding moisture correction factor (mcf) for analytical results or
the multiplication factor for the amount of sample to be weighed in for analysis is:
Moisture correction factor =
100
% 100 moisture +
Normally, soil moisture is expressed on oven-dry basis. However, for
certain purposes, moisture content is expressed on wet-soil basis. To do so, the
weight of the wet-soil sample (W
2
– W
1
) is used instead of the oven-dry weight
(W
3
– W
1
):
3
W W water of Weight
2
÷ =
1 2
W W soil - wet of Weight ÷ =
100
W W
W W
basis) soil (wet % Moisture
1 2
3 2
×
÷
÷
= ÷
25
4. SOIL TEXTURE – PARTICLE SIZE DISTRIBUTION
4.1. Introduction
Soil texture, or particle size distribution, is a rather stable soil characteristic which
influences the physical and chemical properties of the soil. There is a direct
relation between particle size and the total surface area of particles in a given
weight of soil. As particle size decreases, total surface area, better known as
specific surface area, increases. Since most of the physical and chemical
properties of soil are related to surface activity, determination of particle size
distribution is a standard procedure for characterizing and classifying soils.
As soil particles are freely settling down the water column, they are sorted
according to particle size. Coarse particles, like sand, move down faster than fine
particles. Because of their differential settling rate in water, the size fractions are
sorted into different size ranges. The Bouyoucos Hydrometer is calibrated to read
the amount of solid particles remaining in suspension, hence the method is
known as Bouyoucos Method.
Two basic conditions are required in this method:
- Dispersion of the soil sample into a state of single grain particles
- During sedimentation, particles should be moving down freely
Determination of the particle size distribution of gypsiferous-calcareous
soils is a tedious and time-consuming process. Gypsum, which inhibits soil
dispersion, is usually removed from soil samples before analysis, although
gypsum has marked effects on the physical properties of soils and it is most
desirable to determine the particle size distribution without removing the gypsum
fraction. Hesse (1974) and Matar and Douleimy (1978) developed methods for
the preparation of a stable suspension of gypsiferous soils without removing the
gypsum fraction. Vielliefom (1979) gave a substantially improved method based
on that of Hesse. So far, no method for the determination of the particle size
distribution of gypsiferous-calcareous soils is entirely satisfactory.
The estimation of texture under field conditions is misleading because of
the presence of gypsum crystals in various sand-sized fractions. The forms and
degree of crystallization of gypsum particles influence the feel of the soil and as a
result field estimates of texture are generally coarser than indicated by laboratory
determinations.
Based on the experience gained from the analysis of a large number of
gypsiferous soil samples, the following can be concluded:
26
1. The sum of the various size-fractions of gypsiferous horizons may be
less than 100 percent due to dehydration of CaSO
4
.2H
2
O during oven
drying at 105°C.
2. The distribution of gypsum within the various size-fractions depends on
the total amount of gypsum (Vieillefon, 1979). The difference between
the weight of such fractions obtained after treatment at 50°C and
105°C shows the following:
- The fraction less than 20 μm in diameter is greater when the
total content of gypsum is about 10 percent, and decreases with
the increase of gypsum content to about 25 percent. This
fraction does not change as gypsum content increases from 25
to 45 percent, but it increases again as gypsum content goes
above 45 percent.
- The amount of the fractions greater than 20 μm in diameter
increases as the total amount of gypsum increases. For most
samples with gypsum content between 10 and 25 percent, the
relationship is not significant.
3. Gypsum is found in all size fractions, but it is mostly present in the
coarse and fine sand fractions (0.02-2.0 mm) followed by the silt
fraction.
4.2. Dispersion
Individual soil particles must be separated from each other, and kept separated
during the determination in order to correctly measure particle size distribution.
Since aggregates of solid particles are usually held together by some kind of
binding agent, it is first necessary to remove these substances, or at least render
them ineffective. Once the soil aggregates are separated into individual particles,
they are described as dispersed particles.
Dispersion is achieved by chemical and mechanical means. Sodium-
hexametaphosphate is an effective chemical dispersing agent for two reasons:
1. The sodium monovalent cation replaces the usual polyvalent cations
adsorbed on soils, thereby breaking interparticle linkages. The
polyvalent cations are also reduced in activity as a result of reaction
with the phosphorus and consequent precipitation.
2. The adsorbed sodium cations raise the electronegativity of colloids
until these particles repel each other and remain dispersed.
After the binding agents are removed, aggregates breakdown is further
facilitated by mechanical stirring. The mixture of dispersed soil particles in water
is called a soil suspension.
27
4.3. Sedimentation
In sedimentation techniques, the settling rates of dispersed particles in water are
measured. Large particles are known to settle out of suspension more rapidly
than do small particles. This is because larger particles have less specific surface
area and hence less buoyancy than small particles. Stocke's law is used to
express this relationship:
n
) d g(d r
x
9
2
V
2 1
2
÷
=
The formula shows that settling velocity, V, is directly proportional to the
square of the particle's effective radius, r; the acceleration of gravity, g; and the
difference between the densities of the particle, d
1
, and that of the liquid, d
2
; but
inversely proportional to the viscosity of the liquid, n. Density of water and its
viscosity are both affected by temperature, and thus, particles settle faster with
increased temperature. This is why it is necessary to apply correction for
temperature.
In practice, the amount of material remaining in suspension at any time is
measured with a hydrometer, which indicates the density of the suspension at
the hydrometer's centre of buoyancy. Bouyoucos determined that after 40
seconds all sand-sized particles (0.02 mm and larger) settle out of the
suspension and do not influence the hydrometer reading. After two hours,
particles larger than clay (0.002 mm) settle out of the suspension and do not
affect the hydrometer reading any more.
4.4. Bouyoucos Method
Apparatus
- Electric mixer (stirrer), with baffled stirring cup
- Settling cylinder
- Graduated cylinder, 1 litre, with 1 000 ml mark 36 ±2 cm from bottom
- Bouyoucos Hydrometer calibrated at 200°C
- Thermometer C°
Reagent
- Sodium hexametaphosphate, Na
6
O
18
P
6
solution (examples of commercial
names: Calgon, Graham’s salt, glassy sodium): Dissolve 50 g of Calgon in
water and dilute the solution to a volume of 1 litre
28
Procedure
1. Weigh 50 g oven dried fine textured soil (100 g of coarse textured soil) into
a baffled stirring cup. Fill the cup to its half with distilled water and add 10
ml of sodium hexametaphosphate solution.
2. Place the cup on stirrer and stir until soil aggregates are broken down.
This usually requires 3-4 minutes for coarse textured soils and 7-8 minutes
for fine textured clay.
3. Transfer quantitatively the suspension to the settling cylinder by washing
the cup with distilled water. Fill the cylinder to the lower mark with distilled
water after placing the hydrometer in the liquid. If 100 g of coarse textured
sample was used, fill to the upper mark on the settling cylinder.
4. Remove hydrometer and shake the suspension vigorously in a back and
forth manner. Avoid creating circular currents in the liquid, as they will
influence the settling rate.
5. Place the cylinder on a table and record the time. After 20 seconds,
carefully insert the hydrometer and read the hydrometer at the end of 40
seconds.
6. Repeat step 4 and 5 to obtain hydrometer readings within 0.5 g
differences from each other. The hydrometer is calibrated to read grams of
soil material in suspension.
7. Record the readings on the Data Sheet for Hydrometer Readings (a
sample is shown in Figure 5).
8. Measure the temperature of the suspension. For each degree above 20°C
add 0.36 to the hydrometer reading, and for each degree below 20°C,
subtract 0.36 from the hydrometer reading. This is the corrected
hydrometer reading.
9. Re-shake the suspension and place the cylinder on a table where it will
not be disturbed. Take a hydrometer reading exactly two hours later.
Correct for temperature as described above.
10. From the percentage of sand, silt and clay as calculated on the Data
Sheet, use the diagram for textural triangle (Figure 6) to determine the
textural class of the soil.
29
(1)
Soil sample identification number
(2)
Soil weight (g)
(3)
Forty second hydrometer reading (g)
(4)
Temperature of suspension (C°)
(5)
Corrected 40-second hydrometer reading (g)
(6)
Two hours hydrometer reading (g)
(7)
Temperature of suspension (C°)
(8)
Corrected 2-hour hydrometer reading (g)
(9)
Grams of sand (the sand settles to the bottom of the cylinder
within 40 seconds, therefore, the 40-second corrected
hydrometer reading actually gives the grams of silt and clay in
suspension. The weight of sand in the sample is obtained by
subtracting line 5 from line 2)
(10)
Grams of clay (the corrected hydrometer reading at the end of
two hours represents grams of clay in the suspension since all
sand and silt has already settled by this time).
(11)
Percent sand (line 9 ÷ line 2) × 100
(12)
Percent clay (line 10 ÷ line 2) × 100
(13)
Percent silt (find the silt by difference. Subtract the sum of the
percent sand and clay from 100).
(14)
Soil class (as per Figure 6)
Figure 5. Data sheet for recording of hydrometer readings
Some experienced field men take a sample of soil in their hand, feel it with
their fingers when dry, and then inspect its stickiness after wetting, and then they
come up with a skilled guess about the textural class of the soil (Figure 7).
30
Figure 6. Texture triangle showing the percentages of sand, silt and clay in
the textural classes
(the intersection of the dotted lines shows that a soil with 55 percent clay, 32
percent silt and 13 percent sand has a clay texture).
Figure 7. Modified textural triangle for determining soil texture by the feel
method (Source: Foth et al., 1977)
31
4.5. Gypsum Removal from Soil
For certain gypsiferous soils, it is recommended that gypsum be removed from
the soil sample prior to its analysis for particle size distribution. The following are
the methods that could be used for this purpose. Method 4.5.3 is preferred
because gypsum is not removed from the sample and the results are closer to
the field conditions.
4.5.1. Gypsum Removal by Ammonium Oxalate (Coutinet,
1965)
1. Weigh 40 g of soil in an Erlenmeyer flask, and add to it about 40 ml of
distilled water.
2. Bring to boiling while stirring. Then add 2–3 ml of hydrogen peroxide
(H
2
O
2
) to destroy the organic matter. Repeat the addition of H
2
O
2
until
effervescence stops.
3. Transfer the content into a 600 ml Erlenmeyer flask, by repeated washing
of the soil with distilled water.
4. Add more distilled water to bring the total volume to about 300 ml.
5. If the gypsum content is not more than 25 percent (based on pre-
estimation to know the range), add 5 g of ammonium oxalate and boil the
mixture for one hour. Discard the supernatant.
6. Repeat steps 4 and 5 until no more calcium sulphate crystals are seen in
solution.
7. Add 20 ml of sodium-hexametaphosphate solution (40 g/l) and boil the
mixture for 3 hours.
8. Wash the content and quantitatively decant into the cylinder, then proceed
to determine the particle-size fractions.
9. If gypsum content is more than 25 percent, follow the same procedure as
above, but use sodium chloride solution (131.6 g/l) instead of ammonium
oxalate.
4.5.2. Gypsum Removal by Hydrochloric Acid (Loveday, 1974)
This procedure is used for soils containing visible gypsum crystals, and having
an electrical conductivity (EC
1:5
) >3 mS/cm.
1. Weigh 25 g of air-dry soil and transfer into an 800 ml Erlenmeyer flask.
2. Add 25 ml of 2M HCl to the flask and gently swirl to destroy the CaCO
3
content of the soil. Allow to stand for 2-3 minutes.
3. Add 5 drops of H
2
O
2
and gently swirl the flask to destroy organic matter.
Add more drops until effervescence stops.
32
4. Add 500 ml distilled water and place on a magnetic stirrer. Stir for one
hour, allow to settle and decant the clear supernatant.
5. Repeat step 4 until the crystals of gypsum do not show anymore on the
sides of the beaker.
6. Add 5 ml of 1M NaOH and 10 ml of 10% sodium-hexametaphosphate,
swirl gently and leave for 20 minutes to allow the dispersing of the soil
sample.
7. Wash the content and quantitatively decant into the cylinder, then proceed
to determine the particle-size fractions.
4.5.3. Pre-treatment of Soil with BaCl
2
to Coat Gypsum with
BaSO
4
(Hesse, 1974)
1. Transfer 10 g of soil into a 100 ml centrifuge tube, and then add 40 ml of a
solution containing 50 g/l barium chloride (BaCl
2
) and 20 ml of 45 ml/l tri-
ethanolamine, and shake gently for one hour.
2. Centrifuge and decant the supernatant.
3. Add 40 ml water in the tube, then shake and decant. Repeat washing the
soil with water until no more barium ions can be detected in the
supernatant. The presence of Ba can be confirmed if after adding a few
drops of potassium chromate solution a yellow precipitate forms.
4. Add 15 ml of a solution containing 40 g/l sodium hexametaphosphate, 10
g/l anhydrous sodium carbonate, and 10 percent sodium hydroxide to the
treated soil, and disperse by shaking for 30 minutes.
5. Transfer the tube content by several washings with distilled water into the
graduated cylinder for particle-size determination, and proceed as in
procedure in section 4.4.
4.5.4. Pre-treatment of Soil with BaCl
2
Solution followed by
Ethanol (Mater and Douleimy, 1978)
1. Place 10 g of soil in a small funnel fitted with a filter paper, and slowly
leach with 0.1M BaCl
2
solution.
2. Leach the excess Ba ions with pure ethanol until no more Ba is detected
in the filtrate. The presence of Ba in the solution can be determined as
indicated in 4.5.3
3. Transfer the soil into the suspension cylinder and stir the suspension for
12 minutes after adding distilled water and 10 ml of sodium-
hexametaphosphate (40 g/l).
4. Proceed to determine the particle-size fractions.
33
4.5.5. Pre-treatment with BaCl
2
Solution (Modified Method by
Vieillefon, 1979)
1. Shake 10 g soil with 10 ml BaCl
2
(50 g/l) and 20 ml triethanolamine
[(HOCH
2
CH
2
)
3
N], in a centrifuge tube.
2. Shake for 1 hour and then centrifuge the suspension.
3. Discard the supernatant liquid.
4. Add 40 ml distilled water, centrifuge, and discard the supernatant liquid.
5. Add 15 ml of dispersing solution [4% sodium hexametaphosphate + 1% of
sodium carbonate (Na
2
CO
3
)], adjust pH to 8.2 and shake.
6. Determine the various particle-size fractions.
34
5. SOIL DENSITY AND TOTAL PORE SPACE
5.1. Introduction
Soil bulk density (BD) is defined as the mass of oven-dried solids divided by the
bulk volume of the solids plus pore space at a specified soil water content,
usually the moisture content at sampling.
Soil particle density (PD) is defined as the mass of oven-dried solids
divided by the volume of the solid particles alone. Actually, it is the density of the
soil particles, irrespective of the volume of voids between particles. The
magnitude of PD depends on the type of minerals in the particles, and the
content of organic matter in the soil. The particle density of most mineral soils is
about 2.65 g/cm
3
. It varies little from soil to soil and, therefore, is of little practical
significance. It is used with bulk density to calculate soil porosity.
Bulk density is an extremely useful parameter, as it indicates soil structure
and void space. It is required to calculate porosity when particle density is known,
to convert weights to volumes, and to estimate weights of soil volumes too large
to weigh. It is also required to convert weight-based determinations to a volume-
based figure, which are often, more interesting. For example, the volumetric
content of water in a soil layer is obtained by multiplying the gravimetric water
content by the product of the bulk density and the volume of the layer.
A medium textured mineral soil that is in good structural condition for plant
growth contains about 50% total pore space on volume basis. This pore space is
important for gas exchange (O
2
and CO
2
) between the soil and the atmosphere,
and water storage and movement. The total pore space consists of the pore
spaces between adjacent sand, silt and clay particles and those between
aggregates. Therefore, texture and structure are the main factors governing the
amount of pore space in soil. Organic matter affects pore space indirectly by
improving structure.
Bulk density is an indirect measure of the total pore space in the soil and
is also affected primarily by texture and structure. If the aggregation of a
particular soil is increased, the total pore space will be increased, and the weight
per unit volume or bulk density of the soil will decrease. The bulk density of fine
texture mineral soils ranges from about 1.0 to 1.3 g/cm
3
, and that of sandy soils
ranges between 1.3 and 1.7 g/cm
3
. The bulk density of organic soils is usually
much less than that of mineral soils and may be as low as 0.4 g/cm
3
. Bulk density
and total pore space are readily altered by tillage operations.
35
5.2. Measurement of Bulk Density
Two methods are commonly used to determine soil bulk density: one uses
samples of disturbed soil, and the other uses samples of undisturbed soil. The
second method uses consolidated soil masses, like clods and cores.
5.2.1. Bulk Density of a Disturbed Soil Sample
This method is used when it is not possible to take a consolidated sample of soil,
as in sandy soils and soils of greenhouses and nurseries because they are loose
and very friable.
Procedure
1. Fill a pre-weighed 100 ml graduated cylinder with air-dry soil.
2. Compact the soil in the cylinder by tapping the cylinder firmly 15 times on
the palm of the hand.
3. Record the volume of the packed soil in the cylinder.
4. Record the weight of the cylinder and the soil.
5. Calculate the weight of the soil.
6. On a separate sample, determine the moisture content of the soil sample
and calculate the oven-dry weight of the soil in the cylinder.
7. Calculate bulk density.
Calculation
)
3
3
(cm sample soil of Volume
(g) soil dry - oven of Weight
) (g/cm BD =
Note: Bulk density is commonly calculated on oven-dry basis, but for certain
uses it is calculated on a wet-soil basis.
5.2.2. Bulk Density of an Undisturbed Soil Sample
Two methods are used to determine the bulk density of an undisturbed soil
sample: the soil clod or ped method, and the core method.
5.2.3. The Clod or Ped Method
Reagent
36
- A resin, such as Dow Saran F 310 (general purpose non-crystalline co-
plolymer), is dissolved in acetone at a saran:solvent ratio of 1:7. Acetone
is flammable, therefore, this mixture should be prepared in a fume hood
and it should be kept in a tightly closed container to prevent volatilization.
Melted wax, by heating on medium flame, could be used as a replacement
to the dissolved saran resin.
Procedure
1. Carefully collect soil clods from a soil profile. If roots are present, cut them
carefully with scissors.
2. Tie and hold the clod with a fine copper wire and weigh it.
3. Dip the clod in the saran solution, hang it to dry for 30 minutes. Additional
saran coatings may be applied to make the clod more waterproof.
4. Weigh the coated clod and wire in air (W
a
).
5. To determine the volume of the clod, weigh it while suspended in water
with a balance that can accept the clod hanging on the balance beam by
the thin copper wire (W
w
). The drop in weight (W
a
– W
w
) is equal to the
weight or volume of the water displaced, which is the volume of the clod.
6. If such a balance is not available, immerse the clod completely in a
graduated cylinder half full with water, and detect the change in volume of
water in the cylinder (V).
7. Break the clod and take a sample for the determination of soil moisture
content. This is needed to calculate the oven-dry weight of the soil (W
od
).
Calculation
( )
w a
od
W W
W
BD
÷
=
W
od
is the mass of solid particles in the clod in grams.
(W
a
– W
w
) is the weight of the water displaced by the clod in grams, or volume of
the clod in cm
3
.
If the volume of the clod is measured as indicated in step 6:
BD = W
od
/ V
V is the change in volume of water in the graduated cylinder in cm
3
.
Note: The clod method may yield higher BD values than other methods.
37
5.2.4. The Core Method
Procedure
1. Carefully drive a thin-walled steel tubing or pipe (of known weight and
volume) into the soil with a block of wood and a hammer. Be careful to
avoid compaction of the soil during collection of the cores. After careful
removal of the soil core, examine it and trim the ends carefully.
2. Weigh the soil and tubing. Calculate the weight of the soil sample alone by
subtracting the weight of the steel tubing.
3. Take a portion of this soil for the determination of soil moisture.
4. Knowing the moisture content of the soil core, calculate the oven-dry
weight of the soil sample.
5. Calculate the bulk density in g/cm
3
by dividing the weight of soil core, on
oven dry basis, by the volume of the soil core, which is the volume of the
steel tube.
)
3
(cm core soil of Vol.
(g) basis) (dry core soil of Wt.
)
3
(g/cm BD =
Values of BD of undisturbed cores are of practical significance as it indicates soil
aggregation and structure under field conditions.
5.3. Measurement of Particle Density
Two methods for the determination of particle density (PD) are discussed. In the
first method a graduated cylinder is used, in the second method a volumetric
flask is employed. Both analyses are very simple and rapid. The particle density
of most soils varies from 2.60 to 2.75 g/cm
3
. An average particle density value of
2.67 is commonly used as the specific gravity of soils.
5.3.1. The Graduated Cylinder Method
Procedure
1. Weigh 40 g of soil in a 100 ml graduated cylinder.
2. Add 50 ml of water to the soil in the cylinder. Be sure that no soil
material is on the inner walls of the cylinder.
3. Stir thoroughly with a stirring rod to displace the air, and rinse the
stirring rod and the inner walls of the cylinder with 10 ml water.
4. Allow the mixture to stand for 5 minutes and record the volume of
the soil plus 60 ml water.
38
5. Determine separately the moisture content of the soil sample by the
gravimetric method. The amount of moisture should be added to
the amount of added water to obtain the total amount of water
used.
Calculation
( ) water added of Volume water soil of Volume solids total of Volume ÷ + =
Volume of (soil + water) = as shown on graduated cylinder
Volume of added water = 60 ml + soil moisture (ml)
) (cm solids total of Volume
(g) soil of dry wt - Oven
g/cm (PD), Density Particle
3
3
=
5.3.2. The Volumetric Flask Method
Procedure
1. Fill a pre-weighed 100 ml volumetric flask to the mark with boiled distilled
water cooled to room temperature.
2. Weigh the flask plus water (W
1
), and then discard the water and dry the
flask thoroughly.
3. Weigh accurately 50 g of soil and transfer quantitatively to the volumetric
flask (W
s
).
4. Pipette 50 ml of water into the volumetric flask, washing down any soil
particles adhering to the neck.
5. Heat the flask gently on a hot plate until the water starts to boil in
order to drive out air from the soil.
6. Cool the content and bring up to the 100 ml mark with boiled
distilled water cooled to room temperature.
7. Weigh the volumetric flask with its content (W
2
).
8. Determine on a separate sample the moisture content of the soil by
the gravimetric method to find the oven-dry weight of the soil in the
flask.
9. Calculate first the volume of soil particles and then particle density
(PD).
Calculation
( )
2 1 s
3
W W W (cm particles soil of Volume ÷ + = )
39
( )
2 1 s
s 3
W W W
W
g/cm (PD), density Particle
÷ +
=
5.4. Calculation of Percent Pore Space
The pore space (voids) is the portion of bulk soil volume not occupied by solid
particles. It is filled with air and water. Depending on pore size, pore spaces are
given the name macropores (large) or micropores (small). There is no sharp line
of demarcation between the two pore sizes.
Calculation
X100
PD
BD PD
(PS) Space Pore %
÷
=
Example
A soil sample weighs 110 g and contains 15% moisture. The volume of the soil
sample is 75 ml. The sample displaced 36.8 ml water. Calculate BD, PD and
%PS
- Oven-dry wt = 110 x 100/115 = 95.65 g
- BD = 95.65 ÷ 75 = 1.3 g/cm
3
- PD = 95.65 ÷ 36.8 = 2.6 g/cm
3
- %PS = 100(2.6-1.3) / 2.6 = 50
40
6. ANALYSIS OF SATURATION PASTE EXTRACT
6.1. Introduction
A good method for estimation of soil salinity is the measurement of the electrical
conductivity of the saturation extract because it is related to the field conditions.
Over considerable textural range of soils, the soil moisture of the saturation paste
is approximately equal to two times soil moisture at field capacity and four times
of the wilting point. For this reason the conductivity of the saturation extract
(ECe) can be used for estimating the soil salinity in the field.
6.2. Preparation of Saturation Paste
Apparatus
- Balance
- Enamelled cup or 600 ml evaporating dish
- Spatula
- Graduated cylinder or burette - 100 ml
Procedure
1. Weigh 300 g of air-dry
*
soil and transfer into an enamelled cup.
2. Using a graduated cylinder, or a burette, slowly add distilled water to the
sample while stirring the soil with a spatula until a condition of saturation is
reached. Record the amount of water used to reach the saturation point.
3. At saturation point, the soil paste, glistens as it reflects light, flows slightly
when the container is tipped, slides freely off the spatula, and consolidates
easily by tapping the container after a trench is formed in the paste with
the flat side of the spatula.
4. After the paste is prepared, cover the container with aluminium foil and
allow it to stand overnight to permit the soil to imbibe water.
5. The following day, recheck the criteria for saturation as described above. If
the sample hardened, add more water and mix it again. Alternatively, if
more water has been added to the paste, add an additional weighed
quantity of air dry soil and mix. Recheck again the criteria for saturation.
Record the total amount of water used to prepare the saturation paste.

*
Soil samples should not be oven-dried before being used to make a paste because
heating to 105°C partially converts gypsum, CaSO
4
2H
2
O to CaSO
4
½H
2
O. This partially
hydrated gypsum CaSO
4
.½H
2
O is more soluble in water than the fully hydrated gypsum,
CaSO
4
.2H
2
O.
41
6.2.1. Calculation of Saturation Percentage
Saturation percentage (SP) is calculated by dividing the total amount of water
added (ml) by the oven-dry weight of the soil (g) used and multiplying by 100.
Soil moisture, as determined on a separate sample, is taken into consideration
by adding it to the amount of water used in preparing the saturation paste.
Example
The weight of a soil sample (air-dry) used is 300 g, and 121 ml of distilled water
was required to prepare the saturation paste. Moisture content of the air-dry soil
is 8% on oven-dry basis. What is the saturation percentage?
Calculation
Let X be the weight of oven-dry soil.
( )
soil dry - oven of g 277.78
1.08
300
X
g 300 1.08X
g 300 0.08X X
g 300 8%X X
= =
=
= +
= +

Amount of water in the soil sample is: 300 - 277.78 = 22.22 ml
Total amount of water in the soil saturation paste is: 121 + 22.22 = 143.22 ml
Saturation percentage is:
51.6 X100
277.78
143.22
SP = =
6.2.2. Determination of Soil pH
Apparatus
- pH meter with glass electrode
- Glass beakers - 25 ml
Reagent
- Standard pH buffer solutions. Since soils of arid and semi-arid regions are
alkaline in reaction, it is recommended to use, beside the pH 7 standard
buffer solution, another standard solution in the pH range of 8.8 – 9.2 to
calibrate the pH meter.
Procedure
1. Standardize the pH meter using the standard pH buffers, with ample
rinsing of the electrode with distilled water each time it is dipped into a
42
buffer solution. Make sure to make adjustment for temperature correction
according to instruction usually provided with the buffer.
2. Transfer a portion of the already prepared saturated paste to fill about 3/4
of a 25 ml tall beaker.
3. Rinse the electrode carefully with distilled water and immerse into the
paste.
4. Raise and lower the beaker repeatedly to have better contact between the
electrode and the paste. Record the pH reading.
Note: pH can also be measured in the filtrate of 1:2 soil:distilled water or
soil:CaCl
2
(0.01M) suspension. In case of saturation paste, it can also be
measured in the filtrate. KCl can also be used instead of CaCl
2
.
6.3. Preparation of Saturation Extract
Determination of electrical conductivity in saturation extract is recommended for
soil salinity appraisal because saturation percentage (SP) is directly related to
field moisture range. For example, permanent wilting point (PWP) is about one
fourth of SP, and field capacity (FC) is about one half of SP. The extract is also
used for the determination of some of the soluble constituents (Na, K, Ca, Mg, Cl,
SO
4
, NO
3
, HCO
3
, and CO
3
) as an assessment of their availability.
For correlation of soluble salt concentration with plant growth, the
electrical conductivity should be determined in extracts obtained when soil water
tension is in the range of 0.33 – 2.0 atmospheres, similar to that at which plants
grow.
Apparatus
- Extraction unit fitted with Buchner funnel and receiving bottles.
- Suction system and flasks.
Procedure
1. Transfer the saturated paste into a Buchner funnel fitted with Whatman
No. 41 filter paper and connected to a suction system.
2. Apply suction and collect the filtrate in 50 ml receiving bottles. Stop the
filtration when air starts to pass through the soil cake.
3. If the filtrate is turbid, pour it on the soil cake in the Buchner funnel and
filter again.
4. Save the extract for the determination of soluble cations, anions and
electrical conductivity.
43
5. To inhibit the precipitation of calcium during storage, add to each 25 ml of
the extract one drop of 1 g/l solution of sodium hexametaphosphate, and
store in glass bottles at 4°C.
6.3.1. Determination of Soil Salinity (Electric Conductivity)
Electrical conductivity (EC) of a soil solution or extract indicates the concentration
of total soluble salts in solution, thus reflecting the degree of soil salinity.
The unit of measurement is called millimhos per centimeter (mmhos/cm),
or millisiemen per centimeter (mS/cm). The EC is reported to a standard
temperature of 25°C by adjustment factors according to Appendix F.
Salinity affects plants at all stages of development and for some crops
sensitivity varies from one growth stage to another. For example barley, wheat,
and maize are more sensitive to salinity during early seedling growth than during
germination or at advanced stages of growth and grain development (Maas and
Hoffman, 1977).
Soil salinity is extremely important during germination and emergence of
seedlings. Failure in germination and emergence leads to poor stand and
significant reduction in yield (Maas and Hoffman, 1977). Maas and Hoffman
further stated that rootstock differences are an important factor in the salt
tolerance of fruit trees and grapevine. They also stated that fruit trees are not
only sensitive to salinity per se, but are particularly susceptible to the toxic effects
of sodium and chloride ions.
Apparatus
- Electrical conductivity meter
Reagents
1. Standard potassium chloride (KCl) solutions; 0.01 and 0.1 M:
A. For the 0.1 M solution (12.9 mS/cm at 25°C), dissolve 7.456 g of KCl in
distilled water, and then fill the 1 litre volumetric flask to the mark.
B. For the 0.01 M solution (1.412 mS/cm at 25°C), transfer 100 ml of
solution A into a 1 litre volumetric flask, mix well and bring to volume.
Or, dissolve 0.7456 g KCl in 1 litre distilled water as in A.
Procedure
1. Wash the conductivity electrode with distilled water and rinse with solution
B.
2. Pour some of solution B into a 25 ml beaker and dip the electrode in the
solution, and adjust the conductivity meter to read 1.412 mS/cm, corrected
to 25
o
C.
3. Wash the electrode, and dip it in the saturated paste extract.
44
4. Record the digital display corrected to 25
o
C. The reading in mS/cm of
electrical conductivity is a measure of the soluble salts content in the
extract, and an indication of salinity status of the soil.
6.3.2. Determination of Soluble Sodium and Potassium
Apparatus
- Flame photometer
Reagents
1. Standard K and Na solutions: Prepare a series of K and Na standard
solutions in the range of 0 – 2 meq/l of K, and 0 – 4 meq/l of Na. For better
results, add 212.5 mg LiCl in each standard to yield a final concentration
of about 5 meq/l of LiCl. For the preparation of 2 meq K/l, dissolve 149.2
mg KCl in a litre of distilled water and for the preparation of 4 meq Na/l,
dissolve 234 mg NaCl in a litre of distilled water.
Procedure
1. Switch on the flame photometer and let it warm-up for 15 minutes.
2. Calibrate the instrument with blank and standard solutions.
3. Fill the capsules with the soil extracts. Insert the suction tubing in the
capsule and record the reading. Dip the tubing in distilled water to wash
the system, and then read the sample.
4. The readings for samples express the concentration of K or Na as meq/l of
the saturation extract.
Calculation
1000
SP X meq/litre
soil g K/100 or Na soluble of meq =
6.3.3. Determination of Soluble Calcium and Magnesium
Water-soluble calcium and magnesium are measured in the soil saturation
extract. Exchangeable Ca and Mg are determined in ammonium acetate
extraction solution.
Concentration of Ca and of Mg can be determined by atomic absorption
spectrophotometric techniques. Usually titration methods are used because
these cations are present in high concentrations in arid and semi-arid soils. To
use an atomic absorption spectrometer, a number of dilutions are required.
45
Apparatus
- Microburette - 10 ml
Reagents
1. Ammonium chloride - Ammonium hydroxide buffer solution: Dissolve 67.5
g of ammonium chloride in 570 ml of concentrated ammonium hydroxide
and dilute to 1 litre.
2. Sodium hydroxide (NaOH) 4 M: Dissolve 160 g of sodium hydroxide in 1
litre distilled water.
3. Calcium chloride (CaCl
2
) standard 0.01 N: Dissolve 0.5 g of pure calcium
carbonate crystals in 10 ml of approximately 3 M hydrochloric acid and
dilute to 1 litre.
4. Eriochrome black T indicator: Dissolve 0.5 g of Eriochrome black T and
4.5 g of hydroxylamine hydrochloride in 100 ml of 95% ethanol.
5. Calred indicator, 2-Hydroxy-1-(2-Hydroxy-4 Sulfo-1-Naphthyle 20)-3-
Naphtholic acid-original salt.
6. Ethylenediaminetetraacetic acid (EDTA) 0.01 N: Dissolve 2.0 g of EDTA in
water and make up to 1 litre. Standardize the solution against 0.005 M
standard CaCl
2
solution
Procedure
a. Determination of calcium
1. Pipette an aliquot (2 to 5 ml) of soil extract in 50 ml white porcelain dish.
2. Dilute with distilled water to a volume of approximately 25 ml.
3. Add 2 ml of 4 M NaOH and 2-3 mg of calred indicator.
4. Titrate the contents slowly with 0.01 N EDTA until a sky-blue end point is
obtained.
5. If the sample is over titrated with EDTA, it can be back titrated with the
standard 0.01 N calcium chloride solution.
6. Prepare a blank using 2 – 5 ml distilled water, and follow steps 2 to 4.
7. Express the Ca in meq/litre of the saturation extract.
Calculation
46
( )
( ) aliquot taken sample of ml
soln. EDTA of N X blank for EDTA ml extract soil for used EDTA ml
X 1000
Ca/litre of meq
÷
=
b. Determination of Calcium and Magnesium
1. Pipette an aliquot (2 - 5 ml) into 50 ml porcelain evaporating dish.
2. Dilute with distilled water to a volume of about 25 ml and add 5 ml of
ammonium chloride - ammonium hydroxide buffer solution and 3 to 4
drops of Eriochrome black T indicator.
3. Titrate the contents with 0.01 N EDTA until a sky-blue end point is
obtained.
4. Prepare a blank using 2–5 ml distilled water, and follow steps 2 and 3.
5. Express the amount of Ca + Mg in the sample in meq/l.
Calculation
( )
( )
( ) aliquot taken sample of ml
soln. EDTA of N X blank for EDTA ml extract soil for used EDTA ml
X 1000
meq/litre Mg Ca
÷
= +
Determination of Magnesium
Concentration of Mg, as meq/l, is calculated by subtracting meq/l of Ca from
meq/l of (Ca + Mg). The difference is the concentration of Mg as meq/l.
6.3.4. Determination of Carbonate and Bicarbonate
Carbonate and bicarbonate ions are species of the same acid, carbonic acid.
Their proportionate content is a function of pH. The CO
3
2-
starts to form as pH
rises above 8.4.
Apparatus
- Magnetic stirrer
- Microburette - 10 ml
- White Porcelain crucibles
47
Reagents
1. Sulphuric acid (H
2
SO
4
) standard solution, 0.01 M. Dilute 0.56 ml of conc.
sulphuric acid in 1 litre distilled water and standardize using a primary
standard to determine exact molarity.
2. Phenophthalein indicator: Dissolve 0.25 g of phenolphthalein in 100 ml of
60% alcohol.
3. Methyl orange indicator: Dissolve 0.1 g of methyl orange in 100 ml of
water.
Procedure
1. Pipette 5 ml of extract into 50 ml Erlenmeyer flask and dilute with boiled
distilled water to a volume of approximately 25 ml.
2. Add 3 or 4 drops of phenolphthalein indicator. The appearance of a pink
colour indicates the presence of carbonates in the sample.
3. Place the flask on a magnetic stirrer and titrate the content in the flask with
0.01 M H
2
SO
4
by adding one drop every 2-3 seconds until the pink colour
disappears.
4. Record the volume of H
2
SO
4
titrant used (V
ph
).
5. To the colourless solution add 2 or 3 drops of methyl orange indicator.
6. Continue the titration, without refilling the burette, to the pink end point.
7. Record the total volume of H
2
SO
4
used (V
t
).
Save the solution for chloride determination. Make a blank correction for
the methyl orange titration. Express the amount of CO
3
2-
and HCO
3
-
in the
sample as meq/l.
Calculation
a. For CO
3
2-
concentration, the phenolphthalein end point is considered:
( )
4 2 ph 3
SO H of M X V 2 X
aliquot ml 5
ml 1000
CO of meq/litre =
÷ 2
For HCO
3
-
concentration, the methyl orange endpoint is considered:
( )
ph t 4 2 3
2V V SO H of M X
aliquot ml 5
ml 1000
HCO of meq/litre ÷ =
÷
48
6.3.5. Determination of Chloride
Chloride is usually determined in soil saturation extract to assess the
concentration of soluble salts. Estimation by silver nitrate tiration method is
described.
Apparatus
- 10 ml microburette
Reagents
1. Potassium Chromate (K
2
CrO
4
) indicator 5%: Dissolve 5 g of K
2
CrO
4
into
90 ml water. Add a saturated AgNO
3
solution until some brownish red
AgCrO
4
precipitate forms. Place the solution in dark for 24 hours, filter and
make the volume to 100 ml.
2. Silver nitrate (AgNO
3
) standard, 0.005 M: Dissolve 0.8495 g of AgNO
3
in
distilled water and dilute to 1 litre.
Procedure
1. Add 5 drops of K
2
CrO
4
indicator to the solution saved after the titration of
the carbonate and bicarbonate, or start with another 5 ml aliquot of the
extract.
2. Titrate the contents under bright light with the standard AgNO
3
to a
brownish-reddish end point.
3. Prepare a blank in order to (a) correct for the amount of Ag
2+
used to form
the silver chromate (Ag
2
CrO
4
) red precipitate, and (b) to use as a
reference for the end point. The volume of solution at the end of titration of
the blank should be almost equal to that of the unknown.
Calculation
3 3
AgNO of M 0.005 X used AgNO of ml X
aliquot ml 5
ml 1000
Cl/litre of meq =
49
7. CALCIUM CARBONATE
Calcium carbonate, a major component of calcareous soils, ranges from a few
percent in slightly calcareous soils to more than 80 percent in some extremely
calcareous soils. The amount and form of calcium carbonate (total versus active)
and its distribution down the soil profile, affect soil physical and chemical
characteristics. It was found that when total CaCO
3
was above 20%, active
CaCO
3
was more than 10%. Carter (1981) gave 11 to 30% total carbonate and 7
to 9% active CaCO
3
as the critical levels that adversely affected crop growth.
The authors showed that soil retention of P, Mn, Zn and Cu was directly
related to carbonate content and to the distribution of total and active calcium
carbonate between the clay and silt fractions. When total CaCO
3
was less than
20%, the retention of those elements was affected mainly by the total amount of
carbonates, but, when it was above 20%, nature of the carbonates was more
important in governing retention. The active CaCO
3
was more than 10% when
the total CaCO
3
was above 25% in the studied soils. Therefore, one could give
the limit of about 10% active CaCO
3
, which will contribute significantly to the
retention of certain essential elements in calcareous soils.
Physical effects: The active-CaCO
3
portion and the distribution of CaCO
3
in the
different particle size fraction affects the properties (soil-water relationships) of
calcareous soil (Deb and Chadha, 1970; Thabet, 1975). Calcareous soils with
15% calcium carbonate content have higher water diffusivity and faster water
movement than non-calcareous soils of similar texture. Evidently, CaCO
3
assists
in the formation of stable soil aggregates. But, increased CaCO
3
content (25% or
more) tends to precipitate within the capillary tubes causing an increase in the
proportion of micropores, thus reducing the percolation of water.
Effect on plants: Continuous horizons of carbonate accumulation in soil profile
may prevent root penetration and thus may retard the degree of plant
development and reduce the yield. Sys (1975) classified the sensitivity of crops
to CaCO
3
into three groups as follows:
1. Tolerant crops: wheat, alfalfa, figs, olives and dates
2. Moderately tolerant crops: barley, clover, cotton, maize, millets, rice,
grapes, sugarcane, sugar beet, watermelons, lettuce, tomatoes,
beans, artichokes, tobacco and onions.
3. Sensitive crops: citrus, banana and potatoes.
50
7.1. Determination of Total Calcium Carbonate
Apparatus
- 25 ml and 100 ml Erlenmeyer flasks
- Burette, 25 ml
Reagents
1. Hydrochloric acid (HCl) Standard 1 M: Add 81 ml HCl to about 500
ml water in a 1 litre volumetric flask, cool and make to volume with
distilled water. Standardize it against a primary standard.
2. Sodium hydroxide (NaOH) Standard 0.5 M: Dissolve 20 g NaOH in
800 ml distilled water in a 1 litre volumetric flask, cool and dilute to
1 litre. Standardize it against a primary standard.
3. Phenolphthalein indicator 1% in 60% ethanol: Weigh 1 g
phenolphthalein crystals in 100 ml volumetric flask add 60 ml of
ethyl alcohol and dilute to volume with distilled water. Shake the
flask until the crystals dissolve completely.
Procedure
1. Weigh 5 g of soil and transfer into a 250 ml Erlenmeyer
flask.
2. Add 100 ml of 1.0 M HCl.
3. Cover the flask with aluminium foil and keep it overnight or
heat it to boiling for 5 minutes and let it cool to room
temperature.
4. Filter, and pipette 10 ml of the filtrate into a 100 ml
Erlenmeyer flask.
5. Add 2 or 3 drops of phenolphthalein to the content and titrate
with 0.5 M sodium hydroxide.
Calculation
( ) ( ) | |
( ) ( ) | | 10 5 . 0 1 10 %
100
2 1000
100
10
100
5 0 1
3
3
× × ÷ × =
×
×
× × × ÷ × =
mlNaOH CaCO
l g Wt. of soi
g
ml) te ( ate aliquo Vol. filtr
ml) Vol. HCl (
M . mlNaOH M mlHCl % CaCO
7.2. Determination of Active Calcium Carbonate (modified
Drouineau method)
51
Reagents
1. Ammonium Oxalate (NH
4
)
2
C
2
O
4
0.2N: Dissolve 12.61 g (NH
4
)
2
C
2
O
4
in 1 litre of distilled water.
2. Sulphuric Acid Concentrated (analytical grade).
3. Potassium Permanganate (KMnO
4
) 0.1N: Dissolve 3.16 g KMnO
4
in
1 litre of distilled water. Keep the solution at a gentle boil for about
1 hour, cover and let stand overnight. Filter and store in amber
glass bottle.
The potassium permanganate can be standardized by titrating with the
primary standard sodium oxalate, Na
2
C
2
O
4
, which is dissolved in
sulphuric acid to form oxalic acid:
5H
2
C
2
O
4
+ 2MnO
4
-
+6H
+
Æ 10CO
2
+ 2Mn
2+
+ 8H
2
O
The solution must be heated to 80 – 90
o
C for rapid reaction. The
reaction is catalyzed by Mn
+2
produced and it goes very slowly at first
until some Mn
+2
is formed. The first persistent pink colour (30 sec.)
should be taken as the end point. Determine a blank by titrating an
equal volume of 1 M H
2
SO
4.
Procedure
1. Weigh accurately 2.5 g of soil (sieved through a 2 mm sieve) into a 500 ml
Erlenmeyer flask.
2. Add 250 ml of the ammonium oxalate solution and shake for two hours.
3. Filter the suspension and collect the filtrate (discard the first few ml).
4. Pipette 10 ml of the filtrate into an Erlenmeyer flask.
5. Add to it 100 ml of distilled water and 5 ml of concentrated sulphuric acid
and heat to a temperature of 60 - 70°C.
6. Titrate with KMnO
4
(0.02 M) to a pink endpoint, and note down the volume
used (V
sample
).
7. Prepare a blank in the same manner using 10 ml of the ammonium
oxalate solution, and record the volume of the titrant used (V
blank
).
8. Calculate percent of active calcium carbonate content of the soil.
Calculation
( )
1000
5
X
g 2.5
g 100
X
(ml) aliquote filtrate
(ml) O C NH
X )
sample
V
blank
(V N
3
CaCO Active %
2 4
KMnO
4
4 2
÷ =
Since 0.1 meq MnO
4
2-
reacts with 5mg CaCO
3
Therefore,
52
1000
5
X
g 2.5
g 100
X X )
sample
V
blank
(V N
3
CaCO Active %
4
KMnO
ml 10
ml 250
÷ =
5 X )
sample
V
blank
(V N
3
CaCO Active %
4
KMnO
÷ =
Note: The maximum concentration of active calcium carbonate that can be
dissolved by the above method is 20%. If active CaCO
3
content obtained is
greater than 17%, then the analysis should be repeated with a smaller amount of
soil or larger volume of oxalate extractant.
53
8. CATION EXCHANGE CAPACITY (CEC)
Presence of high concentrations of calcium, especially in the form of gypsum
interferes with the determination of cation exchange capacity, which is an
important parameter for soil fertility and mineralogical characterization.
The exchangeable cations and cation exchange capacity (negative charges on
the surface of soil particles) are expressed in terms of milliequivalents of negative
charge per 100 g of oven-dried soil (1 meq/100 g soil = 1 cmol/kg in SI system).
The unit meq/100 g has been used in this manual because most of the soil
testing laboratories in the Near East still use and are familiar with meq/100g for
CEC and exchangeable cations measurements.
The definitions of equivalent and equivalent weight are as follows:
ƒ Atomic weight: Weight in grams of 6 × 10
23
atoms of the substance. One
mole of substance is 6×10
23
atoms, molecules, ions, compounds and so
on; therefore, units of atomic weight are grams per mole (g/mole).
molecules or ions 10 6 per grams ght Atomic Wei
23
× =
ƒ Equivalent weight: Quantity (mass) of a substance (e.g. cation, anion,
compound, etc.) that will react with or displace one gram of hydrogen (H
+
),
which equals Avogadro’s number of charges (+ or -). This is equal to the
weight in grams of 6×10
23
charges, therefore, units of equivalent weight
are grams per equivalent (g/eq).
) or ( charges 10 6 per grams Weight Equivalent
23
÷ + × =
The use of equivalents to express concentrations or quantities of nutrients in soil
is very convenient and widely used in soil testing laboratories (one Ca
2+
cation
replaces two K
+
cations, but one equivalent of Ca
2+
replaces one equivalent of K
+
or one equivalent of any other cation). Thus, for clarity, it will be followed in this
manual also.
X of Valence
X of ght Atomic wei
X of weight Equivalent =
Examples:
g/eq 39.1
eq/mole 1
g/mole 39.1
K of wt. Equivalent = =
+
g/eq 20
eq/mole 2
g/mole 40
Ca of wt. Equivalent
2
= =
+
g/eq 9
eq/mole 3
g/mole 27
Al of wt. Equivalent
3
= =
+
54
8.1. Determination of Cation Exchange Capacity (CEC)
Apparatus
- Centrifuge
- 50 ml round bottom centrifuge tubes
- Mechanical shaker
- Flame photometer
Reagents
1. Sodium acetate (NaOAc) 1.0 M: Dissolve 136.08 g of sodium
acetate trihydrate in distilled water and bring volume to 1 litre.
Adjust the pH to 8.2.
2. Ethanol 95%
3. Ammonium acetate (NH
4
OAc) 1.0 M: Dissolve 77.09 g of
ammonium acetate in distilled water and dilute to 1 litre. Adjust pH
to 7.0. Or, add 57 ml of conc. acetic acid (analytical grade) to 700-
800 ml distilled water in 1 litre beaker. Then, with constant stirring,
add 68 ml of conc. ammonium hydroxide. Add more distilled water
to bring the volume close to 1 litre, and adjust pH to 7.0 by the
addition of more ammonium hydroxide or acetic acid.
4. Na standard solution: Refer 6.3.2.
Procedure
1. Weigh accurately about 5 g soil and transfer the sample to a 50 ml
centrifuge tube.
2. Add 30 ml of 1.0 M sodium acetate solution to the tube, stopper and shake
in a mechanical shaker for 5 minutes.
3. Centrifuge at 2000 rpm for 5 minutes or until the supernatant liquid is
clear.
4. Decant the liquid completely and repeat the extraction three more times.
Discard the decants.
5. Repeat steps 2 – 4 with ethanol or isopropyl alcohol until the EC of the
decant reads less than 40 mS/cm (usually it takes 4 to 5 washings).
6. To displace the adsorbed Na, repeat steps 2 – 4 using the ammonium
acetate solution. Collect the decants in 100 ml volumetric flask fitted with a
funnel and filter paper. Make up to volume with ammonium acetate
solution.
55
7. To determine sodium concentration by flame photometry (see section
6.3.2), prepare a series of Na standard solutions in the range of 0 – 4
meq/l of Na. For better results, add LiCl in each standard to yield a final
concentration of about 5 meq/l of LiCl.
Calculation
(g) soil of Wt.
10 X R
(g) soil of Wt.
g 100
X
ml 1000
ml 100
X meq/l) (R Reading Emission soil g Na/100 of meq
=
=
Where, R is the meq/l of Na as determined by the flame photometer.
The displaced Na is actually a measure of the Cation Exchange Capacity
(CEC) of the soil. So, the meq/100 g of Na is actually meq/100 g exchangeable
cations (Ca, Mg, Na and K).
8.2. Determination of CEC in Gypsiferous and Calcareous
Soils
Apparatus
- Centrifuge
- 50 ml round bottom centrifuge tubes
- Mechanical shaker
- Flame photometer
Reagents
1. Sodium oxalate (Na
2
C
2
O
4
) saturated solution: Add 10 g sodium oxalate
crystals to 100 ml distilled water. Allow to stand with occasional shaking
for 8 hrs or longer. Let it settle until clear or filter.
2. Ethanol 95% or isopropyl alcohol
3. Ammonium acetate (NH
4
OAc) 1.0 M solution: Add 57 ml of conc. acetic
acid (reagent grade) to 700-800 ml distilled water in a 1 litre beaker. Then,
with constant stirring, add 68 ml of conc. ammonium hydroxide. Bring the
volume close to 1 litre, and adjust pH to 7.0 by the addition of more
ammonium hydroxide or acetic acid. Or, dissolve 77.09 g of ammonium
acetate in distilled water and dilute to 1 litre. Adjust pH to 7.0.
4. Na standard solution: Refer 6.3.2.
56
Procedure
1. Weigh accurately 4 g of soil and transfer to a 50 ml centrifuge tube.
2. Add 30 ml of saturated sodium oxalate solution to the tube, stopper and
shake for two hours.
3. Centrifuge at 2000 rpm for 5 minutes or until the supernatant liquid is
clear.
4. Decant the liquid completely and repeat the extraction three more times.
Discard the decants.
5. Repeat steps 2 – 4 with ethanol 95% or isopropyl alcohol until the EC of
the decant reads less than 40 mS/cm (takes 4 to 5 washings).
6. To displace adsorbed sodium, repeat steps 2 – 4 using ammonium
acetate solution. Collect the decants in a 100 ml volumetric flask fitted with
a funnel and filter paper. Make up to volume with ammonium acetate
solution.
7. Determine sodium concentration as in section 6.3.2.
Calculation
(g) soil of Wt.
10 X R
(g) soil of Wt.
g 100
X
ml 1000
ml 100
X meq/l) (R Reading Emission soil g Na/100 of meq
=
=
Where R is the meq/l of Na as determined by the flame photometer.
As was explained above (section 8.1), meq/100 g of Na displaced by NH
4
,
is actually the meq/100 g of exchangeable cations (Ca, Mg, Na and K) or the
CEC of the soil.
8.3. Exchangeable Sodium Percentage
Exchangeable Sodium Percentage (ESP) is the relative amount of exchangeable
Na to the sum of exchangeable cations, or CEC.
As more and more of the cation exchange capacity of soil becomes
satisfied with Na on the expense of Ca, Mg and K, the clay fraction become
dispersed and deflocculated causing the destruction of soil structure.
Some critical values were internationally given to ESP for the classification
of sodium-affected soils and its effect on soil structure and plant growth.
However, it is a common observation in the sandy soils of the Persian Gulf
Countries, and in the Fezzan province of Libya, that ESP may be as high as 50
percent or more, but soil structure is not impaired and so is plant growth and
yield. The reason, probably, is the single grain structure of the predominantly
57
sandy soils. In contrast, soil structure of clayey soils in Sudan would be seriously
impaired at ESP values of only 8 percent due to de-flocculation of the clay
fraction. Accordingly, ESP values that are critical in clayey soils are tolerated in
sandy soils.
Calculation
100 X
g) (meq/100 CEC
g) (meq/100 Na le Exchangeab
ESP =
58
9. SOIL GYPSUM
Precise determination of gypsum in soils is difficult, because of inherent errors
involved in the extraction of this mineral with water. The factors, other than the
solubility of gypsum, that may influence the amount of Calcium and Sulphate
extracted from gypsiferous soils are (1) the solution of calcium and sulphate from
sources other than gypsum, (2) exchange reactions in which soluble calcium
replaces other cations, such as sodium and magnesium.
Conventional standard methods for the determination of gypsum in soils
do not extract the total amount. Results are, therefore, lower than the real
amounts present. Sayegh et al. (1978) improved gypsum determination by
grinding the soil sample to 270 mesh (0.053 mm) instead of 100 (2.0 mm), and
by using a larger volume of water. Figure 8 shows the higher values obtained for
gypsum content with increasing water to soil ratio, and also with increased mesh
size. Determination of soil gypsum by precipitation with acetone is described
here.
0
10
20
1:50 1:100 1:200 1:300 1:400 1:500
SOIL:WATER RATIO
%

G
Y
P
S
U
M
Mesh10
Mesh 50
Mesh 100
Mesh 170
Mesh 270
Figure 8. Effect of soil:water ratio and particle size on total gypsum
extraction
Apparatus
- Centrifuge
- Centrifuge tubes – 50 ml
- Mechanical shaker
59
Reagent
- Acetone (analytical grade).
Procedure
1. Place 1 g of air-dried soil, ground to pass through a 270 mesh (0.053 mm)
sieve, in an Erlenmeyer flask.
2. Add 500 ml of distilled water, stopper the flask, and shake for 20 minutes
on a mechanical shaker.
3. Filter the content through Whatman No. 41 filter paper.
4. Transfer 20 ml aliquot of the filtered extract into a 50 ml centrifuge tube.
5. Add 20 ml of acetone, mix and allow to stand for 15 minutes or until the
precipitate flocculates.
6. Centrifuge the content at 2000 rpm for 3 minutes, carefully decant the
supernatant, then invert the tube on a clean filter paper and let it drain for
5 minutes.
7. Wash the sides of the tube with 10 ml acetone and disperse the
precipitate.
8. Repeat step 6.
9. Add 40 ml of distilled water to the tube, stopper and shake until the
precipitate is completely dissolved.
10. Measure the EC of the solution and correct conductivity reading to 25°C.
11. Determine the gypsum concentration in solution from Table 2, which
shows a direct relationship between the EC of the extract and its gypsum
content.
Table 2. Electrical conductivity values for different CaSO
4
concentrations in
water
CaSO
4
concentration (meq/l) EC at 25°C (mS/cm)
1 0.121
2 0.226
5 0.500
10 0.900
20 1.584
30.5 2.205
Source: Richards, 1954.
60
Calculation
Gypsum content per 100 g soil is calculated as follows:
ml 1000
used water of ml
X reading EC from CaSO of meq/l aliquot in CaSO of meq
4 4
=
used extract water of ml X ratio water : Soil
aliquot in CaSO of meq X 100
soil g gypsum/100 of meq
4
=
20
500 X aliquot in CaSO of meq X 100
4
=
61
10. SOIL ORGANIC MATTER
10.1. Walkley – Black Wet Combustion Method
Soil organic matter is defined as the organic fraction of soil including plant,
animal and microbial residues at all stages of decomposition including fresh and
humus fractions. Organic matter can be estimated in soils by determination of the
change in weight of a soil sample resulting from destruction of organic
compounds by H
2
O
2
treatment or by ignition at high temperature. The H
2
O
2
method does not quantitatively remove all organic matters, while the ignition
method gives an overestimate because inorganic fractions may also be lost
during ignition. The wet combustion analysis of soils by chromic acid digestion
has been accepted as a standard method for determining total C, as it gives
acceptable results. The organic matter content of a soil may be estimated by
multiplying the organic carbon concentration by a constant factor based on the
percentage of Carbon (C) in organic matter. Published organic C to total organic
matter conversion factors for surface soils vary from 1.724 to 2.0. In the soils of
arid and semi-arid regions, a value of 1.724 is an acceptable factor and is
commonly used, although whenever possible the appropriate factor must be
determined experimentally for each type of soil. In the following procedure the
factor 1.724 is used for calculation.
Apparatus
ƒ Erlenmeyer flasks, 500 ml
ƒ Magnetic stirrer
ƒ Burettes, 10 ml
ƒ Thermometer, 200°C
Reagents
1. Potassium dichromate (K
2
Cr
2
O
7
) solution, 0.1667 M: Dissolve 49.04 g of
potassium dichromate in water and dilute to 1 litre.
2. Sulphuric acid concentrated, containing silver sulphate: Dissolve 25 g
silver sulphate in a litre of sulphuric acid (96%, reagent grade).
3. Ferroin indicator (ortho-phenanthroline ferrous sulphate, 0.025 M):
Dissolve 14.85 g o-phenanthroline monohydrate and 6.95 g ferrous
sulphate in water and dilute to 1 litre.
4. Ferrous sulphate (FeSO
4
.7H
2
O), 0.5 M: Dissolve 140 g of FeSO
4
.7H
2
O in
water, add 15 ml of concentrated sulphuric acid, cool to room temperature,
and dilute to 1 litre. Standardize this solution daily against 10 ml of 0.1667
M potassium dichromate, as given in the procedure below.
62
Procedure
1. Grind the soil to pass through 0.5 mm screen, avoiding contact with iron or
steel.
2. Transfer a weighed sample, not exceeding 5 g and containing from 10 to
25 mg of organic carbon (always a few trial samples are to be done in an
unknown situation) to a 500 ml wide mouth Erlenmeyer flask (1.0 g for
clay soil and 2-3 g for sandy soil).
3. Add 10 ml of 0.1667 M potassium dichromate. Swirl to disperse the soil,
then add 20 ml of conc. H
2
SO
4
.
4. Swirl the flask, insert a thermometer, and heat gently to a temperature of
150°C. Keep contents of flask in motion in order to prevent local
overheating, which results in error caused by thermal decomposition of
dichromate.
5. Place the flask on an asbestos pad, and allow to cool to room temperature
slowly.
6. Add 200 ml of water and 4 to 5 drops of Ferroin indicator.
7. Titrate with 0.5 M ferrous sulphate until colour changes from green to red.
8. Since some soils adsorb the o-phenanthroline indicator, the titration may
be improved by a prior filtration, using a rapid filter paper in a Buchner
funnel. In that case, filter after the addition of water and add the indicator
to the filtrate.
9. Make a blank determination in the same manner, but without soil, to
standardize the reagents.
10. If more than 80% of the dichromate solution is reduced, then the analysis
should be repeated with a smaller amount of soil or larger volume of
dichromate.
Calculation
(g) soil dry - Oven
0.336 X ) FeSO of meq - O Cr K of (meq
% C Organic
4 7 2 2
=
1.724 X % C Organic % matter Organic =
Remarks: The Walkley - Black method for the determination of organic carbon in
soils has been found to give approximately 89% recovery of carbon as compared
to the dry combustion method. The conversion factor 0.336 was obtained by
dividing 0.003, the milliequivalent weight of carbon, by 89 and multiplying by 100
to convert to percent. Chloride interference is eliminated by the addition of the
silver sulphate to the digesting acid as indicated. The presence of nitrates and
carbonates up to 5 percent and 50 percent, respectively, do not interfere.
However, in a study by Sayegh and Salib (1969) on calcareous Lebanese
soils collected from the Beka'a Valley, it was found that recovery of organic
63
carbon when measured by the wet combustion method was 78% of the dry
combustion method.
64
11. SOIL NITROGEN
11.1. Total Nitrogen (Kjeldahl method)
Apparatus
- Kjeldahl digestion unit
- Ammonium-N distillation unit
Reagents
1. Sulphuric - salicylic acid: Dissolve 1 g of salicylic acid in 30 ml of
concentrated sulphuric acid.
2. Sodium thiosulphate (Na
2
S
2
O
3
.5H
2
O): Twenty-mesh dried powdered
crystals.
3. Sulphate mixture: Mix 10 parts of potassium sulphate, 1 part of ferrous
sulphate and 1/2 part of copper sulphate, grind the mixture and pass
through a 40-mesh screen.
4. Sodium hydroxide (NaOH) 45% solution: Dissolve 450 g NaOH in 1 litre of
distilled water.
5. Mossy Zinc pieces.
6. Boric acid 4% solution: Dissolve 40 g of boric acid in 1 litre of distilled
water.
7. Sulphuric acid (H
2
SO
4
) standard solution, 0.05 M: Dissolve 2.8 ml H
2
SO
4
in 1 litre of distilled water and standardize using a primary standard.
8. Bromocresol green - red methyl mixed indicator: Mix both indicators at a
ratio of 1:1 in powder form.
Procedure
1. Weigh 10 g of soil (which has been passed through a 20 mesh sieve) and
transfer into an 800 ml Kjeldahl flask.
2. Add 50 ml of sulphuric-salicylic acid mixture to the flask and swirl to bring
the sample quickly into intimate contact.
3. Allow it to stand overnight. Add 5 g of sodium thiosulphate and heat gently
for about 5 minutes, taking care to avoid frothing.
4. Cool the flask, add 10 g of the sulphate mixture and digest on the Kjeldahl
apparatus gradually raising the temperature until the digest becomes
clear. Digest further at full heat.
65
5. Cool, add 300 ml of distilled water and mix. Slowly add 100 ml of
concentrated sodium hydroxide by letting it run down the neck and settle
in the bottom of the flask.
6. Add a large piece of mossy zinc and a spoon of glass beads, connect the
flask to the distillation unit, shake by swirling, turn on heat, and distil 150
ml into an Erlenmeyer flask containing 50 ml of 4 percent boric acid
solution.
7. Add 10 drops of bromocresol green-methyl red indicator and titrate with
the 0.05 M standard sulphuric acid solution to the first faint pink.
8. Titrate a blank prepared in the same manner but without adding a soil
sample.
Calculation
S
2.8
X M X B) (T (%) N Kjeldahl ÷ =
T = ml of standard acid with sample titration
B = ml of standard acid with blank titration
M = molarity of sulphuric acid
S = weight of soil sample in g
11.2. Determination of Mineral Nitrogen
Inorganic N in soil is present predominantly as nitrates NO
3
-
and ammonium ions
NH
4
+
. Nitrite is seldom present in detectable amounts, and its determination is
normally unwarranted except in neutral to alkaline soils following the application
of NH
4
or NH
4
-forming fertilizers (Keeney and Nelson, 1982).
Nitrate is highly soluble in water, and a number of solutions including
water have been used as extractants. These include, saturated 0.35%
CaSO
4
.2H
2
O solution, 0.03 M NH
4
F, 0.015 M H
2
SO
4
, 0.01 M CaCl
2
, 0.5 M
NaHCO
3
pH 8.5, 0.01 M CuSO
4
, 0.01 M CuSO
4
containing Ag
2
SO
4
and 2.0 M
KCl.
Exchangeable NH
4
is defined as NH
4
that can be extracted at room
temperature with a neutral K salt solution. Various extractants at different
molarities have been used, such as 0.05 M K
2
SO
4
, 0.1 M KCl, 1.0 M KCl, and 2.0
M KCl.
The methods for the determination of NO3
-
and NH4
+
-N are even more
diverse than the methods of extraction (Keeney and Nelson, 1982). These range
from specific ion electrode to manual colorimetric techniques, micro-diffusion,
steam distillation, and flow injection analysis. Steam distillation is still a preferred
method when using N
15
; however, for routine analysis automated colorimetric
techniques and phenoldisulfonic acid colorimetric methods are commonly used.
66
11.2.1. Determination of Nitrate by the Phenoldisulfonic Acid
Method
One of the major difficulties in estimating NO
3
in soils by colorimetric methods is
obtaining a clear colourless extract with low contents of organic and inorganic
substances, which interfere with the colorimetric method. In arid and salt affected
soils, chloride (Cl) is the major anion, which interferes with colour development of
the phenoldisulfonic acid method. Therefore, if the chloride concentration is more
than 15 μg/g, it should be removed before analysis by the use of Ag
2
SO
4
to
precipitate chloride as AgCl. The Ag
2
SO
4
is added to the extract or to the reagent
used for extraction, and the AgCl is removed by filtration or centrifugation after
precipitation of the excess Ag
2
SO
4
by an alkaline reagent such as Ca(OH)
2
or
MgCO
3
. It is necessary to remove the excess silver ions before analysis of the
extract because they interfere with the phenoldisulfonic acid method of
determining NO
3
.
Apparatus
- Reciprocating shaker
- Heavy-duty hot plate
- Spectrophotometer
- Dispenser
Reagents
1. Phenoldisulfonic acid (phenol 2,4-disulfonic acid): Transfer 70 ml of pure
liquid phenol (carbolic acid) to an 800 ml Kjeldahl flask. Add 450 ml
concentrated H
2
SO
4
while shaking. Add 225 ml fuming H
2
SO
4
(13-15%
SO
3
). Mix well. Place the Kjeldahl flask (loosely stoppered) in boiling water
in a beaker and heat for 2 hours. Store the resulting phenoldisulfonic acid
[C
6
H
3
OH(HSO
3
)
2
] solution in a glass-stoppered bottle.
2. Dilute ammonium hydroxide solution (NH
4
OH), about 7.5 M: Mix one part
NH
4
OH (sp. gr. 0.90) with one part H
2
O.
3. Copper sulphate (CuSO
4
) solution, 0.5 M:. Dissolve 125 g CuSO
4
.5H
2
O
per 1 litre of distilled water.
4. Silver sulphate (Ag
2
SO
4
) solution (0.6%): Dissolve 6.0 g Ag
2
SO
4
per 1 litre
of distilled water. Heat or shake well until all the salt is dissolved.
5. Nitrate-extracting solution: Mix 200 ml of a 0.5 M copper sulphate solution
and 1 litre of a 0.6% silver sulphate solution and dilute to 10 litres with
water. Mix well.
6. Standard nitrate solution (100 μg NO
3
-N/ml stock solution): Dissolve
0.7221 g KNO
3
(oven dried at 105°C) in water and dilute to 1 litre. Mix
thoroughly.
67
7. Standard nitrate solution (10 μg NO
3
-N/ml working solution): Dilute 100 ml
of 100 μg NO
3
-N/ml stock solution to 1 litre with water. Mix well.
8. Calcium hydroxide, reagent-grade powder (free of NO
3
).
9. Magnesium carbonate, reagent-grade powder (free of NO
3
).
Procedure
1. Place about 5 g soil in an Erlenmeyer flask.
2. Add 25 ml 2M KCl solution and shake for 10 minutes.
3. Add 0.2 g Ca(OH)
2
and shake for 5 minutes.
4. Add 0.5 g MgCO
3
and shake for 10-15 minutes.
5. Allow to settle for a few minutes.
6. Filter through a Whatman filter paper No. 42.
7. Pipette 10 ml of the clear filtrate into a 100 ml beaker. Evaporate to
dryness on a hot plate at low heat in a fume hood free of HNO
3
fumes. Do
not continue heating beyond dryness.
8. Let the beaker cool and add 2 ml phenoldisulfonic acid rapidly (from a
burette having the tip cut off or a dispensette) covering the residue quickly.
Rotate the beaker so that the reagent comes in contact with all the
residual salt. (Caution: the phenoldisulfonic acid is very corrosive).
9. Allow to stand for 10-15 minutes.
10. Add 16.5 ml of cold water. Rotate the beaker to dissolve the residue (stir
with a glass rod until the entire residue is in solution).
11. Cool the beaker to room temperature and add dilute NH
4
OH slowly until
the solution is distinctly alkaline, as indicated by the development of a
stable yellow colour (15 ml).
12. After beakers are cool, add 16.5 ml of water (volume becomes = 50 ml).
Mix thoroughly.
13. Read the concentration of NO
3
-N at 415 nm.
14. Standards: evaporate 0, 2, 5, 8, and 10 ml of the 10 μg NO
3
-N/ml working
solution after adding 10 ml NO
3
-extracting solution in 100 ml beakers and
evaporate to dryness. Follow steps 9 to 13. These standard solutions have
0, 0.40, 1.00, 1.60, and 2.00 μg NO
3
-N per ml.
68
Calculation
(g) soil dried oven of Wt.
(ml) soln. extracting of Vol.
X
(ml) evaporated Vol.
(ml) t developmen colour after Vol.
X g/ml) ( soln. test in N
3
NO
g/g) ( soil in N -
3
NO
÷
µ
÷
= µ
÷
-
11.2.2. Determination of Nitrate by the Specific Ion Electrode
The concentration of nitrate-nitrogen (NO
3
-N) is estimated by comparison of the
electromotive force (emf in millivolts) in the unknown with that in the NO
3
-
-N
standards prepared by the same method.
Apparatus
- pH – millivolt meter or specific ion meter, with specific nitrate electrode
and reference electrode.
Reagents
1. Standard nitrate-nitrogen (NO
3
-N) solutions: Prepare a series of standards
in water ranging from 1 to 100 mg NO
3
-
-N per litre..
2. Ammonium sulphate [(NH
4
)
2
SO
4
], 2 M (for ionic strength adjustment):
Dissolve 264 g of reagent grade (NH
4
)
2
SO
4
in 1 litre of water.
Procedure
1. Add 20 g of soil and 40 ml of distilled water to a 100 ml beaker. Stir the
mixture intermittently for an hour (two to three times).
2. Place the beaker on a magnetic stirrer, insert the electrodes into the
suspension and start the stirring. Record the millivolt reading (if using a
calibration curve standardization method), or read the concentration
directly (if using a specific ion meter calibrated to take into account the 1:2
dilution).
Note: Manufacturer instructions should be consulted for details of electrode
assembling, storage and standardization. If interference are suspected (high
soluble salts, Cl
-
or NO
2
-
), specific treatment of the extract may be required. If
NH
4
+
-N is to be determined by an electrode on the same sample, the
analysis must be made before the NO
3
-
analysis, because significant sample
contamination by the external filling solution of the reference electrode may
occur. The presence of soil solids does not markedly affect NO
3
-
electrode
determinations.
69
11.3. Extraction of Exchangeable Ammonium and Nitrate
Apparatus
- Erlenmeyer flasks
- Pipettes
- Mechanical shaker
Reagent
- Potassium chloride (KCl) solution, approximately 2 M: Dissolve 150 g of
reagent-grade KCl in 1 litre of distilled water.
Procedure
1. Place 10 g of soil in a 250 ml, wide mouth Erlenmeyer, and add 100 ml of
2 M KCl.
2. Stopper and shake the flasks on a mechanical shaker for 1 hour.
3. Allow the soil-KCl suspension to settle and for the supernatant to clear
(usually about 30 min).
4. If the KCl extract cannot be analyzed soon after its preparation (within 24
hours), filter the soil-KCl suspension (Whatman no. 42 filter paper) and
store in a refrigerator.
5. Aliquots from this extract will be used for the following assays.
11.3.1. Determination of Ammonium by Indophenol Blue
Method
The phenol reacts with NH
3
in the presence of an oxidizing agent such as
hypochlorite to form a coloured complex in alkaline conditions. The addition of
sodium nitroferricyanide dihydrate, also known as sodium nitroprusside as a
catalyst in the reaction between phenol and NH
3
increases the sensitivity of the
method several folds. The addition of EDTA is necessary to complex divalent and
trivalent cations present in the extract. Otherwise, it forms a precipitate at the pH
of 11.4–12 used for colour development, and this turbidity would interfere with the
formation of the phenol-NH
3
complex.
Apparatus
- Variable wavelength spectrophotometer, equipped with 1 cm light path
and capable of measuring absorbance at 636 nm.
Reagents
70
1. Potassium chloride (KCl) solution, 2 M: Dissolve 150 g reagent-grade KCl
in 1 litre of distilled water.
2. Standard ammonium (NH
4
+
) solution: Dissolve 0.4717 g of ammonium
sulphate (NH
4
)
2
SO
4
in distilled water and dilute to a volume of 1 litre. If
pure, dry (NH
4
)
2
SO
4
is used, the solution contains 100 μg of NH
4
+
-N/ml.
Store the solution in a refrigerator. Immediately before use, dilute 4 ml of
the stock NH
4
+
solution to 200 ml. The resulting working solution contains
2 μg of NH
4
+
-N/ml.
3. Phenol-nitroprusside reagent: Dissolve 7 g of phenol and 34 mg of sodium
nitroprusside [disodium pentacyanonitrosylferrate, Na
2
Fe(CN)
5
NO.2H
2
O]
in 80 ml of deionised water, and dilute to 100 ml. Mix well and store in a
dark-coloured bottle in a refrigerator.
4. Buffered hypochlorite reagent: Dissolve 1.480 g of sodium hydroxide
NaOH in 70 ml of deionised water, add 4.98 g of sodium monohydrogen
phosphate (Na
2
HPO
4
) and 20 ml of sodium hypochlorite (NaOCl) solution
(5-5.25% NaOCl). Use less or more hypochlorite solution if the NaOCl
concentration is higher or lower than that indicated. Check the pH to
ensure a value between 11.4 and 12.2. Add a small amount of additional
NaOH if required to adjust the pH. Dilute to a final volume of 100 ml.
5. Ethylenediaminetetraacetic acid (EDTA) reagent: Dissolve 6 g of
ethylenediaminetetraacetic acid disodium salt (EDTA disodium) in 80 ml of
deionised water, adjust to pH 7, mix well, and dilute to a final volume of
100 ml.
Procedure
1. Pipette an aliquot (not more than 5 ml) of the filtered 2 M KCl extract (see
11.3) containing between 0.5 and 12 μg of NH
4
+
-N into a 25 ml volumetric
flask. Aliquots of s3 ml normally contain sufficient NH
4
+
-N for
measurement.
2. Add 1 ml of the EDTA reagent, and mix the contents of the flask.
3. Allow the flask contents to stand for 1 minute, then add 2 ml of the phenol-
nitroprusside reagent, followed by 4 ml of the buffered hypochlorite
reagent, and immediately make up to volume with deionised water and
mix well.
4. Place the flask in a water bath at 40°C for 30 min.
5. Remove the flask from the bath, cool to room temperature, and determine
the absorbance of the coloured complex at a wavelength of 636 nm
against a reagent blank solution.
6. Determine the NH
4
+
-N concentration of the sample by reference to a
calibration curve plotted from the results obtained from the measurement
of known concentrations of NH
4
+
-N.
71
7. To prepare a standard curve, add 0, 1, 2, 3, 4, 5, and 6 ml of the 2 μg/ml
NH
4
+
-N solution to the series of 25 ml flasks.
8. Add an appropriate amount of 2 M KCl solution (same volume as that
used for aliquots of soil extract) to the 25 ml volumetric flasks.
9. Measure the intensity of blue colour developed with these standards by
the procedure described for the analysis of unknown extracts.
11.3.2. Determination of Ammonium by Specific Ion Electrode
Ammonium-N concentration is also estimated by comparison of the electromotive
force (emf, in millivolts) in the unknown with that obtained by analysis of NH
4
+
-N
standards by the same method. The sample or standard is made alkaline by the
addition of NaOH (pH 11-12), because the electrode responds only to NH
3
activity.
The meter should be calibrated immediately before each series of
analysis. Measurements should be made within 1-2 minutes after the addition of
NaOH to ensure no loss of NH
3
. If Hg
+
is present in the sample, sodium Iodide
(15 g of NaI/l) can be added to the 0.25 M NaOH. Iodide forms complexes with
Hg
+
. Care must be taken to prevent air bubble entrapment under the electrode.
This is easily accomplished by inserting the electrode at about a 20° angle with
respect to vertical.
Apparatus
- Ammonia electrode
- pH-millivolt meter with sensitivity of ± 0.1 mV
Reagents
1. Sodium hydroxide (NaOH), 0.25 M: Dissolve 10 g of NaOH in 800 ml of
distilled water and dilute to 1 litre.
2. Standard NH
4
+
-N solutions: Prepare a series of standards in 2 M
potassium chloride (KCl) ranging from 0.1 to 10 μg of NH
4
+
-N/ml (using
NH
4
working solution, as described under 11.3.1). If an extract other than 2
M KCl is used, prepare the standards in this solution.
Procedure
1. Place a 20 ml aliquot of the soil extract in a 50 ml beaker containing a
Teflon-coated stirring bar.
2. Place the beaker on a magnetic stirrer, add 2 ml of 0.25 M NaOH and
insert the NH
3
electrode connected to a pH-millivolt meter.
72
3. Stir the solution for 1 min., record the electrode potential value and
calculate NH
4
+
-N in the sample by comparison of this value to a calibration
curve (as described under 11.3.1).
73
12. SOIL PHOSPHOROUS
In general, arid and semi-arid soils are low in available phosphorus and plants
respond to application of phosphatic fertilizers. Applied fertilizer phosphate
quickly reverts to insoluble forms. The amounts of the various discrete chemical
fractions of P, which are formed in soil determine the relative effectiveness of
phosphatic fertilizers on crop growth (Lindsay and De Ment, 1961), and are
related to the genesis of soils (Westin and Buntley (1966). The retention of
phosphorus in soils is the result of chemical precipitation and physico-chemical
sorption (Hemwall, 1957). Bashour and Al-Jaloud (2000) studied the fate of
applied phosphorus in arid calcareous soils of Saudi Arabia and found that 1/3 of
the applied P fertilizers was taken up by plants and about 1/3 was retained in the
soil as calcium phosphate. Most of the remaining 1/3 was converted into organic-
P and NaHCO
3
extractable-P. Sayegh and Abdul Majid (1969) studied
phosphorus fractionation and retention in soils of the semi-arid region, and the
results are briefly indicated below.
12.1. Fractionation of Soil Phosphorous
Phosphorus characterization indicated that the water-soluble and easily
replaceable P increased while Al-P, Fe-P, reductant soluble Fe-P, and occluded
Al-Fe-P decreased with an increase of CaCO
3
content. The Ca-P in the soils
increased with the increase of CaCO
3
content, amounting to 88 percent of the
total phosphorus in highly calcareous soils. In the alkaline low calcareous soils
Ca-P was the least, amounting to 5 percent, while Fe-P amounted to 19 percent
of the total phosphorus suggesting a comparatively high iron content which is
supported by the soil analysis and by the dark reddish brown colour. Thus, the
considerable differences in the proportions of the various P fractions were
associated with the degree of calcareousness.
12.2. Fate of Applied Phosphatic Fertilizer
The applied phosphorus was mainly converted to the forms of Ca-P, water
soluble P and easily replaceable P in the highly calcareous soils. In the slightly
calcareous soils, the distribution of the applied P was mainly in the forms of Ca-P
and Al-P followed by water soluble P. In contrast to the calcareous soils, in the
alkaline non-calcareous soils with iron and aluminium oxides, the applied P was
distributed in a variety of forms decreasing in the following order: residual-P > Fe-
P > Al-P > Ca-P> organic P.
74
12.3. Influence of Soil Parent Materials on the Distribution of
the Inorganic P-fractions
The highly calcareous soils had the highest percentage of Ca-P, and no Fe-P,
reductant soluble Fe-P, and occluded Al-Fe-P. In contrast, the soil developed
from the hard Eocene calcareous rock had a greater percentage of all the P
fractions except for the Ca-P. The soil derived from hard siliceous calcareous
beds contained intermediate amounts of P fractions.
12.4. Phosphorous Retention
Phosphorus retention of the soils increased with the increase of iron and
aluminium oxides. The retention of P was more rapid in the alkaline non-
calcareous soils, which contained larger amounts of iron and aluminium oxides
than in the low and high calcareous soils. The slower retention in the calcareous
soils might be due to the continued slow precipitation of calcium phosphates in
the course of time.
The removal of the amorphous materials from the clay fractions of the low
and high calcareous soils increased P retention from 2 to 70 percent upon the
addition of 250 μg/g of P, in the highly calcareous soils. The slight difference in
the cation exchange capacity between the clays without any amorphous material
or clays containing little quantity of amorphous material (partially clean and clean
clays) did not appear to provide an adequate explanation for the large difference
in phosphorus retention. It was, therefore, postulated that the retention capacity
of the Ca-saturated samples was due to a surface reaction, thus the removal of
amorphous materials resulted in increased effective surface area and more
retention reaction. On the other hand, removal of the amorphous materials from
the clay fractions of the non-calcareous soils, which are rich in iron and
aluminium oxides, resulted in less P retention. This was attributed to the
presence of comparatively high amounts of iron and aluminium in the amorphous
materials.
12.5. Iron and Aluminium Amorphous Phosphate in
Calcareous Soils
Most text books state that iron phosphates and aluminium phosphates and their
intergrades are found in acidic soils where conditions are favourable for the
presence of Al and Fe. While in neutral to alkaline soils, calcium phosphate is
present where conditions are favourable for the presence of calcium. But they fail
to mention the importance of iron and aluminium amorphous materials on
phosphorus retention, which coat the clays, silt and sand fractions in the neutral
and alkaline soils (Sayegh and Abdul Majid, 1969).
Tisdale and Nelson (1993) reported that in general the inorganic
phosphorus content in arid soils is higher than the organic phosphorous content.
75
Brady (1990) and Soltanpour et al. (1988) have reported that the Aridisols and
Andisols have 64% and 63% of inorganic phosphorus, respectively.
12.6. Determination of Available Phosphorous (Olsen’s
method)
Of the many extractants proposed for estimating available soil P, the NaHCO
3
solution (Watanabe and Olsen, 1965) is the most commonly used in calcareous
soils.
Apparatus
- Mechanical Shaker
- Spectrophotometer
- Funnels and filter papers
Reagents
1. Sodium bicarbonate (NaHCO
3
) solution, 0.5 M: Dissolve 42.0 g NaHCO
3
in 1 litre of distilled water. Before bringing it to volume, adjust pH to 8.5
with 1 M NaOH. This may need about 20 ml/l. Avoid exposure of the
solution to air. It can be stored up to 1 month if kept in glass bottle and
more than 1 month if stored in polyethylene containers. However, the pH
needs to be checked before use.
2. Ammonium molybdate solution: Dissolve 12 g of ammonium molybdate in
250 ml of distilled water, and 0.2908 g of antimony potassium tartrate in
100 ml distilled water. Add both solutions to 1 litre of 2.5 M H
2
SO
4
(140 ml
conc. H
2
SO
4
per litre), mix, make the volume to 2000 ml. Store in a Pyrex
bottle in the refrigerator.
3. Ammonium molybdate - ascorbic acid solution: Dissolve 1.056 g of
ascorbic acid in 200 ml of ammonium molybdate solution and mix.
Prepare only as much as needed, as this solution is not stable for more
than 24 hours.
4. Standard phosphate solution: Dissolve 0.4393 g of KH
2
PO
4
(dried at 40°C)
in distilled water and make the volume to 1 litre. This solution contains 100
μg of P/ml.
5. Working standard (dilute) phosphate solution: Dilute 50 ml of the standard
phosphate solution to one litre. This solution contains 5 μg of P/ml.
6. Sulphuric Acid (H
2
SO
4
), 2.5 M: Add 140 ml of conc. (18 M) H
2
SO
4
to 800
ml of distilled water. When cool, make the volume to 1 litre.
Procedure
1. Weigh 5.0 g soil sample in 250 ml Erlenmeyer flask.
2. Add 100 ml of NaHCO
3
extracting solution to it.
76
3. Shake on a mechanical shaker for 30 minutes. (sources of error: the
amount of P extracted increases with time and intensity of shaking, and
with temperature, 0.4 μg P/g per degree °C).
4. Filter the suspension through Whatman No. 40 filter paper into clean and
dry 125 ml Erlenmeyer flask. Shake the suspension by hand immediately
before pouring it into the funnel and discard the first 5 to 10 ml of filtrate if
turbid.
5. Transfer 10.0 ml of filtrate to a 50 ml volumetric flask; acidify to pH 5 by
adding 1.0 ml of 2.5 M H
2
SO
4
. Swirl carefully in the beginning, then
vigorously to remove residual carbonates.
6. Make volume to 40 ml with distilled water; add 8 ml of the ammonium
molybdate – ascorbic acid solution. Bring the volume to 50 ml, mix well,
and let stand for 10 minutes.
7. Read absorbance at 882 nm on the spectrophotometer. The colour is
stable for 24 hours and maximum intensity is obtained in 10 minutes.
8. Determine P concentration of the sample from a calibration curve relating
the readings of absorption units to concentration in μg P/ml.
9. Preparation of the standard curve: i) add 0, 2, 5, 10, 15 and 20 ml of 5 μg
P/ml standard stock solution to a series of labelled 50 ml volumetric flasks;
ii) add 10 ml of the NaHCO
3
extracting solution, 1 ml of 2.5 M H
2
SO
4
, and
develop colour as described above
Calculation
( )
soil g 5
ml 100
X
ml 10
ml 50
X ȝg/ml P soil ȝg/g P =
77
13. SOIL POTASSIUM
13.1. Determination of Available Potassium
The determination of plant available K is complicated as, in addition to K soluble
in water, it includes part of the exchangeable K. Another factor which complicates
the determination of plant available K in arid and semi-arid regions is that
extracting solutions used for exchangeable K may also extract part of the non-
exchangeable K from K-aluminium silicate clay minerals, like K-feldspars and
micas. Plants in the field do not benefit from this form of K. Moreover, moisture
content of the soil sample, and the manner of drying the sample also affects K
extractability.
In general, routine laboratory tests for determining plant available K do not
reflect the true situation under field conditions, because of the variation in the
clay mineralogy of the soils.
The following procedure is suggested for determining plant available K in
soils of the arid and semi-arid regions, and it may also apply to Ca and Mg.
Apparatus
- Centrifuge
- Round bottom centrifuge tubes - 50 ml
- Mechanical shaker
- Flame photometer
Reagents
1. Ammonium acetate (NH
4
OAc), 1.0 M solution: Add 57 ml of conc. acetic
acid to 700-800 ml distilled water in a 1-litre beaker. Then, with constant
stirring, add 68 ml of conc. ammonium hydroxide. Bring the volume close
to 1 litre, and adjust pH to 7.0 by the addition of more ammonium
hydroxide or acetic acid. Or, dissolve 77.09 g of ammonium acetate in
distilled water and dilute to 1 litre. Adjust pH to 7.0.
2. Potassium chloride (KCl) 0.02 M in 1.0 M ammonium acetate: Dissolve
1.491 g of potassium chloride in one litre of 1.0 M NH
4
OAc solution to be
used for preparing standard curve.
3. Lithium Chloride (LiCl), 0.05 M: Dissolve 2.12 g of lithium chloride in
distilled water and dilute to 1 litre.
Procedure
1. Weigh accurately 5 g of soil and transfer into a 50 ml centrifuge tube.
78
2. Add 20 ml of 1.0 M ammonium acetate solution to the tube; stopper and
shake in a reciprocal shaker for 5 minutes.
3. Centrifuge at 2000 rpm for 5 minutes or until the supernatant is clear.
4. Decant the supernatant into a 100 ml volumetric flask.
5. Repeat steps 2 – 4 three more times.
6. Make up the supernatant volume to 100 ml by adding ammonium acetate
solution.
7. Prepare a series of working K standard solutions in the range of 0 – 2
meq/l of K from stock solution of 0.02 M KCl already prepared. For better
results, add LiCl in each standard to yield a final concentration of about 5
meq/l of LiCl.
8. Determine K concentration in the extract by flame photometer as in
section 6.3.2 and 8.1.
Calculation
(g) soil of Wt.
10 X R
(g) soil of Wt.
g 100
X
ml 1000
ml 100
X (meq/l) Reading soil g K/100 of meq
=
=
13.2. Determination of Fixed Potassium
Apparatus
- Flame photometer or atomic absorption spectrophotometer.
Reagents
1. Nitric acid (HNO
3
), 1.0 M: Dilute approximately 62 ml of conc. HNO
3
to a
volume of 1 litre.
2. Nitric acid (HNO
3
), 0.1 M: Dilute 6.2 ml of conc. HNO
3
to a volume of 1
litre.
3. Potassium standard solutions in the working linear range of the
instrument, like 0.5 – 10 μg K/ml.
4. Lithium Chloride (LiCl), 0.05 M: Dissolve 2.12 g of lithium chloride in
distilled water and dilute to 1 litre.
Procedure
1. Weigh accurately 2.5 g of finely ground soil (70 mesh) and transfer into a
200 ml beaker. Add 40 ml of 1.0 M nitric acid to the beaker and place it in
79
an oil bath at 113°C for about 25 minutes. Remove the beaker and wipe
oil from outside.
2. Filter the contents into a 100 ml volumetric flask and wash the soil four
times with 10 ml portions of 0.1 M nitric acid, each time filtering into a 100
ml flask. Cool the solution, dilute to volume and mix thoroughly.
3. Prepare K standard solutions in the recommended range of the
instrument, like 0, 0.5, 1, 2, 3, 5, 7 and 10 μg K/ml. Add the same volumes
of nitric acid solutions that were added in the samples. To suppress
ionization and interference, add LiCl solution to yield a final concentration
of about 5 meq/l (in case AAS is used, LaCl
3
(Lanthanum Chloride) is
added as the suppressing agent).
4. Refer to section 6.3.2 for the flame-photometry determination of K.
Calculation
soil g 2.5
ml 100
X solution in g/ml) ( K soil) g/g ( K Fixed µ µ =
Note: This is in case no dilution was made on the sample prior to K
measurement.
80
14. SOIL SULPHUR
Sulphur (S) is present in soils in organic and inorganic forms. Organic S is an
important constituent of proteins and amino acids. The major inorganic sources
of S include gypsum (CaSO
4
), and pyrite (Fe
2
S). Sulphur is also added to soil as
a result of the use of fertilizers containing S, such as K
2
SO
4
, and some
pesticides. It exists in soil and soil solution mainly as the SO
4
2-
anion in
combination with the cations, Ca
2+
, Mg
2+
, K
+
, Na
+
or NH
4
+
. When present in the
form of elemental sulphur (S), it will be oxidized under aerobic condition to form
SO
4
2-
. Under anaerobic condition, SO
4
2-
will be reduced by microorganisms into
SO
3
2-
and S
2-
. Hydrogen sulphide (H
2
S) is formed especially in swamps and
other areas with stagnant water. Waterlogged and paddy soils provide a suitable
environment for the formation of H
2
S. In soils rich in iron, H
2
S usually precipitates
as FeS, which imparts to soils a black colour. When H
2
S is allowed to
accumulate, it is not only toxic to soil organisms, but also it creates
environmental problems. A group of bacteria present in soils is capable of
oxidizing the H
2
S into elemental S and SO
4
2-
.
Away from arid and semi-arid regions, probably in some acid soils, further
formation of sulphuric acid (H
2
SO
4)
will lower soil pH to about 2, resulting in the
formation of acid sulphate soils, sometimes called cat-clays. In addition to the
toxicity created by the extremely low pH, the acidity will liberate very high levels
of Al and Fe, which may reach toxic levels to plant growth.
The total S content in soils varies widely from soil to soil. Sandy soils in
the humid regions are generally low in S (0.002%). In contrast, soils in arid
regions may contain 5% SO
4
2-
-S. Plants absorb S mostly in the sulphate SO
4
2-
form, which is the available form of S. Sulphate is extractable by water, NaCl,
CaCl
2
, NH
4
OAC, NaHCO
3
and Ca(H
2
PO
4
)
2
solutions.
Concentration of SO
4
2-
is determined as follows:
Apparatus
- Spectrophotometer
- Mechanical shaker
- Volumetric flask
Reagents
1. Mono-Calcium Phosphate (Ca(H
2
PO
4
)
2
.H
2
O) solution: Weigh 2.03 g of
Ca(H
2
PO
4
)
2
.H
2
O and dissolve it in 800 ml distilled water with constant
stirring. Transfer to a 1-litre volumetric flask and make up to volume with
distilled water. This solution contains 100 mg P/l.
2. Acetic acid (CH
3
COOH), 50%: Add 50 ml acetic acid to 50 ml distilled
water.
81
3. Concentrated. Ortho-Phosphoric acid (H
3
PO
4
).
4. Barium chloride crystals, BaCl
2
: The crystals are ground to pass a 0.5 mm
sieve, and retained on a 0.25 mm sieve.
5. Gum acacia solution, 0.25% (w/v) in water.
6. Standard sulphate solution: Dissolve 147.9 mg anhydrous Na
2
SO
4
in
distilled water and dilute to 1 litre. This solution contains 100 μg SO
4
/ml.
Procedure
1. Weigh 5 g of soil into a 100 ml polyethylene centrifuge tube, add 50 ml
Ca(H
2
PO
4
)
2
solution, and shake the mixture for 30 minutes on a
mechanical shaker. Filter into 50 ml volumetric flask.
2. Pipette 5 ml of the extract into a 50 ml volumetric flask, add 5 ml of acetic
acid, 1 ml of H
3
PO
4
and 1 g of BaCl
2
crystals. The phosphoric acid will
decolourise any Fe present in solution. Mix gently by inverting the flask
several times. Add 2 ml of gum acacia solution and make up to volume
with distilled water.
3. Mix gently again and at 5 +/- 0.5 minutes, measure BaSO
4
turbidity with a
spectrophotometer at 420 nm.
4. Estimate SO
4
2-
concentration in sample by comparing turbidity with a
calibration curve prepared by carrying sulphate standards through the
entire procedure.
Calculation
(g) soil of Wt.
10
X sample in /ml SO ȝg
ȝg/mg 1000
mg 1
X
(g) soil of Wt.
g 100
X
ml 5
ml 50
X
ml 5
ml 50
X ml 50 X sample in /ml SO ȝg
soil g /100 SO mg
4
4
4
=
=
82
15. GYPSUM REQUIREMENT
Although gypsum is sparingly soluble in water, it is one of the most suitable
chemicals used in reclaiming sodic and saline-sodic soils. Its solubility never
exceeds 2.4 mg/litre. However, the problem is not mainly concerned with the
degree of solubility of calcium sulphate, but to a great extent on the difficulty in
replacing sodium by calcium in the colloidal complex. This difficulty is the main
problem in the use of gypsum in reclaiming sodic soils, especially in calculating
the actual amount of gypsum which should be added to such soils in order to
react with Na
2
CO
3
and sodium clay so as to bring its pH to about 8, i.e. to reclaim
them. This difficulty increases when these soils are rich in soluble salts, i.e.
saline-sodic soils.
The common procedure in such cases is to determine the soil content of
Na
2
CO
3
, and then calculate the equivalent amount of calcium sulphate needed to
affect the transfer of Na
2
CO
3
to Na
2
SO
4
. This calculation is essentially theoretical
and the amount of gypsum thus calculated varies greatly from the actual amount
needed to reclaim such soils under field conditions. This is mainly due to the fact
that the following factors are usually not taken into consideration:
1. The soluble sodium salts which accumulate in the soil during the
process of salinization, eventually leading to alkalinization of such
soils.
2. The percentage of exchangeable sodium in the colloidal complex of
the soil.
3. The amount of colloidal material in the soil.
4. The calcium carbonate content of the soil.
Therefore, in general, it is recommended to multiply the theoretical
quantity of gypsum by three or four to obtain the practical amount of gypsum
actually required. A practical method was developed by Schoonover, 1953 to
determine gypsum requirement, which is given below.
Apparatus
- Erlenmeyer flasks
- Pipettes
- Filter papers
Reagents
1. Ammonium chloride – ammonium hydroxide buffer solution: Dissolve 6.75
g of ammonium chloride in 57 ml of concentrated ammonium hydroxide
and dilute to 100 ml.
2. Saturated gypsum solution: Add about 40 g gypsum (CaSO
4
2H
2
O) to 10
litres of water. Allow to stand with occasional shaking for 8 hours or
83
longer. Let settle until clear or filter. Determine calcium concentration
(meq/l) using EDTA trisodium salt (C
10
H
13
N
2
Na
3
O
8
, commonly known as
trisodium versenate) titration method.
3. Trisodium versenate solution (EDTA), 0.03 N: Dissolve 6.0 g of analytical
reagent disodium dihydrogen ethylenediaminetetraacetic acid in 1 litre of
distilled H
2
O. Standardize this solution against standard CaCl
2
solution.
4. Eriochrome black T indicator: Dissolve 0.5 g Eriochrome black T and 4.5 g
hydroxylamine hydrochloride in 100 ml of 95 percent ethanol.
Procedure
1. Weigh 5 g of soil into a 200 ml Erlenmeyer flask.
2. Add 100 ml saturated gypsum solution, stopper flask, and shake at
intervals for 10 minutes.
3. Filter and pipette 10 ml of the filtrate to 200 ml Erlenmeyer flask.
4. Add 50 ml distilled water, 0.5 ml of ammonium chloride-ammonium
hydroxide buffer solution, and 4 to 5 drops of Eriochrome black T
indicator.
5. Determine calcium plus magnesium in solution by titration with 0.03 N
trisodium versenate solution (at the end point, the solution will have a
distinct blue colour with no trace of pink or violet). Record the ml of titrant
used (V).
6. Titrate 10.0 ml of saturated gypsum solution. Record the ml of titrant used
(B).
Calculation
Gypsum meq/100g = (Ca meq/l in gypsum solution) – (Ca + Mg meq/l in
filtrate) X 2
(B - V) × 0.03 N × 382 = tonnes gypsum/ha (15 cm soil depth)
(B - V) × 0.03 N × 764 = tonnes gypsum/ha (30 cm soil depth)
Note: Iron, aluminium, and manganese when present in concentrations greater
than 20 mg/kg, and copper in concentrations greater than several tenths of
mg/kg, interfere with the performance of the Eriochrome black T indicator.
Usually the concentrations of these metals in water and ammonium acetate
extracts of soils of arid regions are insufficient to cause interference. If
interference is encountered, then Ca and Mg should be determined by atomic
absorption spectrophotometer.
84
16. SOIL MICRONUTRIENTS
16.1. Iron, Zinc, Manganese and Copper
16.1.1. Iron
Iron (Fe) is the third most abundant element in earth crust. The most important
iron minerals in soil are hematite (Fe
2
O
3
) and magnetite (Fe
3
O
4
). The hydrated
form of hematite is often called limonite (2Fe
2
O
3
.3H
2
O). Hematite is red in colour
and its presence gives the soils a red colour. Magnetite is black in colour and
crystalline in nature. It has strong magnetic properties. Another iron mineral is
pyrite (FeS
2
), which occurs in soils as yellow crystals with a metallic luster similar
to gold, hence the name fool's gold. Ilmenite (FeTiO
3
) is another important iron
mineral, and is a valuable source for the production of many industrial products.
In addition, Iron occurs in soils in an amorphous form coating soil particles and,
also, as organic complexes. The granular soil structure in Oxisols is believed to
be stabilized by iron coatings around the structural units.
In soil solution iron exists in two oxidation states, ferrous Fe
2+
and ferric Fe
3+
.
Under anaerobic conditions, Fe
2+
is the dominant species, whereas under
aerobic conditions Fe
3+
is the dominant species. The concentration of Fe
2+
and/or
Fe
3+
in soil solution is very low, due to the highly insoluble nature of Fe
2
O
3
minerals. The concentration of soluble Fe in river water and ground water is
estimated to range from 0.1 to 10 mg/l (Krauskoph, 1973; Tan, 1994).
Iron is an essential micronutrient for plant growth. It is needed for chlorophyll
formation. In animals, iron is present in the blood hemoglobin, which acts as a
carrier of oxygen. The normal iron concentration in plant tissue varies
considerably with plant species from 100 μg/g dry matter of grasses to 1000 μg/g
in alfalfa dry matter. Iron concentration of <20 μg/g in plant tissue is considered
deficient, and may result in development of chlorosis, frequently manifested as
yellow stripes on young leaves. Iron deficiency in soils can be induced by over-
liming, and the presence of high amounts of phosphates. Iron deficiency often
occurs on plants growing in alkaline calcareous soils. Therefore, iron deficiency
is most likely a problem in the calcareous soils of arid and semiarid regions.
16.1.2. Zinc
Zinc (Zn) is present in small quantities in igneous and sedimentary rocks.
Concentration of Zn is usually higher in basic igneous rocks, such as basalt, than
in acid igneous rocks, such as granite. The major inorganic sources of Zn are
sphalerite, ZnS, smithsonite, ZnCO
3
, and hemimorphite [Zn
4
(Si
2
O
7
)(OH)
2
.H
2
O].
Hydrozincite [Zn
5
(CO
3
)
2
(OH)
6
] is another Zn mineral frequently mentioned, but
85
this mineral is considered similar to smithsonite (Hurlbut and Klein, 1977). All the
minerals stated above are very rare in soils, and occur only in large amounts as
Zn ore deposits.
The concentration of total Zn in soils is approximately in the range of 10
μg to 300 μg/g. The average Zn content in normal agricultural soils is 50 μg/g
(Brady, 1990). In soil solution, Zn is present as the divalent Zn
2+
ion. Most Zn
compounds are sparingly soluble in water. Because of its cationic nature, the Zn
ion is adsorbed by the negatively charged surfaces of soil colloids, and is then
called exchangeable Zn. The concentration of Zn ions is dependent upon pH, as
is the case with all the other microelements. At low pH, Zn
2+
concentration is very
high in soils, whereas at high pH, Zn
2+
concentration is low. At pH 9.5, Zn
2+
exhibits minimum solubility and precipitates as Zn(OH)
2
. Therefore, high soluble
Zn contents occur in acid soils, whereas low soluble Zn contents are found more
in basic soils, especially in Aridisols. For example, the concentration of Zn
2+
ions
in neutral and alkaline calcareous soils is in the range of 1 × 10
-8
to 1 × 10
-10
M
(Norvell, 1973). Consequently, Zn deficiency is found in alkaline calcareous soils.
Zinc is a micronutrient to plants, and is needed only in very small
amounts. The element functions as a catalyst. It is present in several plant
enzymes, e.g. dehydrogenase, proteinase, and peptidase. Zinc is also essential
for seed and grain production, and development of growth hormones.
The normal concentration of Zn in most plants ranges on the average from
15 to 125 μg/g. Zn concentration of < 15 μg/g of leaf dry matter cause Zn
deficiency, which is manifested as stunted growth. On maize plants, Zn
deficiency produces white to yellow leaves with bleached stripes, a symptom
known as white bud of maize. On the other hand, Zn concentration of > 400 μg/g
of leaf dry matter is considered excessive and may induce Zn toxicity. Zinc
deficiency is common in the calcareous soils of arid and semiarid regions.
16.1.3. Manganese
Manganese (Mn) is present in small quantities in many rocks. It is released into
the soil by rock weathering and is re-deposited in various forms of Mn oxides.
The total Mn content in soils varies considerably from 20 μg/g to 6000
μg/g (Krauskoph, 1973). The element can exist in three oxidation states: Mn
2+
,
Mn
3+
, and Mn
4+
. The divalent manganese ion is the main form of Mn in soil
solution, especially in reduced soil environment. Because of its cationic nature,
Mn
2+
is usually adsorbed on the negatively charged surfaces of soil colloids. It is
then called exchangeable manganese. The trivalent form usually exists as
Mn
2
O
3
, which can be found in substantial amounts in acid soils. The trivalent ion
itself is unstable in soil solution. The tetravalent form (MnO
2
), is perhaps the most
stable and inert form of manganese.
The concentration of Mn
2+
in soil solution is very low, seldom exceeding
0.05 mg/l. Its concentration increases at low pH values, and decreases at high
pH values. Therefore, high amounts of manganese may be present in highly
86
weathered acid soils, such as Ultisols and Oxisols. On the other hand, low
amounts of manganese usually occur in Aridisols.
Manganese is an essential micronutrient and is needed by plants to
activate a number of enzymes. It also plays an essential role in photochemistry
and in N-metabolism and assimilation. Manganese is required for plant growth
only in very small amounts. The normal Mn content in plant tissue is 20 - 500
μg/g dry matter. A Mn concentration of < 20 μg/g dry matter is considered
deficient and is usually manifested by development of necrotic spots, known as
marsh spots in pea leaves, and grey specks in oat leaves. Soybean and oats are
especially sensitive to Mn deficiency. Manganese deficiency is likely to occur in
calcareous soils of arid and semiarid regions.
16.1.4. Copper
Copper (Cu), is classified as a native element, meaning that it can occur as a
native element in the earth crust in contrast to such elements as Al, which exist
only in the form of a compound. The most common form of Cu in soils is in the
form of minerals, e.g. in the forms of sulphides, sulphates, oxides, carbonates,
and silicates. The most common Cu mineral in soils is perhaps chalcopyrite
(CuFeS
2
).
The total Cu content in soils is in the range of 10 μg/g to 80 μg/g
(Krauskoph, 1973). In the soil solution, copper exists as Cu
+
(cuprous), or Cu
2+
(cupric) ions. At concentrations > 10
-7
mol/l Cu
+
ions are unstable at ordinary
temperature. However, it can exist at these conditions as a CuCl
2
-
chelate
(Krauskoph, 1973). Cuprous ions are so unstable in aqueous solution that they
will be automatically affected by the soil redox process, called auto-reduction-
oxidation reaction, and converted into Cu and Cu
2+
. Therefore, cupric ions are
more stable and are the major copper ions in the soil solution. However, Lindsay
(1973) noted that Cu
2+
is the dominant ion in soils at pH values < 7.3, whereas
above this pH, Cu(OH)
+
is the major copper ion. The concentration of soluble Cu
ions in soils is on the average 20 mg/l. Because of its cationic nature, Cu
2+
will be
adsorbed by negatively charged surfaces of soil colloids, and are then called
exchangeable Cu. The concentration of free and exchangeable Cu ions is high in
acid soils, and low in basic soils. The Cu
2+
concentrations in many neutral and
calcareous soils are reported to amount only 1 × 10
-12
M (Norvell, 1973).
Therefore, Cu deficiency is more likely to occur in basic soils, e.g. Aridisols,
whereas Cu toxicity may be displayed more by highly weathered acid soils, e.g.
Ultisols and Oxisols.
Copper is a micronutrient, and is needed only in small amounts by plants. The
element is required for chlorophyll formation, hence Cu affects photosynthesis. It
is essential in enzyme reactions, and in the reproductive stages. Cu is noted to
be needed in protein and carbohydrate metabolism, and in nitrogen fixation. The
normal concentration in plant tissue is approximately 4 - 30 μg Cu/g. Present at
concentration < 3 μg/g dry matter, Cu deficiency will occur, which is manifested
by yellowing and curling of leaves, stunted growth and development of short
87
internodes. On the other hand, Cu concentration in leaf tissue of >20 μg/g may
result in Cu toxicity, which is manifested by yellowing of leaves, and poorly
developed roots with frequently discoloration.
16.2. Determination of Available Micronutrients
Available Fe, Zn, Cu and Mn in soils are extracted with several chelating agents,
including EDTA, EDDHA and DTPA. Lindsay and Norvell (1978) developed the
DTPA (diethylenetriaminepentaacetic acid) method and reported good
correlations between DTPA-extractable micronutrients and plant growth. These
elements can also be determined in the soil solution extracted by centrifugation
of a moist soil sample collected directly from the field.
16.2.1. DTPA Extraction Method
Reagents
1. Diethylenetriaminepentaacetic acid (DTPA) solution: Weigh 19.67 g DTPA
and with constant stirring, dissolve in 1 litre of distilled water. Weigh
separately 149.2 g TEA (triethanol amine) and 14.7 g CaCl
2
.2H
2
O, and
dissolve in 1 litre of distilled water. Pour under constant stirring the DTPA
solution to the TEA-CaCl
2
.2H
2
O mixture. After the DTPA has dissolved
completely, dilute the solution to 9 litres. Adjust the pH to 7.3 with 1:1 HCl
(approximately 42 ml required), and make up the volume to 10 litres with
distilled water.
2. Standard solutions of Fe, Zn, Cu and Mn: Stock standard solutions
containing 1000 mg/l of the metals.
Procedure
1. Weigh 5 g of air-dried soil (<2 mm) in a 100 ml polyethylene centrifuge
tube, add 20 ml DTPA solution, and shake for 30 minutes on a mechanical
shaker.
2. Centrifuge, and decant into a sample bottle fitted with funnel and filter
paper.
3. If needed, dilute the extract so that the reading is in the linear working
range of the atomic absorption spectrophotometer.
16.2.2. Measurement of Element Concentration Using Atomic
Absorption Spectroscopy
Atomic absorption spectrophotometry has become a common practice in almost
all laboratories, especially for the measurement of trace elements (Te)
concentration in solution. Each instrument, AA spectrophotometer, has its
88
instruction manual that guide the user to the adjustment and operation of the
instrument, but it is essential to have a general knowledge of the basic principles
of the technology.
Atomic absorption spectroscopy (AAS) uses absorption of light to measure
the concentration of analyte atoms in a flame or graphite furnace. The light
source is usually a hollow-cathode lamp of the element that is being measured.
Lamps convert electrical energy into radiation. Atoms absorb the radiation and
make transitions to higher energy levels. Light absorption is proportional to the
amount of analyte atoms in the path of light. Concentration measurements are
determined from a working curve after calibrating the instrument with standards
of known concentration.
Atomic absorption spectroscopy requires that the analyte atoms be in the
gas phase. Ions or atoms in a sample must undergo vaporization or atomization
in a high-temperature source such as a flame or graphite furnace.
Flame AAS uses a slot type burner to increase the path length, and
therefore to increase the total absorbance. Sample solutions are usually
aspirated with the gas flow into a nebulizing/mixing chamber to form small
droplets before entering the flame.
The furnace AAS is a much more efficient atomizer than the flame and
can directly accept very small quantities of sample. Samples are placed directly
in the graphite tube and the furnace is electrically heated in several steps to dry
the sample, ash organic matter, and vaporize the analyte atoms. While flame
AAS measures concentration of analyte in μg/ml, furnace AAS detects
concentrations in μg/l.
A calibration curve is a plot of the analytical signal (the instrument or
detector response) as a function of analyte concentration. These calibration
curves are obtained by measuring the signal from a series of standards of known
concentration. The calibration curves are then used to determine the
concentration of an unknown sample, or to calibrate the linearity of an analytical
instrument.
Procedure
1. Prepare an intermediate standard solution by pipetting 10 ml from the
1000 μg/ml Stock solution of the analyte Te into a 200 ml volumetric flask,
and dilute to the volume with DTPA solution.
2. Prepare standard solutions in the working range, like 0, 1, 2, 5, 10 μg/ml of
the trace metal. Always dilute with the DTPA solution.
3. Now follow the step by step procedure given in the instruction manual to
optimize the working condition of the instrument.
4. Measure the signals from the series of working standards of known
concentration, and plot the analytical signals (the instrument or detector
response) as a function of analyte concentration.
89
Calculation
soil g 5
ml 20
X Te/ml ȝg soil Te/g ȝg
sample
=
16.3. DTPA Extractability and Availability for Plant Uptake
Lindsay and Norvell (1978) suggested some critical levels for DTPA extractable
micronutrients as a guide to deficiency and availability of these trace elements for
plant uptake and growth:
Micronutrients (μg/g soil)
Availability Zn Mn Fe Cu
Very Low 0 – 0.5 0 – 0.5 0 – 2.0 0 – 0.1
Low 0.6 – 1.0 0.5 – 1.2 2.0 – 4.0 0.1 – 0.3
Medium 1.0 – 3.0 1.2 – 3.5 4.0 – 6.0 0.3 – 0.8
High 3.0 – 6.0 3.5 – 6.0 6.0 – 10.0 0.8 – 3.0
Very High >6.0 >6.0 >10 0 >3.0
90
17. SOIL BORON
Boron (B) is a non-metal, in contrast to the other micronutrient elements. It is
present in small amounts in igneous, sedimentary and metamorphic rocks. In
areas with geothermal activity, gases flowing from inner earth contain B. When
dissolved in hot springs the element becomes boric acid (H
3
BO
3
). However, the
major inorganic sources of B are borate and boron-silicate minerals. Borate
minerals occur mostly in arid regions. They are formed by the evaporation of
water in enclosed salt-water lakes and basins in arid regions. The BO
3
2-
units
polymerize and form a variety of borate crystals. Borax is the most common
among borate minerals.
Total B content in soils is between 7 and 80 μg/mg soil. It is released by
weathering of the minerals in the form of H
3
BO
3
and its concentration is usually
<1×10
-4
M, which equals 0.1 mg/l (Krauskoph, 1973), a very small amount.
Concentration of 1–2 mg B/kg soil is perhaps more representative for surface
soils. In soil solution, B can exist both as H
3
BO
3
and H
2
BO
3
-
. High concentrations
of B are found only in seawater, where an average concentration of 4.6 μg/ml
has been reported (Krauskoph, 1973). Because of its anionic character, BO
3
2-
will
not be attracted by the negatively charged soil colloids. In humid regions borate
ions may tend to leach from soils. Therefore, soluble B concentrations are low in
highly leached soils. Since highly leached soils usually exhibit low soil pH, acid
soils are deficient in B. On the other hand, soluble B concentrations are expected
to be high in soils not affected by leaching. Since arid region soils are usually not
affected by leaching, and are, therefore, strongly basic in reaction, they may
contain excessive amounts of B for plant growth. Therefore, B deficiency is more
likely to occur in Ultisols and Oxisols, whereas B toxicity could be noted in
Aridisols. This is in contrast with the other micronutrients.
Boron is an essential micronutrient element for plant growth. It is needed
for cell division, hence for the growth of young shoots. It is essential in sugar
translocation and in the synthesis of hormones and protein in plants. The normal
B concentration in plant tissue is reported to be between 20 and 100 μg/mg dry
matter of mature leaves. A boron content of <15 μg/mg indicates B deficiency,
whereas a B concentration >200 μg/mg indicates B toxicity. Boron deficiency is
usually manifested in formation of white and rolled leaves. In sugar beets, it
results in rotting of the shoots, a nutritional disease called heart rot.
Boron in soils is primarily of importance in soil fertility and plant nutrition
but is not used as a significant parameter in soil characterization, soil genesis
and classification.
Methods for determination of total B and available B are described here.
17.1. Total Boron by Na
2
CO
3
Fusion
Apparatus
91
- Platinum crucible
- Bunsen burner
- Beakers, flasks and funnels
- Filter papers
Reagents
1. Sodium Carbonate (Na
2
CO
3
) anhydrous, solid crystal powder.
2. Sodium Carbonate (Na
2
CO
3
), 30% solution: Weigh 30 g of Na
2
CO
3
in a
100 ml volumetric flask, add 80 ml of distilled water, and dilute to volume.
Store in a polyethylene vial.
3. Sulphuric Acid (H
2
SO
4
), 2 M: Add 12 ml of conc. H
2
SO
4
to 800 ml distilled
water into a 1 litre volumetric flask, allow the solution to cool and dilute to
volume with distilled water.
4. Hydrochloric Acid (HCl), 0.1 M: Add 8.1 ml conc. HCl to 500 ml distilled
water in a 1 litre volumetric flask, allow the solution to cool and dilute to
volume with distilled water.
5. Ethyl alcohol, 95%.
6. Sodium Hydroxide (NaOH), 0.02 M: Dissolve 800 mg NaOH in a 500 ml
distilled water in a one litre volumetric flask, cool, and dilute to volume.
7. Phenolphthalein solution: Weigh 50.0 mg phenolphthalein in a 100 ml
volumetric flask, add 50 ml ethyl alcohol and dilute to the volume with
distilled water. Shake the flask until the phenolphthalein crystals have
dissolved completely.
8. Standard B solution: Pipette 35 ml of a stock solution containing 1000 μg
B/ml into a 100 ml volumetric flask, and dilute to volume with ethyl alcohol.
This solution, called standard solution, contains 350 μg B/ml.
Procedure
1. Weigh 1.0 g of 100 mesh (2 mm) soil in a platinum crucible.
2. Add 6 g of Na
2
CO
3
powder, mix and heat on a Bunsen burner until the
sample is completely fused with the Na
2
CO
3
.
3. Cool to room temperature, add 10 ml of H
2
SO
4
to disintegrate and
dissolve the melt.
4. Place the crucible on its side in a 250 ml Pyrex beaker, and add 4 ml
increments of 2 M H
2
SO
4
until the solution pH is 6.0-6.5.
5. Filter the solution into a 500 ml volumetric flask fitted with funnel and filter
paper, and wash the contents of the beaker and the crucible with distilled
water into the flask, collecting about 150 ml.
92
6. Dilute with ethyl alcohol to a volume of 400 ml, add a few drops of
phenolphthalein and Na
2
CO
3
solution (30%) to attain a slightly alkaline
reaction, then bring to volume (500 ml) with ethyl alcohol.
7. Prepare a blank by following the same fusion procedure but without soil.
For the measurement of B concentration in the digestion solution, refer to section
17.3.
17.2. Available Boron by Hot Water Extraction
This is the most commonly used method for available B in soil. Extracted B can
then be determined by colorimetric methods using reagents such as carmine or
azomethine-H. Recently, atomic emission spectrometry or inductive coupled
plasma (ICP) is used for boron measurement in laboratories where such
equipment is available.
Apparatus
- Boron-free, alkali-resistant glassware or stainless steel
- Water bath
- Rubber policeman
Reagents
1. Calcium hydroxide (Ca(OH)
2
) suspension: Weigh 400.0 mg Ca(OH)
2
into a
100 ml volumetric flask, and dilute to volume with distilled water.
2. Hydrochloric Acid (HCl), 0.1 M: Measure 8.1 ml of conc. HCl (12.4 M) into
a 1 litre volumetric flask, add 800 ml of distilled water and allow the
solution to cool to room temperature. Dilute to volume with distilled water.
3. Calcium Chloride (CaCl
2
), 0.01 M: Weigh 1.11 g anhydrous CaCl
2
into a 1
litre volumetric flask, add 900 ml distilled water to dissolve under constant
stirring, and dilute to volume with distilled water.
Procedure
1.
Weigh 20 g of air-dry soil into a 250 ml Erlenmeyer flask, and add 40 ml of
hot deionised water (in calcareous soils, dilute 0.01 M CaCl
2
is used
instead of hot deionised water).
2.
Place a refluxing funnel on the Erlenmeyer flask, and heat the mixture to
the boiling point, and reflux the suspension for 5 min.
3.
Cool and filter the suspension into a 50 ml volumetric flask, and dilute to
volume with distilled water.
93
4.
Pipette 25 ml of the filtrate into an evaporating dish, add 2 ml of the
Ca(OH)
2
suspension and evaporate to dryness on a water bath.
5.
Heat the evaporating dish gently over a flame to destroy organic matter.
6.
Cool to room temperature, add 5 ml of HCl (0.1 M) and dissolve the digest
by rubbing with a rubber policeman.
7.
Filter the digest into a 10 ml volumetric flask, and dilute to volume with
distilled water.
17.3. Measurement of Concentration by Colorimetric Methods
For the measurement of B concentration in the digestion solution for total boron,
or in the hot water extract for available B, colorimetric methods are followed. The
following are two procedures, each one of them uses a different compound for
colour development.
17.3.1. Colour Development – Carmine Method
In the presence of B, a solution of carmine in concentrated sulphuric acid
changes colour from a bright red to a blue, depending on concentration of B in
solution.
Apparatus
- Spectrophotometer
- Boron-free, alkali-resistant glassware (flasks, beakers, Pipettes, burettes,
etc.
Reagents
1. Hydrochloric acid (HCl) concentrated.
2. Sulphuric acid (H
2
SO
4
) concentrated.
3. Carmine solution: Dissolve 920 mg carmine in 1 litre concentrated
sulphuric acid. Shake until completely dissolved.
4. Standard boric acid stock solution: Dissolve 0.5716 g of recrystallized
H
3
BO
3
in distilled water and dilute to 1 litre. One ml of this solution
contains 0.1 mg (100 μg) of boron.
Procedure
1. Prepare a series of B standard solutions (1.0, 2.5, 5.0, 7.5, and 10 μg
B/ml) with distilled water using standard boric acid stock solution.
2. Pipette 2 ml of the sample (digestion solution or water extract), which
should contain not more than 0.02 mg B, into a 25 ml volumetric flask.
94
3. Treat the blank and the calibration standards exactly as the sample.
4. Add 2 drops (0.1ml) conc. HCl, carefully introduce 10.0 ml conc. H
2
SO
4
,
mix, and allow to cool to room temperature.
5. Add 10.0 ml of Carmine reagent, make to volume (25 ml) with deionised
water, mix well, and allow to stand for 45 to 60 minutes for colour
development, which is bluish or blue depending on the concentration of B
in the sample.
6. Prepare a standard curve using the blank as a reference and observe
absorbance at 585 nm in a cell of 1 cm or longer light path against each
standard sample containing known amount of B (expressed as μg B/ml).
Determine the B content (as μg B/ml) in the unknown sample from the
standard curve.
Note: Bubbles may form as a result of incomplete mixing. Make sure that
there are no bubbles in the optical cell when absorbance readings are being
made. Check the calibration daily because the carmine reagent deteriorates.
Calculation
100 x ȝg X
X
= =
20
100 x 2 x 10 x
soil g /100 in content B
Where,
X = Reading in μg/ml from the standard curve
Note:
Weight of the soil taken = 20 g
Vol. of the extract = 50 ml
Vol. taken for estimation = 25 ml (this was reduced to 10 ml)
B content in the reduced sample (μg/ml) = X
B content in the 10 ml reduced sample (μg) = X x 10 (quantity present in the
original 25 ml extract)
B content in 50 ml original extract (quantity in μg present in 20 g soil) = X x 10 x 2
B content in 100 g soil (μg) = X x 10 x 2 x 100/20
17.3.2. Colour Development – Azomethine-H Method
Apparatus
- Analytical balance
- Flask or beaker
- Volumetric flask
- Funnels
95
- Whatman No.42 filter paper
- Spectrophotometer
Reagents
- Azomethine-H: Dissolve 0.45 g azomethine-H and 1.0 g L-ascorbic acid in
about 100 ml deionised or double-distilled water. If solution is not clear, it
should be heated gently in a water bath or under a hot water tap at about
30
0
C till it dissolves. Every week a fresh solution should be prepared and
kept in a refrigerator.
- Buffer solution: Dissolve 250 g ammonium acetate in 500 ml deionised or
double-distilled water and adjust the pH to about 5.5 by slowly adding
approximately 100 ml glacial acetic acid, with constant stirring.
- EDTA solution (0.025 M): Dissolve 9.3 g EDTA in deionised or double-
distilled water and make the volume up to 1 litre.
- Standard stock solution: Dissolve 0.8819g Na
2
B
4
O
7
10H
2
O AR grade in a
small volume of deionised water and make volume to 1 000 ml to obtain a
stock solution of 100 µg B/ml.
- Working standard solution: Take 5 ml of stock solution in a 100 ml
volumetric flask and dilute it to the mark. This solution contains 5 µg B/ml.
Procedure
1. Take 5 ml of the clear filtered extract in a 25 ml volumetric flask and add 2
ml buffer solution, 2 ml EDTA solution and 2 ml azomethine-H solution.
2. Mix the contents thoroughly after the addition of each reagent.
3. Let the solution stand for 1 hour to allow colour development. Then, the
volume is made to the mark.
4. Intensity of colour is measured at 420 nm.
5. The colour thus developed has been found to be stable up to 3-4 hours.
6. Preparation of standard curve: Take 0, 0.25, 0.50, 1.0, 2.0 and 4.0 ml of 5
µg B/ml solution (working standard) to a series of 25 ml volumetric flasks.
Add 2 ml each of buffer reagent, EDTA solution and azomethine-H
solution. Mix the contents after each addition and allow to stand at room
temperature for 30 minutes. Make the volume to 25 ml with deionised or
double-distilled water and measure absorbance at 420 nm. This will give
reading for standard solution having B concentration 0, 0.05, 0.10, 0.20,
0.40 and 0.80 µg B/ml.
96
Calculations
Weight of the soil taken = 25 g
Volume of extractant (water) added = 50 ml
First dilution = 2
Volume of the filtrate taken = 5 ml
Final volume of filtrate after colour development = 25 ml
Second dilution = 5
Total dilution = 2x5 = 10 times
Absorbance of the soil solution as read from the spectrophotometer = X
Concentration of B as read from the standard curve against X = C µg/ml
Content of B in the soil (µg /g or mg/kg) = C x 10
Note:
1. The use of azomethine-H is an improvement over that of carmine, quinalizarin
and curcumin, since the procedure involving this chemical does not require
the use of concentrated acid.
2. The amount of charcoal added may vary with the organic matter content of
the soil and should be just sufficient to produce a colourless extract after 5
min. of boiling on a hot plate. Excess amounts of charcoal can result in loss of
extractable B from soils.
18. SOIL MOLYBDENUM
Molybdenum (Mo) is a rare element in soils, and is present only in very small
amounts in igneous and sedimentary rocks. The major inorganic source of Mo is
molybdenite (MoS
2
). The total Mo content in soils is perhaps the lowest of all the
micronutrient elements, and is reported to range between 0.2 µg/g and 10 µg/g.
In the soil solution, Mo exists mainly as HMoO
4
ion under acidic condition,
and as MoO
4
2-
ion under neutral to alkaline conditions. Because of the anionic
nature of Mo, its anions will not be attracted much by the negatively charged
colloids, and therefore, tend to be leached from the soils in humid region.
Molybdenum can be toxic due to greater solubility in alkaline soils of the
arid and semi-arid regions, and deficient in acid soils of the humid regions.
In plants a deficiency of Mo is common at levels of 0.1 µg/g soil or less.
Molybdenum toxicity (molybdenosis) is common when cattle graze forage plants
with 10-20 µg Mo/g.
Determination of available Mo by ammonium acetate extraction is described
here.
Apparatus
- Centrifuge and 50 ml centrifuge tubes
97
- Automatic shaker
- Atomic Absorption Spectrophotometer
Reagents
1. Ammonium acetate solution (NH4OAc), 1.0 M: Dissolve 77.09 g of
ammonium acetate in 1 litre of distilled water and adjust pH to 7.0.
Procedure
1. Weigh accurately 5 g soil and transfer it into a 50 ml centrifuge tube.
2. Add 33 ml of 1.0 M ammonium acetate solution to the tube, stopper and
shake in a mechanical shaker for 5 minutes.
3. Centrifuge at 2000 rpm for 5 minutes or until the supernatant is clear.
4. Decant the solution into a 100 ml volumetric flask.
5. Repeat steps 2 – 4.
6. Make up the volume to 100 ml with ammonium acetate.
7. Determine Mo concentration in the extract by the atomic absorption
spectrophotometer, as described under 16.2.2.
98
19. SOIL SELENIUM
Determination of total selenium (Se) in soils is of little value in predicting Se
uptake. Cary and Allaway (1969) have shown that plant uptake of Se is closely
correlated to the water-soluble Se fraction in soils high in Se content. This
correlation has not been demonstrated for soils low in Se content.
The most commonly used extractants are: Ammonium Bicarbonate –
DTPA, hot water, saturated paste extract, DTPA (2 hrs), and 0.5 M Na
2
CO
3
.
The above five extractants, when tested on soils high in Se, showed high
correlation with Se in wheat plant (Jump and Sabey, 1989). However, Se in
saturated paste extract expressed as mg Se/l of extract was found to be the best
indicator of Se uptake in Se-accumulating plants. The data of Jump and Sabey
(1989) suggested that soil or mine-spoil materials that have more than 0.1 mg
Se/l of saturated extract might cause Se toxicity in plants.
The ammonium bicarbonate-DTPA method showed that Se in extract
correlates better with Se in wheat grain, better when soil samples were taken
from the 0 – 90 cm depth as opposed to 0 – 30 cm depth (Soltanpour et al.,
1982b). This was found to be particularly useful to screen soils and overburden
material for potential toxicity of Se. Concentration of 0.05 μg Se/g or less in feed
and forage plants is in the deficient range and-4 – 5 μg Se/g or more are in the
toxic range.
Procedure
The ratio of soil to any of the extractant listed above varies from 1:2 to 1:5, and
the extraction time from 15 min to 2 hrs. The filtered extract can be analyzed for
Se using a hydride generating system attached to an ICP emission spectrometer
(Soltanpour et al., 1982 a) or hydride generating system attached to atomic
absorption spectrophotometer.
Note:
1. The extracting methods developed for Se have been found to be suitable
for predicting the availability of Se in areas where plants suffer Se toxicity.
Because of rather small quantities of available Se in Se-deficient areas, no
reliable extractant has yet been developed. Therefore, plant Se and total
soil Se will continue to serve as the best tools available for testing the Se
status of Se-deficient soils.
2. Selenium deficiency has implications with respect to livestock and human
nutrition, but not to plant nutrition. So far, there is no known yield response
to Se addition on cultivated crops, and its essentiality to plants is not
established yet.
99
20. POTENTIALLY TOXIC ELEMENTS - CD, CR, NI AND
PB
As a result of on-land application of certain waste products, like digested sewage
sludge contaminated with industrial wastes, soils could become seriously
contaminated with certain potentially hazardous products of the industry, like
cadmium (Cd), chromium (Cr), nikel (Ni) and lead (Pb). In addition to analysis for
plant essential elements, like Fe, Zn, Mn and Cu, soil laboratories are now
charged with a new list of metals considered to be potentially toxic elements.
A total elemental analysis of soil for these elements is not necessary for
the assessment of risk of soil contamination with potentially toxic elements and
its consequent availability for plant uptake. Instead, extraction of a fraction that
would indicate the availability of the metal for plant uptake and consequent
ecotoxicology should be practised. The DTPA extraction procedure used for Fe,
Zn, Mn and Cu is also valid for the assessment of soil contamination with the
potentially hazardous heavy elements. In recent publications the EPA methods
have also been used to determine these elements, and are described below.
Cationic metals are metallic elements that occur predominantly in the soil
solution as cations. Examples are Cd
2+
, Cr
3+
, Ni
2+
Pb
2+
. Oxianions are elements
that are combined with oxygen in molecules with overall negative charge such as
Chromate (CrO
4
-2)
, which is negatively charged and leachable in the soil solution
causing risk to human health and environment (Pierzynski et al., 2000).
The EPA Method (3050)
The United States Environmental Protection Agency (EPA) in 1986 adopted the
following acid digestion procedure for total sorbed metals.
Apparatus
- AAS
- Hotplate
- Beakers
- Watch glass
- Filter papers
Reagents
1. Nitric acid (HNO
3
) concentrated, and 1:1 dilution in deionised water.
2. 30% hydrogen peroxide (H
2
O
2
).
100
3. Hydrochloric acid (HCl) concentrated.
Procedure
1. Add 10 ml of 1:1 HNO
3
to 2 g of air-dried soil (<1 mm) in a 150 ml beaker.
2. Place the sample on a hot plate, cover with a watch glass, and heat
(reflux) at 95°C for 15 minutes.
3. Cool the digest and add 5 ml of concentrated HNO
3
. Reflux for an
additional 30 minutes at 95°C.
4. Repeat the last step, and reduce the solution to about 5 ml without boiling
(by only partially covering the beaker).
5. Cool the digest again and add 2 ml of deionised water and 3 ml of 30%
H
2
O
2
.
6. With the beaker covered, heat the sample gently to start the peroxide
reaction. If effervescence becomes excessively vigorous, remove the
sample from the hot plate. Continue to add 30% H
2
O
2
in 1 ml increments,
followed by gentle heating until the effervescence subsides.
7. Add 5 ml of concentrated HCl and 10 ml of deionised water and reflux the
sample for an additional 15 minutes without boiling.
8. Cool and filter through a Whatman No. 42 filter paper. Dilute to 50 ml with
deionised water. Analyze for Cd, Cr, Ni, and Pb by atomic absorption
spectrophotometer or inductively coupled plasma (ICP) spectroscopy.
The EPA Method (3052)
The United States Environmental Protection Agency adopted the EPA method
No. 3052 for the acid digestion of siliceous and organically based matrices in a
closed vessel device using temperature control microwave heating.
Apparatus
- AAS
- Microwave oven
- Flasks
Reagents
1. Nitric Acid (HNO
3
), 65%
2. Hydroflouric Acid (HF), 40%
Procedure
1. Weigh 0.5 g of sample in a microwave vessel.
101
2. Add 9 ml HNO
3
and 3 ml HF acids, then gently swirl the solution to
homogenize it.
3. Close the vessel and introduce it into the rotor segment
4. Run the microwave programme to completion as suggested by the
microwave manual.
5. Cool the rotor by air or by water until the solution reaches room
temperature.
6. Open the vessel and transfer the solution to a marked flask. Analyze for
Cd, Cr, Ni, and Pb by atomic absorption spectrophotometer or inductively
coupled plasma (ICP) spectroscopy.
Step Time Temperature Microwave power
1 5 min 180
o
C Up to 1000 watt
2 10 min 180
o
C Up to 1000 watt
The EPA Method (3060A) - Alkaline Digestion for Hexavalent Chromium
For the extraction of Cr (VI) the sample is digested using 0.28 M Na
2
CO
3
and 0.5
M NaOH solutions and heating at 90 - 95
o
C for 60 minutes to dissolve the Cr(VI)
and stabilize it against reduction to Cr(III). Cr (VI) can be measured in the extract
by Atomic Absorption Spectrophotometer or ICPMS or other validated analytical
techniques (EPA methods 7196 or 7199).
102
21. IDENTIFICATION OF CLAY MINERALS BY X-RAY
DIFFRACTION (XRD)
The very fine size (<2 microns) of the clay particles give rise to very high specific
surface area. Besides, during its formation, substitution of certain elements for
some higher valence positively charged elements (isomorphous replacement)
occur, and clay particles attain negatively charged surfaces. These phenomena
influence the physico-chemical properties of the soil clay fraction. The nature and
relative presence of clay minerals determine to a great extent soil properties and
characteristics, fertility status, and management practices. For example,
phosphorous, potassium and ammonium retention showed a direct relationship
with the type of clay minerals present in soil (Sayegh and Abdul Majed, 1969;
Sayegh and Rehman, 1969; Schwertmann, 1962; Bajwa, 1980 and Carson and
Dixon, 1972). This is why the U.S. system of soil taxonomy includes the
identification of clay minerals.
Clay minerals are crystalline in structure and built of several planes.
Mineralogical analysis is based on the principle that x-rays will be diffracted by
these planes. Type of clay minerals can then be identified by measuring this
diffraction at different angles. Each mineral type is characterized, depending on
pre-treatment, by a certain pattern of spacing between planes. The diffraction
pattern serves as a fingerprint of each mineral.
The common unit for the measurement of the distance between planes,
known as lattice spacing or intermicellar spacing, is the angstrom unit (1Å = 0.1
nm), which corresponds to the unit of x-ray wavelength. A spacing of 0.715 nm is
characteristic for kaolinite, 1.0–1.2 nm for montmorillonite, and 1.4 nm for
vermicullite. Pre-treatment of the clay sample, like saturation of the mineral with
K, Mg or Mg plus glycolation, and heating at 500
0
C, effects certain shifts in
spacing that are characteristic of the type of mineral.
When a beam of x-rays hits a crystal, x-rays are scattered. A crystal plane
is composed of a systematic and/or periodic arrangement of atoms in space. This
kind of arrangement of atoms is called a crystal lattice. Each atom in the lattice
serves as a scattering point. The coherently scattered waves may constructively
interfere with each other, producing diffraction maxima.
Prior to running an XRD, and in order to enhance the diffraction peaks,
organic matter is removed by treating the clay samples with H
2
O
2
. Removal of
CaCO
3
is done by an acid treatment. Amorphous and free iron may be present
as coatings. The removal of these compounds is usually performed by the
dithionite-citrate-bicarbonate (DCB) method (Jackson, 1956).
For the identification of minerals, a number of XRD runs are made on
differently pre-treated samples. Potassium saturation and glycolation of Mg-
saturated samples are used to distinguish between expanding and non-
expanding minerals. Saturation with K will normally effect a collapse of
103
intermicellar spacing, and the value for d-spacing of 2.0-1.7 nm exhibited by
smectite collapse to 1.0 nm. Reconstitution of the d-spacing to 1.7 nm is
achieved by the glycolation procedure. None of these treatments will have any
effect on the d-spacing of non-expanding minerals, e.g., kaolinite. Table 3
presents the intermicellar spacing for some common clay minerals under
different conditions of pre-treatment.
Table 3. Effect of pre-treatments on the d-spacing of selected clay minerals
d-spacing
nm Clay minerals
K-saturated samples
1.4 Vermiculite, chlorite
1.0-1.2 Smectite, illite
0.72-0.75 Halloysite, metahalloysite
0.715 Kaolinite, chlorite
Mg-saturated samples
1.4 Vermiculite, chlorite, smectite and illite
1.0-1.2 Illite, halloysite
0.72-0.75 Kaolinite, chlorite

Mg-saturated + glycolation
1.7-1.8 Smectite
1.4 Vermiculite
1.0-1.2 Illite, halloysite
0.715 Kaolinite

Heat at 500 °C
1.4 Chlorites
1.0 Vermiculites
0.70 Chlorites (kaolinite and sesquioxides become
amorphous)
The diffractogram is composed of a series of diffraction peaks printed with
the beam angles (2u) on the abscissa, and radiation counts or peak intensities in
104
the y-axis. The position of the diffraction peaks corresponds directly to the d-
spacing. Peaks serve as fingerprints for the identification of the mineral species.
The following illustrations serve as examples (Tan, 1995).
Figure 9, exhibits a diffractogram characteristic of kaolinite clay mineral
characterized by a first-order x-ray diffraction peak of 0.713 nm, which does not
change with pre-treatment.
Figure 9. Identification of kaolinite using its characteristic XRD patterns
(Source: Tan, 1995)
Smectite or montmorillonite mineral type is characterized by a first-order x-
ray diffraction peak of 1.23 nm that shifts to 1.73 nm after solvation or glycolation
of the sample. Saturation with K produces a shift of the peak to 1.0 nm (Figure
10).
105
Figure 10. Identification of smectite using its characteristic XRD patterns
(Source: Tan, 1995)
106
References
Aba-Husayn, M.M. and Sayegh, A.H. 1974. Mineralogy of Al-Hasa Desert soils
(Saudi Arabia). Clays and clay minerals, 25(2):138-147.
Abrukova, L.P. and Isayev, V.A. 1983. Structural mechanical properties of grey-
brown gypsiferous soils. Soviet Soil Science, 15(6):90-100.
Akhvlediani, G.K. 1962. Classification of gypsum-bearing soils in the trans-
caucasus. Soviet Soil Science, 532-534.
Balba, A.M. 1995. Management of Problem Soils in Arid Ecosystem. CRC. Lewis
Publishers, New York, N.Y. USA.
Bajwa, I. 1980. Soil clay mineralogies in relation to fertility management - effect
of soil clay mineral compositions on potassium fixation under conditions
of wetland rice culture. Comm. Soil Sci. Plant. Anal., 11:1019-1027.
Barzangi, A.F. 1973. Gypsiferous soils of Iraq. Ph.D. Thesis. University of Ghent,
Belgium.
Bashour, I.I. 2001. Fertility and fertilizer requirements. In Rural Integrated
Development of the Mountains of Northern Lebanon. FAO Report to
Ministry of Agriculture, Beirut, Lebanon.
Bashour, I.I. and Al-Jaloud, A. 2000. Phosphorus fractionation in calcareous arid
soils in Saudi Arabia. The Land Journal, Vol. 3.1.
Bashour, I.I., Al-Mashhady, A.S., Prasad, J.D., Miller, T. and Mazroa, M. 1983.
Morphology and composition of some soils under cultivation in Saudi
Arabia. Geoderma, 29:327-340.
Bear, F.E. and McClure, G.M. 1920. Sampling soil plots. Soil Sci., 9:65-75.
Boyadgiev, T. 1985. Salty soils of arid and semi-arid regions Sci. Rev. Arid
Zones Res., Vol. 3:1-47. Scientific Publisher, Jodhpur.
Boyadgiev, T. and Sayegh, A.H. 1992. Forms of evolution of gypsum in arid soils
and soil parent materials. Pedologie, XL11-2, pp.171-182.
Brady, N.C. 1990. The Nature and Properties of Soils: Macmillan Publ. Co. New
York, NY.
Bragg, W.L. 1933. The crystalline state. Macmillan Publ. Co., New York, NY,
USA
Brindley, G.W. 1980. Quantitative x-ray mineral analysis of clays. pp. 141-438.
In: Crystal structures of clays Minerals and their x-ray identification.
Mineral. Soc. monograph No. 5. Mineralogical Society, London, England.
Bureau, P. and Roederer, P. 1960. Contribution à l'étude des sols gypseux de la
partie sud du golfe de Gabès. Bull. Assoc. France Etude Sol, 8:145-149.
Section spéc. d'Etudes de pédologie et d'Hydrologie, Es 33.
107
Carson, C.D. and Dixon, J.B. 1972. Potassium selectivity in certain
montmorillonitic soil clays. Soil Sci. Soc. Am. Proc., 36:838-843.
Carter, M.R. 1981. Association of total CaCO
3
and active CaCO
3
with growth of
fine tree species on chernozemic soils. Canadian J. Soil Sci., 61:173-
175.
Cary, E.E. and Allaway, W.H. 1969. The stability of different forms of selenium
applied to low-selenium soils. Soil Sci. Soc. Am. Proc., 33:571-574.
Chang, F.H. 1974. Quantitative interpretation of x-ray diffraction patterns of
mixtures. I. Matrix-flushing method for quantitative multicomponent
analysis. J. Appl. Cryst., 7:519-525.
Cline, M.G. 1944. Principles of soil sampling. Soil Sci., 58:275-288.
Coghill, W.H. and Devaney, F.D. 1937. Ball-mill grinding. U.S. Bureau Mines.
Techn. Paper No. 581.
Coutinet, S. 1965. Méthodes d'analyse utilisables pour les sols salés, calcaires et
gypseux. Agronomie Tropicale, Paris, 12:1242-1253.
Deb, B.G. and Chadha, S.P. 1970. Mechanical analysis of calcareous soils and
distribution of CaCO
3
in various fractions. Journal of Indian Society of
Soil Science, 18:227-232.
Drouineau, G. 1942. Dosage rapide du calcaire actif. Annales Agronomiques,
12:441-450.
Foth H.D., Withee, L.V., Jacobs, H.S. and Thien, S.J. 1977. Laboratory manual
for introductory soil science. W.M. Brown Company Publishers,
Dubuque, Iowa.
Harward, M.E., Carstea, D.D. and Sayegh, A.H. 1969. Properties of vermiculites
and smectites: expansion and collapse. Clays and Clay Minerals,
16:437-447.
Hemwall, J.B. 1957. The fixation of phosphorus by soils. Advances in Agronomy
1957, pp. 95-112.
Hernando, V., Sanchez Conde, M.P. and Contreras, J.G. 1963. Influencia de los
niveles de yeso y de humedad en la fertilidad de un svelo yesoso.
Anales de Edafologia y Agrobiologia, 22:322-337.
Hernando, V., Sanchez Conde, M.P. and Contreras, J.G. 1965. Study of the
mineral nutrition of maize on soils rich in gypsum. Zolfo in Agricultura,
Palermo 1964, pp. 398-411.
Hesse, P.R. 1972. A Textbook of Soil Chemical Analysis. Chem. Publ. Co., New
York, NY.
Hesse, P.R. 1974. Methods of soil analysis-texture analysis of gypsic soils. The
Euphrates pilot irrigation project. FAO, AGON/SF/SYR/67/522.
Hughes, R and Bohor, B. 1970. Random clay powders prepared by spray drying.
Am. Mineral, 55:1780-1786.
108
Hurlbut (Jr.), C.S. and Klein, C. 1977. Manual of Mineralogy. John Wiley & Sons,
New York, NY.
Jackson, M.L. 1956. Soil Chemical Analysis - Advanced Course. Dept. Soils,
Univ. of Wisconsin, Madison, WI.
Jump, R.K. and Sabey, B.R. 1989. Soil test extractants for predicting selenium in
plants. Pages 95-105 in L.W. Jacobs, Ed: Selenium in agriculture and the
environment. Am. Soc. Agr. Inc; SSSA Spec. Publ. 23 Chapter 5.
Keeney, D.R. and Nelson, D.W. 1982. Nitrogen - inorganic forms. pp. 643-698.
In: Methods of Soil Analysis, Part 2, A.L.
Kim, H.T. 1996. Soil Sampling, preparation and analysis. Marcel Dekker Inc.,
New York, NY, 10016.
Krauskoph, K.B. 1973. Geochemistry of micronutrients. pp.7-40. In:
Micronutrients in Agriculture, J.J. Mortvedt (ed). Soil Sci. Soc. Am.,
Madison, WI.
Krumbein, W.C. Pettijohn, F.J. 1938. Manual of Sedimentary Petrology.
Appleton-Century Co., New York, NY.
Lindsay W.L. and De Ment, J.D. 1961. Effectiveness of some iron phosphate as
sources of phosphorus for plants. Plant and Soil, 14:118.
Lindsay, W.L. 1973. Inorganic phase equilibria of micronutrients in soils. pp. 41-
57. In: Micronutrients in Agriculture. J.J. Mordvedt, P.M. Giordano, and
W.L. Lindsay (eds). Soil Sci. Soc. Am. Inc., Madison, WI.
Lindsay, W.L. and Norvell, W.A. 1978. Development of DTPA soil test for zinc,
iron, manganese and copper. Soil Sci. Soc. Am. J., 42:421-428.
Loveday, J. 1974. Methods for analysis of irrigated soils. II: Particle size analysis.
Commonwealth Bureau of Soils Technical Communication N: 5H.
Maas, E.V. and Hoffman, G.Z. 1977. Crop salt tolerance current assessment. J.
of irrigation and drainage division ASCE, 103:115-134.
Marcuse, S. 1949. Optimum allocation and variance components in nested
sampling with an application to chemical analysis. Biometrics, 5:189-206.
Marwan, H.K., Sayegh, A.H., and Atallah, N.J. 1978. The effect of soil
conditioners on pore size distribution and water retention of a calcareous
soil. Aust. J. Soil Res., 29:277-81.
Matar, A.E. and Douleimy, T. 1978. Note on a proposed method for the
mechanical analyses of gypsiferous soils. ACSAD publication. The Arab
Center for the Studies of Arid Zones and Dry Lands, Damascus, Syria.
Norvell, W.A. 1973. Equilibria of metal chelates in soil solution. pp.115-138. In:
Micronutrient in Agriculture, J.J. Mortvedt, P.M. Giordano, and W.L.
Lindsay (eds). Soil Sci. Soc. Am. Inc., Madison, WI, USA.
109
Petersen, R.G. and Chamblee, D.S. 1955. Optimum size of sample for hand
separation of forage crop mixtures into their component species in small
plot experiments. Agron. J., 47:20-23.
Pierzynski, G.M., Sims, J.T. and Vance, G.F. 2000. Soils and Environmental
Quality. CRC Press Washington DC, USA.
Post, A.H. 1924. Soil variability as determined by statistical methods. Soil Sci.,
17:343-357.
Reed, J.F. and Rigney, J.A. 1947. Soil sampling from fields of uniform and no
uniform appearance and soil types. J. Amer. Soc. Agron., 39:26-40.
Richards, L.A. (ed.). 1954. United State Salinity Laboratory Staff, Handbook No.
60. Diagnosis and improvement of Saline and Sodic Soils. United State
Department of Agriculture, U.S. Government Printing Office, Washington
D.C., USA.
Sayegh, A.H., Alban, L.A. and Petersen, R.G. 1958. A sampling study in a saline
and alkali area. Soil Sci. Soc. Am. Proc., 22:252-254.
Sayegh, A.H., Harward, M.E. and Knox, E.G. 1965. Humidity and temperature
interaction with respect to K-saturated expanding clay minerals.
American Mineralogist, 50:490-495.
Sayegh, A.H. and Abdul Majid, A. 1969. Phosphorus fractionation and retention
in alkaline Lebanese soils. Agrochimica, XIII(3):265-276.
Sayegh A.H. and Salib, A.J. 1969. Some physical and chemical properties of
soils in the Beqa'a plain, Lebanon. The Journal of Soil Science,
20(1):167-175.
Sayegh, A.H. and Rehman, H. 1969. Ammonium fixation in alkaline Lebanese
soils. Soil Science, 108:202-208.
Sayegh, A.H. 1975. Suggestion of criteria for sampling and classifying salt
affected soils of the Middle East. International symposium on new
developments in the field of salt affected soils (December 4-9, 1972).
General Organization for Government printing offices, Cairo, Arab
Republic of Egypt.
Sayegh, A.H., Khan, N.A., Khan, P. and Ryan, J. 1978. Factors affecting gypsum
and cation exchange capacity determinations in gypsiferous soils. Soil
Sci., 125(5):194-300.
Sayegh, A.H. 1986. In: Management of gypsiferous soil. FAO Soils Bulletin 62,
Rome, Italy.
Schoonover. 1953. Examination of soils for alkali-quick tests. University of Calif.
Ext. Service, Berkeley, Calif (mimeo).
Schwertmann, U. 1962. Die selective kationensorption der Tonfraktion einiger
Boden aus Sedimenten. Z. Pflan. Dung. Bodenkunde, 97:9-25.
110
Sherman, G.D. and Harmer, P.M. 1943. The effect of manganese sulfate on
several crops growing on organic soil when applied as a stream or spray
on the crop. Soil Sci. Soc. Am. Proc., 8:334-340.
Soltanpour, P.N., Fox, R.L. and Jones, R.C. 1988. A quick method to extract
organic phosphorus from soils. Soil Sci. Soc. Am. J., 51:255-256.
Soltanpour, P.N., Jones, J.B. and Workman, S.M. 1982a. Optical emission
spectrometry. Pages 29-65 in A.L. Page et al, Eds. Method of Soil
Analysis. Part 2. 2
nd
ed. Agronomy No. 9. Amer. Soc. of Agronomy,
Madison, WI.
Soltanpour, P.N., Olsen S.R. and Goos, R.J. 1982b. Effect of nitrogen fertilization
on dryland wheat on grain selenium concentration. SSSAJ., 46:430-433.
Sparks, D.L. (ed). 1996. Methods of Soil Analysis, Part three, Chemical Methods.
ASA, Madison, Wisconsin, USA .
Sys, C. 1975. Land evaluation in Europe. FAO Soils Bulletin 29, pp. 113, Rome,
Italy.
Tan, K.H. 1994. Environmental Soil Science. Marcel Dekker Inc., New York, NY.
Tan, K.H. 1995. Soil Sampling, Preparation, and Analysis. Marcel Dekker Inc.,
New York, N.Y. USA.
Tarzi, G.J. 1984. Procedures for collecting soil samples for different purposes.
Ministry of Agriculture and Water, Directorate of Agricultural Research,
Riyadh, Kingdom of Saudi Arabia.
Thabet, A. 1975. Active and total CaCO
3
in soils. Thesis. American University of
Beirut, Beirut, Lebanon.
Thomson, A.P. Duthie, D.M.L. and Wilson, M.J. 1972. Randomly oriented
powders for quantitative identification by x-ray diffraction. Clay Mineral,
9:345-348.
Tisdale, S.L. and Nelson, W.L. 1993. Soil Fertility and Fertilizers. Macmillan Co.,
New York, N.Y.
Van Alphen, J.G. and Rios Romero, F. 1971. Gypsiferous soils. Bulletin 12,
International Institute for Land Reclamation and Improvement.
Wageningen, the Netherlands.
Van Schuylenborgh, J. 1954. The effect of air-drying of soil samples upon some
physical soil properties. Neth. J. Agri. Sci., 2:50-57.
Vieillefon, J. 1979. Contribution to the improvement of analysis of gypsiferous
soils. Cahiers/ORSTOM, Serie Pedologie, 17:195-223.
Walkley, A. 1947. A critical examination of a rapid method for determining
organic carbon in soils. Effect of variations in digestion conditions and
inorganic soil constituents. Soil Sci., 63:251-263.
111
Watanabe, F.S. and Olsen, S.R. 1965. Test of an ascorbic acid method for
determining phosphorus in water and NaHCO
3
extracts from soil. Soil
Sci. Am. Proc., 29:677-678.
Waynick, D.D. 1918. Variability in soils and its significance to past and future soil
investigations. Univ. of California Pub. in Agr. Sci., 3:243-269.
Westin F.C. and Buntley, G.J. 1966. Soil phosphorus in South Dakota I: inorganic
phosphorus fixation of some soil series. Soil Sci. Soc. Amer. Proc.,
30:245.
Whittig, L.D. and Allardice, W.R. 1986. X-ray diffraction techniques. pp.331-362.
In: Methods of Soil Analysis, Part 1, A. Klute (ed.). Agronomy series No.
9. Am. Soc. Agronomy and Soil Sci. Soc. Am., Inc., Madison, WI.
Willard, H.H. and Diehl, H. 1943. Advanced Qualitative Analysis. Van Nostrad,
New York, NY.
112
Appendix A. List of the atomic weights of the elements
Element Symbol Atomic
Number
Atomic
Weight
Element Symbol Atomic
Number
Atomic
Weight
Actinium Ac 89 (227) Mercury Hg 80 200.59
Aluminium Al 13 26.98 Molybdenum Mo 42 95.94
Americium Am 95 (243) Neodymium Nd 60 144.24
Antimony Sb 51 121.75 Neon Ne 10 20.183
Argon Ar 18 39.948 Neptunium Np 93 (237)
Arsenic As 33 74.92 Nickel Ni 28 58.71
Astatine At 85 (210) Niobium Nb 41 92.91
Barium Ba 56 137.34 Nitrogen N 7 14.007
Berkelium Bk 97 (249) Nobelium No 102 (253)
Beryllium Be 4 9.012 Osmium Os 76 190.2
Bismuth Bi 83 208.98 Oxygen O 8 15.9994
Boron B 5 10.81 Palladium Pd 46 106.4
Bromine Br 35 79.909 Phosphorus P 15 30.974
Cadmium Cd 48 112.40 Platinum Pt 78 195.09
Calcium Ca 20 40.08 Plutonium Pu 94 (242)
Californium Cf 98 (251) Polonium Po 84 (210)
Carbon C 6 12.011 Potassium K 19 39.102
Cerium Ce 58 140.12 Praseodymium Pr 59 140.91
Cesium Cs 55 132.91 Promethium Pm 61 (147)
Chlorine Cl 17 35.453 Protactinium Pa 91 (231)
Chromium Cr 24 52.00 Radium Ra 88 (226)
Cobalt Co 27 58.93 Radon Rn 86 (222)
Copper Cu 29 63.54 Rhenium Re 75 186.23
Curium Cm 96 (247) Rhodium Rh 45 102.91
Dysprosium Dy 66 162.50 Rubidium Rb 37 85.47
Einsteinium Es 99 (254) Ruthenium Ru 44 101.1
Erbium Er 68 167.26 Samarium Sm 62 150.35
Europium Eu 63 151.96 Scandium Sc 21 44.96
Fermium Fm 100 (253) Selenium Se 34 78.96
Fluorine F 9 19.00 Silicon Si 14 28.09
Francium Fr 87 (223) Silver Ag 47 107.870
Gadolinium Gd 64 157.25 Sodium Na 11 22.9898
Gallium Ga 31 69.72 Strontium Sr 38 87.62
Germanium Ge 32 72.59 Sulfur S 16 32.064
Gold Au 79 196.97 Tantalum Ta 73 180.95
Hafnium Hf 72 178.49 Technetium Tc 43 (99)
Helium He 2 4.003 Tellurium Te 52 127.60
Holmium Ho 67 164.93 Terbium Tb 65 158.92
Hydrogen H 1 1.0080 Thallium Tl 81 204.37
Indium In 49 114.82 Thorium Th 90 232.04
Iodine I 53 126.90 Thulium Tm 69 168.93
Iridium Ir 77 192.2 Tin Sn 50 118.69
Iron Fe 26 55.85 Titanium Ti 22 47.90
Krypton Kr 36 83.80 Tungsten W 74 183.85
Lanthanum La 57 138.91 Uranium U 92 238.03
Lawrencium Lw 103 (257) Vanadium V 23 50.94
Lead Pb 82 207.19 Xenon Xe 54 131.30
Lithium Li 3 6.939 Ytterbium Yb 70 173.04
Lutetium Lu 71 174.97 Yttrium Y 39 88.91
Magnesium Mg 12 24.312 Zinc Zn 30 65.37
Manganese Mn 25 54.94 Zirconium Zr 40 91.22
Mendelevium Md 101 (256)
Numbers in parentheses indicate mass of most stable known isotopes.
113
Appendix B. pH indicators
1
pH Indicators pH transition intervals
Name Colour pH pH Colour
Cresol red pink 0.2 1.8 yellow
m-Cresol purple red 1.2 2.8 yellow
Thymol blue red 1.2 2.8 yellow
p-Xylenol blue red 1.2 2.8 yellow
Triphenylcarbinol red 1.2 3.2 Colourless
2,4-Dinitrophenol Colourless 2.8 4.7 Yellow
4-Dimethylaminoazobenzene Red 2.9 4.0 Yellow-orange
Bromochlorophenol blue Yellow 3.0 4.6 Purple
Bromophenol blue Yellow 3.0 4.6 Purple
Methyl orange Red 3.1 4.4 Yellow-orange
Bromocresol green Yellow 3.8 5.4 Blue
2,5-Dinitrophenol Colourless 4.0 5.8 Yellow
Alizarinsulfonic acid sodium salt Yellow 4.3 6.3 Violet
Methyl red Red 4.4 6.2 Yellow-orange
Methyl red sodium salt Red 4.4 6.2 Yellow-orange
Chlorophenol red Yellow 4.8 6.4 Purple
Hematoxylin Yellow 5.0 7.2 Violet
Litmus extra pure Red 5.0 8.0 Blue
Bromophenol red Orange-yellow 5.2 6.8 Purple
Bromocresol purple Yellow 5.2 6.8 Purple
4-Nitrophenol Colourless 5.4 7.5 Yellow
Bromoxylenol blue Yellow 5.7 7.4 Blue
Alizarin Yellow 5.8 7.2 Red
Bromothymol blue Yellow 6.0 7.6 Blue
Phenol red Yellow 6.4 8.2 Red
3-Nitrophenol Colourless 6.6 8.6 Yellow-orange
Neutral red Bluish-red 6.8 8.0 Orange-yellow
4,5,6,7-Tetrabromophenolphthalein Colourless 7.0 8.0 Purple
Cresol red Orange 7.0 8.8 Purple
1-Naphtholphthalein Brownish 7.1 8.3 Blue-green
m-Cresol purple Yellow 7.4 9.0 Purple
Thymol blue Yellow 8.0 9.6 Blue
P-Xylenol blue Yellow 8.0 9.6 Blue
Phenolphthalein Colourless 8.2 9.8 Red-violet
Thymolphthalein Colourless 9.3 10.5 Blue
Alizarin yellow GG Light yellow 10.2 12.1 Brownish-yellow
Epsilon blue Orange 11.6 13.0 Violet

1
Adapted from pH Indicators, E. Merck and Co.
114
Appendix C. Properties of laboratory materials
Material
Max. Working
Temperature,
°C
Sensitivity to
Thermal
Shock
Chemical Inertness Notes
Borosilicate glass 200
150°C change
OK
Attacked to certain
degree by
alkali solutions while
heating
Trademarks: pyrex (Corning
Glass Works)
Kimax (Owens-Illinois)
Soft glass Low
Attacked by alkali
solutions
Alkali-resistant
glass
More sensitive
than
borosilicate
Boron-free. Trademark:
Corning
Fused quartz 1050 Very High
Resistant to most acids,
halogens
Quartz crucibles used for
fusions
High-silica
glass
1000 Very High
More resistant to alkalis
than borosilicate
Similar to fused quartz
Trademark: Vycor
(Corning)
Porcelain
1100 (glazed)
1400 (unglazed)
High High
Platinum 1500
Resistant to most acids,
molten salts. Attacked by
aqua regia, fused
nitrates, cyanides,
chlorides at >1000°C.
Alloys with gold, silver,
and other metals
Usually alloyed with
iridium or rhodium to
increase hardness. Platinum
crucibles for fusions and
treatment with HF
Nickel and iron
Fused samples
contaminated with the
metal
Ni and Fe crucibles used for
peroxide fusions
Stainless steel 400-500 High
Not attacked by alkalis
and acids except conc.
HCI, dil. H
2
SO
4
, and
boiling conc. HNO
3
Polyethylene 115
Not attacked by alkali
solutions or HF. Attacked
by many organic solvents
(acetone, ethanol OK)
Flexible plastic
Polystyrene 70
Not attacked by HF.
Attacked by many
organic solvents
Somewhat brittle
Teflon 250 Inert to most chemicals
Useful for storage of
solutions and reagents for
trace metal analysis
115
Appendix D. Grades of chemicals
Grade Purity Notes
Technical or commercial Indeterminate quality
May be used in preparation of cleaning solution
only
C.P. (Chemically pure)
More refined, but still
unknown quality
U.S.P.
Meets minimum purity
standards
Conforms to tolerance set by the United States
Pharmacopoeia for contaminants dangerous to
health
A.C.S. reagent
Reagent grade
High purity
Conforms to minimum specifications set by the
Reagent Chemicals Committee of the American
Chemical Society
Primary standard
Analytical grade
Highest purity
Required for accurate volumetric analysis (for
standard solutions)
Concentrations of Commercial Reagent-Grade Acids and bases
a
Reagent F. Wt.
b
M
c
% by Wt. Density (20°), g/cm
3
H
2
SO
4
98.08 17.6 94.0 1.831
HClO
4
100.5 11.6 70.0 1.668
HCl 36.46 12.4 38.0 1.188
HNO
3
63.01 15.4 69.0 1.409
H
3
PO
4
98.00 14.7 85.0 1.689
HC
2
H
3
O
2
60.05 17.4 99.5 1.051
NH
3
17.03 14.8 28.0 0.898
a
These are approximate concentrations and cannot be used for preparing standard solutions.
b
Formula weight.
c
Molarity.
NBS Tolerances for Volumetric Glassware, Class A
a
Tolerances, ml Capacity, ml
(Less than and Including) Volumetric Flasks Transfer Pipettes Burettes
1000 ±0.30
500 ±0.15
100 ±0.08 ±0.08 ±0.10
50 ±0.05 ±0.05 ±0.05
25 ±0.03 ±0.03 ±0.03
10 ±0.02 ±0.02 ±0.02
5 ±0.02 ±0.01 ±0.01
2 ±0.006
a
Corning Pyrex glassware and Kimball KIMAX, Class A, conform to these tolerances.

116
Appendix E. Nutrient range in soils, mg/kg (Bashour, 2001)
Nutrient
Very
Low
Low Medium High
Very
High
Nitrate, NO
3
-N 0 – 5 5 – 15 15 – 30 30 – 40 >40
Phosphorus
Olson method
0 – 3 3 – 8 8 – 14 4 – 20 >20
Potassium
NH4OAC- extractable
0 – 85 85 – 150 150 – 250 250 – 450 >450
Magnesium
Exchangeable
0 – 85 85 – 180 180 – 300 300 – 500 >500
Calcium
Exchangeable
0 – 500 500 – 1200 1200 – 2500 2500 – 3500 >3500
Sulphur
Water soluble
0 – 10 10 – 20 20 – 35 35 – 45 >45
Sodium
Water Soluble
0 – 300 >300
117
Appendix F. Temperature factors (f
t
) for correcting resistance and
conductivity data on soil extracts to the standard temperature of 25°C
EC
25
= EC
t
× f
t
; EC
25
= (k/R
t
) × f
t
; R
25
= R
t
/f
t
°C °F. f
t
°C °F. f
t
°C °F. f
t
3.0 37.4 1.709 22.0 71.6 1.064 29.0 84.2 0.925
4.0 39.2 1.660 22.2 72.0 1.060 29.2 84.6 0.921
5.0 41.0 1.613 22.4 72.3 1.055 29.4 84.9 0.918
6.0 42.8 1.569 22.6 72.7 1.051 29.6 85.3 0.914
7.0 44.6 1.528 22.8 73.0 1.047 29.8 85.6 0.911

8.0 46.4 1.488 23.0 73.4 1.043 30.0 86.0 0.907
9.0 48.2 1.488 23.2 73.8 1.038 30.2 86.4 0.904
10.0 50.0 1.411 23.4 74.1 1.034 30.4 86.7 0.901
11.0 51.8 1.375 23.6 74.5 1.029 30.6 87.1 0.897
12.0 53.6 1.341 23.8 74.8 1.025 30.8 87.4 0.894

13.0 55.4 1.309 24.0 75.2 1.020 31.0 87.8 0.890
14.0 57.2 1.277 24.2 75.6 1.016 31.2 88.2 0.887
15.0 59.0 1.247 24.4 75.9 1.012 31.4 88.5 0.884
16.0 60.8 1.218 24.6 76.3 1.008 31.6 88.9 0.880
17.0 62.6 1.189 24.8 76.6 1.004 31.8 89.2 0.877

18.0 64.4 1.163 25.0 77.0 1.000 32.0 89.6 0.873
18.2 64.8 1.157 25.2 77.4 0.996 32.2 90.0 0.870
18.4 65.1 1.152 25.4 77.7 0.992 32.4 90.3 0.867
18.6 65.5 1.147 25.6 78.1 0.988 32.6 90.7 0.864
18.8 65.8 1.142 25.8 78.5 0.983 32.8 91.0 0.861

19.0 66.2 1.136 26.0 78.8 0.979 33.0 91.4 0.858
19.2 66.6 1.131 26.2 79.2 0.975 34.0 93.2 0.843
19.4 66.9 1.127 26.4 79.5 0.971 35.0 95.0 0.829
19.6 67.3 1.122 26.6 79.9 0.967 36.0 96.8 0.815
19.8 67.6 1.117 26.8 80.2 0.964 37.0 98.6 0.801

20.0 68.0 1.112 27.0 80.6 0.960 38.0 100.2 0.788
20.2 68.4 1.107 27.2 81.0 0.956 39.0 102.2 0.775
20.4 68.7 1.102 27.4 81.3 0.953 40.0 104.0 0.763
20.6 69.1 1.097 27.6 81.7 0.950 41.0 105.8 0.750
20.8 69.4 1.092 27.8 82.0 0.947 42.0 107.6 0.739

21.0 69.8 1.087 28.0 82.4 0.943 43.0 109.4 0.727
21.2 70.2 1.082 28.2 82.8 0.940 44.0 111.2 0.716
21.4 70.5 1.078 28.4 83.1 0.936 45.0 113.0 0.705
21.6 70.9 1.073 28.6 83.5 0.932 46.0 114.8 0.694
21.8 71.2 1.068 28.8 83.8 0.929 47.0 116.6 0.683
Source: Agricultural Handbook 60, U.S. Dept of Agriculture
118
Appendix G. Conversion factors for SI and non-SI units (Soil Science Society
of America Journal)
To convert Column
1 into Column 2,
multiply by
Column 1
SI Unit
Column 2
Non-SI Unit
To convert Column
2 into Column 1
multiply by
Length
0.621 kilometer, km (10
3
m) mile, mi 1.609
1.094 meter, m yard, yd 0.914
3.28 meter, m foot, ft 0.304
1.0 micrometer, μm (10
-6
m) micron, μ 1.0
3.94 × 10
-2
millimeter, mm (10
-3
m) inch, in 25.4
10 nanometer, nm (19
-9
m) angstrom, å 0.1
Area
2.47 hectare, ha acre 0.405
247 square kilometer, km
2
(10
3
m)
2
acre 4.05 × 10
-3
0.386 square kilometer, km
2
(10
3
m)
2
square mile, mi
2
2.590
2.47 × 10
-4
square meter, m
2
acre 4.05 ×10
3
10.76 square meter, m
2
square foot, ft
2
9.29 × 10
-2
1.55 × 10
-3
square millimeter, mm
2
(10
-3
m)
2
square inch, in
2
645
Volume
9.73 × 10
-3
cubic meter, m
3
acre-inch 102.8
35.3 cubic meter, m
3
cubic foot, ft
3
2.83 × 10
-2
6.10 × 10
4
cubic meter, m
3
cubic inch, in
3
1.64 × 10
-5
2.84 × 10
-2
liter, L (10
-3
m
3
) bushel, bu 35.24
1.057 liter, L (10
-3
m
3
) quart (liquid), qt 0.946
3.53 × 10
-2
liter, L (10
-3
m
3
) cubic foot, ft
3
28.3
0.265 liter, L (10
-3
m
3
) gallon 3.78
33.78 liter, L (10
-3
m
3
) pint (fluid), pt 0.473
Mass
2.20 × 10
-3
gram, g (10
-3
kg) pound, lb 454
3.52 × 10
-2
gram, g (10
-3
kg) ounce (avdp), oz 28.4
2.205 kilogram, kg pound, lb 0.454
0.01 kilogram, kg quintal (metric), q 100
1.10 × 10
-3
kilogram, kg ton (2000 lb), ton 907
1.102 megagram, Mg (tonne) ton (U.S.), ton 0.907
1.102 tonne, t ton (U.S.), ton 0.907
Yield and Rate
0.893 kilogram per hectare, kg ha
-1
pound per acre, lb acre
-1
1.12
7.77 × 10
-2
kilogram per cubic meter, kg m
-3
pound per bushel, lb bu
-1
12.87
1.49 × 10
-2
kilogram per hectare, kg ha
-1
bushel per acre, 60 lb 67.19
1.59 × 10
-2
kilogram per hectare, kg ha
-2
bushel per acre, 56 lb 62.71
1.86 × 10
-2
kilogram per hectare, kg ha
-1
bushel per acre, 48 lb 53.75
0.107 liter per hectare, L ha
-1
gallon per acre 9.35
893 tonnes per hectare, t ha
-1
pound per acre, lb acre
-1
1.12 × 10
-3
893 megagram per hectare, Mg ha
-1
pound per acre, lb acre
-1
1.12 × 10
-3
0.446 megagram per hectare, Mg ha
-1
ton (2000 lb) per acre, ton acre
-1
2.24
2.24 meter per second, m s
-1
mile per hour 0.447
119
APPENDIX G. (continued)
To convert Column
1 into Column 2,
multiply by
Column 1
SI Unit
Column 2
Non-SI Unit
To convert Column
2 into Column 1
multiply by
Specific Surface
10 square meter per kilogram, m
2
kg
-1
square centimeter per gram, cm
2
g
-1
0.1
1000 square meter per kilogram, m
2
kg
-1
square millimeter per gram, mm
2
g
-1
0.001
Pressure
9.90 megapascal, MPa (10
6
Pa) atmosphere 0.101
10 megapascal, MPa (10
6
Pa) bar 0.1
1.00 megagram per cubic meter, Mg m
-3
gram per cubic centimeter, g cm
-3
1.00
2.09 × 10
-2
pascal, Pa pound per square foot, lb ft
-2
47.9
1.45 × 10
-4
pascal, Pa pound per square inch, lb in
-2
6.90 × 10
3
Temperature
1.00 (K - 273) Kelvin, K Celsius, °C 1.00 (°C + 273)
(9/5 °C) + 32 Celsius, °C Fahrenheit, °F 5/9 (°F - 32)
Plane Angle
57.3 radian, rad degrees (angle), ° 1.75 × 10
-2
Electrical Conductivity, Electricity, and Magnetism
10 siemen per meter, S m
-1
millimho per centimeter,
mmho cm
-1
0.1
10
4
tesla, T gauss, G 10
-4
Water Measurement
9.73 × 10
-3
cubic meter, m
3
acre-inches, acre-in 102.8
9.81 × 10
-3
cubic meter per hour, m
3
h
-1
cubic feet per second, ft
3
s
-1
101.9
4.40 cubic meter per hour, m
3
h
-1
U.S. gallons per minutes, gal min
-1
0.227
8.11 hectare-meters, ha-m acre-feet, acre-ft 0.123
97.28 hectare-meters, ha-m acre-inches, acre-in 1.03 × 10
-2
8.1 × 10
-2
hectare-centimeters, ha-cm acre-feet, acre-ft 12.33
Concentrations
1 centimole per kilogram, cmol kg
-1
(ion exchange capacity)
milliequivalents per 100 grams,
meq 100 g
-1
1
0.1 gram per kilogram, g kg
-1
percent, % 10
1 milligram per kilogram, mg kg
-1
parts per million, ppm 1
Radioactivity
2.7 × 10
-11
becquerel, Bq curie, Ci 3.7 × 10
10
2.7 × 10
-2
becquerel per kilogram, Bq kg
-1
picocurie per gram, pCi g
-1
37
100 gray, Gy (absorbed dose) rad, rd 0.01
100 sievert, Sv (equivalent dose) rem (roentgen equivalent man) 0.01
Plant Nutrient Conversion
Element Oxide
2.29 P P
2
O
5
0.437
1.20 K K
2
O 0.830
1.39 Ca CaO 0.715
1.66 Mg MgO 0.602
9 7 8 9 2 5 1 0 5 6 6 1 5
TC/M/A0955E/1/01.07/200
ÌSBN 978-92-5-105661-5

METHODS OF ANALYSIS FOR SOILS OF ARID AND SEMI-ARID REGIONS

by

Issam I. Bashour
and

Antoine H. Sayegh
American University of Beirut

Beirut, Lebanon

Food and Agriculture Organization of the United Nations Rome, 2007

..1................................................................ 40 6..........................................................................................4..4......................... Methods of Sampling ......2............ Introduction ..........5...................................2....................................... Soil Sampling Tools .......................... Sedimentation .......... 32 4......... Gypsum Removal from Soil .... 31 4................................................ 34 5.. 13 1. 16 2.. 1 ACKNOWLEDGEMENTS ..................... 15 2...................................................................1..... Calcareous Soils ....................................................... 21 2.. 38 5......... Calculation of Saturation Percentage........ 35 5...........5................3.2............................. Preparation of Soil Samples..4................................................. Preparation of Saturation Paste ........ Bouyoucos Method ........... 31 4...........5........ Measurement of Bulk Density ... 27 4............................. 17 2....................... 13 2...........................................2............................................................................. 16 2........ Bulk Density of an Undisturbed Soil Sample.2........... 19 2...... 40 6................................. Gypsiferous Soils ..5.............................. 13 1................3.................................... Measurement of Particle Density ... SOIL SAMPLING AND PREPARATION ................... Pretreatment with BaCl2 Solution (Modified Method) ........ 26 4..................................................................... SOIL DENSITY AND TOTAL PORE SPACE .................................................................................... 19 2................................ Dispersion .............. Introduction ............................................... 40 6.......................................... SOIL TEXTURE – PARTICLE SIZE DISTRIBUTION .... SOIL MOISTURE ........1....5...........2...... Grinding and Sieving of Soil Samples ......................................................... 22 3.................................................... 5 1.................1...................................................1.........................2........1...........................2................3............... 35 5.......................................................3......... Pretreatment of Soil with BaCl2 Solution followed by Ethanol ................................... 23 4.......... 34 5.................................................................................5..................................................................1......1..........................................................................................................................4............ 33 5....................................................................... 25 4....3...................... 35 5. SOILS OF ARID AND SEMI-ARID REGIONS ................................................................ 37 5................. 39 6............................................TABLE OF CONTENTS PREFACE .......................................... 17 2.............. Calculation of Percent Pore Space ....................................... 13 1. 25 4... Depth of Sampling ............................................ Reduction of Sample Size...........................1.............6............................................. Bulk Density of a Disturbed Soil Sample......................................2.... 3 GENERAL LABORATORY GUIDELINES..2..................... ANALYSIS OF SATURATION PASTE EXTRACT .......................................................... The Graduated Cylinder Method....................... Sampling for Soil Fertility Tests................................................................. 31 4....... 32 4................. 15 2..............................................................................................2......... Salt Affected Soils .3................................. 41 i ......................................... Introduction ........ Pretreatment of Soil with BaCl2 to Coat Gypsum with BaSO4 ...........1. The Volumetric Flask Method ............................................. 2 INTRODUCTION.........2.................. Gypsum Removal by Ammonium Oxalate ............................................... Gypsum Removal by Hydrochloric Acid ...........................................................................................3........2......2...2. 41 6.....................................2.............. 37 5............2............................................................... 27 4........................5.......5............ Determination of Soil pH ................ Soil Sampling for Soil Survey and Classification Studies ..........3............................................. Time of Sampling ....................

.................... SOIL GYPSUM .....3............................................................................................................................................ 80 15............... GYPSUM REQUIREMENT ................. 55 8.....................3... 85 16........................ 74 12...1...3..................3...... 77 13.... 66 11........................4..................................................... 84 16........................ Iron. 46 6.......5.... 65 11.. SOIL SULPHUR..................3.............................. Determination of Nitrate by the Specific Ion Electrode... Determination of Total Calcium Carbonate .......3....................................................2.. Walkley – Black Wet Combustion Method .............1.. SOIL POTASSIUM......5...3.......... Manganese and Copper...........6....................... 84 16... DTPA Extraction Method .... Copper ...............2... Determination of Available Phosphorous (Olsen’s method) ..............1................. CATION EXCHANGE CAPACITY (CEC) ........................................ Iron.. Determination of Ammonium by Specific Ion Electrode .....1......................................................... 71 12............ 78 14..................3............................ 74 12................................... 77 13.........2...................................................................................... Zinc....... Determination of Available Micronutrients................. CALCIUM CARBONATE .......2......3................................................ 44 6......1.................................2................2............ 61 11......4.. Determination of Carbonate and Bicarbonate ............................................................................................... Determination of Soluble Sodium and Potassium ............. 74 12..............2.......1................... 64 11..... SOIL PHOSPHOROUS.3.........................................................................2................ Determination of Mineral Nitrogen .... 43 6..... 56 9......................... Determination of Fixed Potassium ......... 64 11......... Determination of Ammonium by Indophenol Blue Method .............................. SOIL NITROGEN ..................................3............................................................. 44 6......... Determination of Cation Exchange Capacity (CEC)............1...... Preparation of Saturation Extract ............. 68 11........................................................................................................................... Influence of Soil Parent Materials on the Distribution of the Inorganic Pfractions .......4..................................................................................................... 50 8..............1.......1.............................................................................. Phosphorous Retention.................................. Manganese .................................. Determination of Available Potassium................. Determination of Soluble Calcium and Magnesium .... 69 11....1.................. 73 12............. 49 7...................2........................................... 54 8.......................... 84 16..3.. 42 6..................................... 50 7............................................... 75 13....................................................................... 48 7........................................ Determination of Soil Salinity (Electric Conductivity)............................ Iron and Aluminium Amorphous Phosphate in Calcareous Soils ....................... Fractionation of Soil Phosphorous ..2................................. 84 16...........3................1..........................1............................................................. 53 8........ SOIL ORGANIC MATTER ...................... 87 16.................................................... Extraction of Exchangeable Ammonium ...............................................1.......................................... Total Nitrogen (Kjeldahl method) .1...................................................................... 69 11......... Exchangeable Sodium Percentage.................. Determination of Chloride ........................................................ 61 10..........................1.............. 82 16. 87 ii .....................1.................... Determination of CEC in Gypsiferous and Calcareous Soils........ 73 12........................................ 58 10... 73 12...................... 86 16....... Determination of Nitrate by the Phenoldisulfonic Acid Method .....2.........................................................6...............2.... Zinc ................2..................... Fate of Applied Phosphatic Fertilizer . SOIL MICRONUTRIENTS............... Determination of Active Calcium Carbonate .

............... 2001) . Field data sheet..... 106 List of Tables Table 1..................... Temperature factors (ft) for correcting resistance and conductivity data on soil extracts to the standard temperature of 25°C ................1.. 93 17........................... CR............................................................... 59 Table 3............................. SOIL SELENIUM ... 104 Figure 10............................ 30 Figure 8........................................................ Total Boron by Na2CO3 Fusion ..3.......... non-saline sodic and saline sodic soils.2..................................... 96 19.. 94 18...... 93 17....... Grades of chemicals ................ 114 Appendix D............... DTPA Extractability and Availability for Plant Uptake........... Available Boron by Hot Water Extraction ..................... 90 17........................................... 18 Figure 2.............. IDENTIFICATION OF CLAY MINERALS BY X-RAY DIFFRACTION (XRD) .............. Properties of laboratory materials ...............2..... Sampling pattern for fertility test in a non-uniform land ....... SOIL BORON........... 98 20.......... pH indicators ..... 20 Figure 4.................................. 105 List of Appendices Appendix A.......................................................................................... Effect of pretreatments on the d-spacing of selected clay minerals........................2........................3............................. 103 List of Figures Figure 1........ 18 Figure 3.......................................... 113 Appendix C................................................................................. Reduction of sample size by quartering ..2.............. Colour Development – Azomethine-H Method..................... SOIL MOLYBDENUM .......................................................... 115 Appendix E.... mg/kg (Bashour............. 116 Appendix F............................................... 102 References ..... 92 17....... Sampling-sites selection methods for fertility test. 117 iii .. Texture triangle showing the percentages of sand.. Colour Development – Carmine Method............... 14 Table 2.................................................. Chemical characteristics of saline................... 22 Figure 5.......... Identification of kaolinite using its characteristic XRD patterns .................... silt and clay in the textural classes ........................................................ Measurement of Element Concentration Using Atomic Absorption Spectroscopy .....3. Electrical conductivity values for different CaSO4 concentrations in water ........................................ List of the atomic weights of the elements ............ 29 Figure 6. 58 Figure 9............................................... Data sheet for recording of hydrometer readings .......1................................3.... NI AND PB ........... 90 17.......... 99 21.............. 89 17............................... Effect of soil:water ratio and particle size on total gypsum extraction....................... 87 16................. 30 Figure 7............................ Nutrient range in soils........................................... POTENTIALLY TOXIC ELEMENTS ................................................CD........................... Identification of smectite using its characteristic XRD patterns ........................................................... Measurement of Concentration by Colourimetric Methods .......16................................................................................................ Modified textural triangle for determining soil texture by the feel method . 112 Appendix B................................

........................................................................... 118 iv ........... Conversion factors for SI and non-SI units (Soil Science Society of America Journal) ...Appendix G.......

6). It is also hoped that this manual will be a valuable reference to organizations helping in agricultural development projects in these regions. and elevated accumulation of calcium. researchers and chemists working in laboratories for providing soil testing and analytical services to farmers in arid and semi-arid regions. soluble salts accumulate to some high levels in certain areas. The surface layers of most of these soils.8 – 8. A number of books are available describing numerous alternative procedures for soil analysis. markedly influence the physical and chemical properties and the fertility status of these soils. Abundance of lime and gypsum. high evaporation.and magnesium-carbonates. These factors make the management of these soils difficult. sodicity. Because of low rainfall. and restricted leaching. salinity. which have been developed and adapted specially to the particular conditions of these soils. and users are often confused in selecting the appropriate methods. analytical methods. 1 . The saying "test and don't guess" is appropriate for the management of these soils. and sulphates.PREFACE About one fourth of the land surface is in arid and semi-arid regions. and gypsum content. teachers. which contain various kinds of deposits. It is believed that this publication will be of particular interest to students. and demand studies based on rightly adapted methods of soil analysis. and the determination of the problems related to irrigation and drainage. which lead to saline conditions. are described. are coarse textured and low in organic matters. In doing so. This publication aims to establish a middle ground between the so-called “cook-book” and the detailed comprehensive type of manual. and the accumulation of soluble salts. Soils of these regions are generally characterized by their slightly alkaline reaction (pH 7.

N. for further following up of this publication. Special thanks are due to R. Roy. are duly acknowledged.R. C. Motsara and A. 2 . editing and finalizing this document. Hamdallah. for conceptualization and initiation. and M. M. LiconaManzur. Bazza. Shammas for their technical contributions in revising.ACKNOWLEDGEMENTS The contributions of G.

yet little understood. It is difficult to successfully manage salt affected calcareous and gypsiferous soils due to their poor physical conditions. In addition. aeration is seriously hindered. and for what purpose. how it should be used. are carried-out on a trial and error basis without regard to soil properties and its fertilizer needs. Thus. Crop yield. The problem arises partly from the lack of proper methods of soil analysis that reflects the actual soil status. is a function of several factors. Phosphorus retention/fixation (precipitation of available fertilizer-P into less available forms) due to alkaline soil reaction and high Ca2+ activity. like the soil. So is water infiltration and movement because of poor porosity. both quantity and quality. fertilizer requirements of crops differ from one soil to another. soils of arid and semi-arid regions possess chemical properties that would set off certain nutritional problems. However. water. Zn. fertilizer practices. more fertilizers are being applied than before. Ironically. getting worse. An important reason. Yet. such as content of silica. as followed today in the Middle East. The outcome would be water logging and poor aeration. montmorillonite. 3 . Reduction in plant uptake of potassium due to poor aeration resulting from excessive soil moisture content. crop variety. micas. but agriculture production problems are. calcium carbonate and gypsum. in general. gypsum and soluble salts vary from one soil to another.INTRODUCTION With growing dependence on agriculture production in arid and semi-arid regions. use of fertilizers has increased tremendously. In addition to their poor physical conditions. and partly from the misunderstanding of what a fertilizer really is. The sandy soils vary in their chemical composition. etc. chlorite and attapulgite (Aba-Husayn and Sayegh. Mn and Cu under alkaline soil reaction. Micronutrient deficiencies due to reduced solubility of Fe. Soils of the semi-arid and arid regions vary widely in their condition and texture that range from sandy to loamy to clayey. Diagnosis of deficiency can be checked by analysis of plant tissues and by soil analysis that reflect the actual condition of the soil. the proportionate occurrence of calcium carbonate. like: Nitrogen volatilisation losses of surface applied ammonium or ammonium-forming fertilizers due to alkaline soil reaction and high Ca2+ activity. is the improper use of fertilizers when it comes to kind and application rate. A sound soil management programme should provide crops with an adequate amount and in balanced proportion of all essential nutrients for optimum production. which is a range of combinations of kaolonite. it should be recognized that fertility is only one of the major factors affecting crop production. management practices. 1974). The soil clay fraction varies in its mineralogical composition. climate. Because of poor structure.

Similar publication on methods of plant analysis will be considered at a future date. the need and motivation for this publication grew out of the need to establish the use of soil and plant analyses as a guide to fertilizer recommendations. Consequently.Restricted root development due to poor structure and hard pan. The scope of this publication has been kept limited to soil testing methods. 4 .

Thus safe working in a chemical laboratory needs special care. both in terms of design and construction of the laboratory building.GENERAL LABORATORY GUIDELINES In chemical laboratories. maintenance of temperature and humidity as specified is critical. For chemical operations special chambers also need to be provided. Inflammable gases are also used as a fuel/heating source. trapped in acidic/alkaline solutions and washed through flowing water. glassware and miscellaneous items in a laboratory should be maintained. and handling and use of chemicals. handling the chemicals and in waste disposal. An inventory of all the equipment. the use of acids. Care is needed to be taken to store acids and hazardous chemicals in separate and safe racks. Apart from this. Air temperature of the laboratory and working rooms should be maintained at a constant level between 20-250 C. The temperature influences even some chemical operations. Proper air circulation is also important so as hazardous and toxic fumes and gases do not stay in the laboratory for long. nitrous oxide and LPG may be kept under watch and properly sealed/capped and may be stored in ventilated cupboards. Hence. Laboratory Safety Measures Special Care is required while operating equipment. Equipment Electrical cables. Maintenance of clean and hygienic environment in the laboratory is essential for the good health of the workers. Soil samples are often affected by the temperature and humidity. A safe laboratory building should have suitable separate rooms for different purposes and for performing different operations. plugs and tubing need proper check to avoid accident. some chemical reactions during the process of analysis may release toxic gases and if not handled well. Various types of gas cylinders needed in the laboratory like acetylene. may cause explosion. 5 . chemicals. alkalis and some hazardous and explosive chemicals is inescapable. Humidity should be kept at about 50%. The release of gases and fumes in some specific analytical operation are controlled through fume hood.

Read the labels of the bottles before opening them. General Rules and Required Care Learn safety rules and use of first aid kits. hand protection gloves. Cyanides. In wet oxidation method of sample digestion. Use fume hood while handling concentrated acids. selenium. Clean up spillage immediately. Bottles with inflammable substances need to be stored in stainless steel containers. accident and damage to equipment. Keep the first aid kit handy at a conspicuous working place in the laboratory. Avoid direct contact with organic matter/rubber. Use forceps / tongs to remove containers from the hot plates/ovens/furnaces. solutions. Observe normal laboratory safety practice in connecting equipment with power supply. face shield and proper footwear should be used while working in the laboratory. Maintain instrument manual and logbook for each equipment to avoid mishandling. Never open a centrifuge cover until the machine has stopped. Waste Disposal Each country has special rules and methods for disposal of hazardous waste. All electrical work must be done by qualified personnel. vessels and wash bottles containing reagents. 6 . in handling chemicals and preparing solutions of reagents. destroy organic matter first with nitric acid. Wash hands after handling toxic / hazardous chemical. Personal safety aids such as laboratory coat. Chemicals may be properly labelled indicating their hazardous nature. samples and water. Never suck the chemicals with mouth but use automatic pipetting device. Keep the working tables/space clean. bases and hazardous chemicals. safety glasses. Handle perchloric acid in fume hoods. chromates. fume hood may be used. While working with chemicals such as perchloric acid.Chemical Reagents Hazardous chemicals may be stored in plastic bottles. Do not use laboratory glassware for eating/drinking. Always put labels on bottles. arsenic. cobalt and molybdate are very commonly used but hazardous chemicals and should never be disposed off in the laboratory sink but collected in a metal container for proper disposal at the specified places and in the manner as described in the country’s law for waste disposal. Add acid to water and not water to acid while diluting the acid.

which when implemented properly. Check on the performance of the instruments. an effective check on all the activities and processes in a laboratory can only ensure that the results pronounced on a product quality are within the acceptable parameters of accuracy. 7 . the deviated procedure may be fully documented. Registration of samples. Thus. which is defined by ISO as “the operational techniques and activities that are used to satisfy quality requirements”. Procedure for operating instruments. If.Laboratory Quality Control Quality control is an important part of quality assurance. Adoption of sample-check system as a batch control within the laboratory. recorded and reported”. ensure that the results delivered are acceptable and verifiable by another laboratory. In quality control system. for justifiable reasons. which describes the regularly recurring operations relevant to the quality of the investigation. External check – inter-laboratory exchange programme. the laboratory has to run in a well regulated manner where the equipment are properly calibrated and the methods and techniques employed are scientifically sound which will give reproducible results. Thus. The GLP can be defined as “the organizational process and the conditions under which laboratory studies are planned. performed. the following steps are involved. To ensure obtaining accurate and acceptable results of analysis on a sample. SOP may be prepared for: Safety precaution. Standard Operating Procedure A Standard Operating Procedure (SOP) is a document. The purpose of a SOP is to carry out the operation correctly and always in the same manner. Quality assessment or evaluation is necessary to see if the activities performed to verify the quality are effective. Good Laboratory Practice (GLP) has to be followed. any deviation is allowed from SOP. A SOP should be available at the place where the work is done. Calibration or standardization of instruments and chemicals. the GLP expects a laboratory to work according to a system of procedures and protocols whereas the procedures are also specified as the Standard Operating Procedure (SOP). In a laboratory. monitored. Analytical methods and preparation of reagents. For ensuring the high standards of quality.

In quantitative analysis. In ensuring high accuracy in analysis. The mean deviation or the relative mean deviation is a measure of precision. Error. Precision and Accuracy In analysis. when the quantity is measured with the greatest exactness that the instrument. The relative error is the absolute error divided by the true or most probable value. Precision always accompanies accuracy. For all estimation. chemical reagents involved in such aspects must always be of high purity which is referred as ARgrade (Analytical Reagent). The average value is accepted as most probable. There could be a number of factors responsible for this difference which is also referred as ‘error’. all the operations have to be properly documented so as no chance is left for adhocism in any manner. their concentration/strength and the accuracy of the instruments and the skill of the technician are important factors. Precision. but a high degree of precision does not imply accuracy. Accuracy and Detection Limit Error Error is an important component of the analysis. accurate preparation of reagents including their perfect standardization is critical. Not only this. 8 .To sum up. This may not always be true value. it is found that the results of successive determination differ among themselves to a greater or lesser extent. even the purity of chemicals is important. method and observer are capable of. The accuracy of a determination may. be defined as the concordance between it and the true or most probable value. Accuracy expresses the correctness of a measurement. The purity of chemicals. in some cases it may be large. The error in absolute terms is the difference between the observed or measured value and the true or most probable value of the quantity measured. The absolute-error is a measure of the accuracy of the measurement. Precision is defined as the concordance of a series of measurements of the same quantity. the precision of a measurement rarely exceeds 1 to 2 parts per thousand. therefore. while precision expresses the reproducibility of a measurement. In some cases. In any analysis. the difference in the successive values may be small. The error may be caused due to any deviation from the prescribed steps required to be taken in analysis. where actual measurement of a constituent of the sample in terms of the “precipitate formation” or formation of “coloured compound” or “concentration in the solvent” is a part of steps in estimation. other important terms to be understood are precision and accuracy. and the reliability of the result depends upon the magnitude of this difference.

preparation of standard curve and the preparation of reagents may be repeated till acceptable results are obtained on the standard sample. In quantitative terms. the process of calibration. the lowest contents of such analyte may be decided through appropriate research as the values of interpretable significance. need arises to measure very low contents of analytes. The use of ‘sequence control’ samples is made in 9 . Use of blank A blank determination is an analysis without the analyte or attribute or in other words. the remainder of the old ones always has to be measured as a mutual check. The capacity of the equipment and the method may be such that it can detect the traces of analyte in the sample. Apart from independent standard. an analysis without a sample by going through all steps of the procedure with the reagents only. while selecting equipment and the testing method for such purpose. After assuring this. The extent of deviation of analytical value on a standard sample indicates the accuracy of the analysis. However. To check and verify the accuracy of analysis. certified reference samples can also be used as ‘standard’. Once. Such samples are obtained from other selected laboratories where the analysis on a prepared standard is carried out by more than one laboratory and such samples along with the accompanied analytical values are used as a check to ensure the accuracy of analysis. Modern equipment is capable of such estimation. When new standard is prepared. Such limits are called as detection limits or lower limits of detection. analysis on unknown sample has to be started.Detection Limit In the analysis for trace elements in soils. its execution has to be done with utmost care. The service laboratories are generally provided with such limits. If the results are not within the acceptable levels of accuracy. it is important to have information about the lowest limits up to which analytes can be detected or determined with sufficient confidence. Independent standard can be prepared in the laboratory from pure chemicals. Quality Control of Analytical Procedures Independent Standards The ultimate aim of the quality control measures is to ensure the production of analytical data with a minimum of error and with consistency. an appropriate method is selected. Use of blank accounts for any contamination in the chemicals used in actual analysis. plants and fertilizers and for environmental monitoring. independent standards are used in the system. The ‘estimate’ of the blank is subtracted from the estimates of the samples.

hence all types of the laboratories may not be in a position to modify the standard method. They should follow the given method as accepted and practised by most other laboratories. It is essential that analyst is aware of the possible presence of a blind sample but is not able to recognize the material as such. This sample is inserted by the head of the laboratory in batches and times unknown to the analyst. Internal quality control Apart from validation of methods. Validation of procedures of analysis Validation is the process of determining the performance characteristics of a method / procedure. Validation of own procedure In-house validation of method or procedure by individual user laboratory is a common practice. Blind sample A sample with known content of analyte. 10 . The data may be inadequate. Many laboratories use their own version of even well established method for reasons of efficiency. Such changes are often introduced to consider local conditions. Two types of validation are followed. It is a pre-requisite for judgement of the suitability of produced analytical data for the intended use. This requires continuous monitoring of the operation and systematic day to day checking of the produced data to decide whether these are reliable enough to be released. cost and convenience. one with a low content of analyte and another with very high content of known analyte (but the contents falling within the working range of the method) are used as standards to monitor the accuracy of analysis. a system of internal quality control is required to be followed by the laboratories to ensure that they are capable of producing reliable analytical data with minimum of error. Validation of such changes is the part of quality control in the laboratory. Generally two samples. cost of analysis.long batches in automated analysis. It is also a kind of research project. This implies that a method may be valid in one situation and invalid in another. A change in liquid solid ratio in extraction procedures for available soil nutrients and shaking time etc. if the method is less accurate than required. If a method is very precise and accurate but expensive for adoption. it may be used only when the data with that order of precision are needed. Various types of sample material may serve as blind samples such as control samples or sufficiently large leftover of test samples (analysed several times). required accuracy and efficiency. result in changed value. hence needs validation.

the sample preparation may be done with great care to ensure that the: Sample is homogenous. pipettes. glassware may not be properly cleaned and the equipment may be defective or the sample intake tube may be clogged in case of flame photometer or Atomic Absorption Spectrophotometer. Standard may be old or wrongly prepared. Round off the analytical values to the 2nd decimal place. Material has uniform and correct particle size as sieved through a standard sieve. Sample material is stable. the value of second decimal may be raised by 1. If it is more than 5. Pipette may indicate wrong volume. Inter-Laboratory sample and data exchange programme: 11 . and even more when variants of standard procedures are introduced. it requires thorough check on sample identification. Relevant information such as properties of the sample and the concentration of the analyte are available. Validation is not only relevant when non-standard procedures are used but also when standard procedures are used. standards. corrective measures should be taken. As and when an error is noticed in the analysis through internal check. The results of validation tests should be recorded in a validation report from which the suitability of a method for a certain purpose can be deduced. This involves an inter-laboratory programme of testing the method by a member of selected renowned laboratories according to a protocol issued to all participants. The error can be due to calculation or typing. The samples under analysis may also be processed/prepared in such a way that it has similar particle size and homogeneity as that of the standard (control) sample. glassware. Source of error may be detected and samples be analysed again. The value of 3rd decimal place may be omitted if less than 5. Validation of the Standard Procedure This refers to the validation of new or existing method and procedures intended to be used in many laboratories including procedures accepted by national system or ISO. dispensers. Since the quality control systems rely heavily on control samples. If not.Following steps need to be taken for internal quality control: Use a blank and a control (standard) sample of known composition along with the samples under analysis. chemicals. calibration procedure and equipment.

They come under the Wageningen Evaluating Programme for Analytical Laboratories (WEPAL) of the Wageningen Agricultural University. The laboratory exchange programme exists for method performance studies and laboratory performance studies. some laboratories or the organizations have devised the system where periodically samples of known composition are sent to the participating laboratory without disclosing the results. 12 . nationally and internationally. each laboratory will benefit if it becomes part of some sample/method check and evaluation programme. For quality check. Other programmes run by the Wageningen Agricultural University are: International Sediment Exchange for Tests on Organic Contaminants (SETOC). Some of Such Programmes are: International Plant Analytical Exchange (IPE) Programme. It provides a possibility for assessing the accuracy of the method being used by a laboratory and also about the adoption of the method suggested by the lead laboratory. hence doubt may persist. In such exchange programme. Another International Organization operating such laboratory and method evaluation programme is Association of Official Analytical Chemists (AOAC) of USA. International Manure and Refuse Sample Exchange Programme (MARSEP). The results of the other laboratory may or may not be biased. The system of self-check within the laboratory also has to be regularly followed.If an error is suspected in the procedure and uncertainty cannot readily be solved. and International Soil Analytical Exchange (ISE) Program. One of the most popular programme of AOAC is for Fertilizer Quality Control Laboratories and the analytical methods for fertilizer testing. it is not uncommon to have the sample analysed in another laboratory of the same system/organisation. regionally. The participating laboratory will analyse the sample by a given method and find out the results. The sample checks by another accredited laboratory may be necessary and useful to resolve the problem. the Netherlands. An accredited laboratory should participate at least in one inter laboratory exchange programme. Such programmes do exist locally.

SOILS OF ARID AND SEMI-ARID REGIONS The soils of arid and semi-arid regions are the products of several factors. gypsum is present in sedimentary deposits from which the soil was derived and in others it is formed by precipitation of Ca2+and SO42. The CaCO3 rich soils are widely spread in the Near East region due to year-round warm dry climatic conditions and insufficient annual rainfall (less than 400 mm) to dissolve the lime and leach it off the soil profile. Calcareous Soils Most soils of the arid and semi-arid regions in the Near East are high in calcium because they were developed from limestone and sandstone of various hardness.1. low water holding capacity. Salt Affected Soils Since ancient times man had noticed that there are soils that contain excessive amounts of salts. the soils have a potential for agricultural development under rainfed as well as irrigated conditions. Though.3. The amount and form of CaCO3 (total versus active) and its distribution down the soil profile affect soil physical and chemical characteristics.2. Plant growth on these soils is sporadic. Predominantly. production is low and 13 . Solubility of gypsum is low.6 g/litre of CaSO4. mainly climate. 1. (1978). the productivity is limited due to low fertility. prevalence of hardpan and faulty irrigation practices. parent materials and topography. like 2. 1. In some soils. Gypsiferous Soils Gypsum is found in soils of the arid and semi-arid regions in amounts ranging from traces to high level. Measurement of total gypsum in soils by conventional methods is unreliable as was proven by Sayegh et al.(during salinization) when the ground water is brought upward by capillary action to replace water lost by evaporation. the following types of soils are found in arid and semi-arid regions 1. The dominant rocks are limestone.1.2H2O in distilled water at 25 C. sandstone and metamorphic rocks. Figures quoted in the literature for gypsum contents are commonly much lower than the actual amount present. with the same amount of CaCO3. Gypsiferous soils have different forms of gypsum in soils because of the varied sources and conditions under which it forms (Boyadgiev and Sayegh. have less active CaCO3 than the soils derived from soft limestone (marl). shallow soil depth. 1992). soils derived from hard limestone. Continued irrigation of gypsiferous soil lead to subsidence and collapse of the irrigation and drainage systems. Wind-blown sand constitutes a major part of the soil material. According to the research done in Lebanon by the authors. Gypsum is encountered in variable depths and salts accumulate because leaching is not active.

0 <4.5 <8.2 and 0. Introduction of irrigation without providing efficient drainage changes the natural water balance in the newly irrigated areas causing the ground water level to rise up with water logging. salinization or sodification.03 < P/ET < 0.0 >4.5 14 .5 >8. Chemical characteristics of saline. In arid and semi-arid regions “P/ET” (the ratio of precipitation to evapotranspiration) is 0. non-saline sodic and saline sodic soils Soil Saline Sodic (nonsaline) Saline Sodic Source: Richards. 1954 EC dS/m >4.0 ESP <15 >15 >15 pH <8. 1995). The chemical properties of salt affected soils are summarized in Table 1 Table 1.2 < P/ET < 0.5.farmers usually abandon such lands to let them eventually become a barren desert. The primary salinity usually spreads out in poorly drained lowlands in arid and semi-arid regions. respectively (Balba.

It is not effective on sandy or gravelly soils. so. Various types of hand augers. The sub-sample analyzed represents the gross sample accurately. SOIL SAMPLING AND PREPARATION Soils are sampled for different purposes and. that the tool allows for a uniform slice to be taken from the surface to the depth of insertion of the tool. 15 . but will not collect samples in dry non-coherent soils unless they are wetted during boring.1. gravelly or stony soils or on dry soils of any texture. Therefore. such as: Bucket auger: This is a cylindrical auger with specially designed cutting bits at the lower end. If the collected soil samples are not truly representative samples.2. This type is the most suitable for medium textured soils. According to Cline (1944). Screw auger: The screw auger is of limited value for soil observation because of the severe disturbance of the sample during collection. 2. different methods are employed to satisfy the purpose for which the sample is collected. In general. Dutch auger: This auger is particularly effective on coherent moist and rather wet soils of high clay content. Bucket auger. It can be useful in collecting samples for fertility evaluation and rapid soil examination to check map boundaries. No changes occur in the gross and sub-samples prior to analysis. It is not effective on sandy. results of the analyses will not reflect the properties of the soil under investigation. and second. collecting a representative soil sample from the field is the most important aspect of soil analysis. The analytical data produced are truly measuring the soil parameter under investigation. It penetrates most soils and is particularly effective in gravelly soils. Sampling errors are often greater than analytical errors. soil-sampling tools are divided into four major groups: 1. Jarret auger: This is an open bucket auger with side cutters of robust design. shovels or garden trowels have proven to be useful tools in sampling arid and semi-arid soils. that the same volume of soil be taken from each sampling point. the analytical values can serve as an accurate description of the soil property under investigation if: The gross (or bulk) sample accurately represents the whole soil from which it was taken. Soil Sampling Tools Tarzi (1984) reported two important requirements of a soil sampling tool: first.

shovels. However. However. 2. How well does the soil sample represent the field in question? The analytical aspect of soil testing may correlate perfectly with crop response. In most instances this is often enough to determine whether the fertilization programme is adequate. 2. The reason for the lower values for available-P in spring could be the increased soil microbiological activities. and whether there is need for an increase or decrease in the rate of application. then the soil test result cannot have much value. 2.Tube sampler: This sampler is useful for rapid sampling of topsoil in medium textured soils. knives. It is not effective on non-coherent soils. 3. It is usually recommended that each field be tested once every three years. Blades.2. It is important to take this into consideration in the evaluation. Sampling for Soil Fertility Tests Chemical analysis of soil samples is a prime source of information on the relative availability of plant nutrients. would give lower values of available-P than samples collected in autumn when soil temperature is low. which use up part of the soil-P. samples collected in spring.2. but if the soil sample is unrepresentative. and core samplers. For example. hard clays or gravelly soils. spades. Tubes and cylinders. then the soil test will not be very useful and it may be misleading. A key point is to collect samples in time to be analyzed for deciding fertilizer application rates and their application. Time of Sampling The correct time of sampling cannot be decisively specified. if soil test correlations are weak or soil samples unrepresentative. When the soil test is calibrated with crop response and soil samples are properly obtained. does the soil test correlate with fertilizer requirements and crop performance in the field? 2.1. sampling after fertilization should be avoided. This leads to the following questions: 1. the test results can be a strong pivotal point around which management decisions on fertilizer application and soil fertility management can be taken. Samples can be taken during crop growing period when soil content of nutrients is stressed. Does the soil nutrient level indicated by the chemical analysis actually have a relationship to the nutrient uptake and growth of plants? In other words. 16 . as soil starts warming up. Hydraulic equipment.

Methods of Sampling A field can be sampled to estimate its fertility through soil analysis by several methods. the most commonly recommended sampling procedure is the composite sample. For example. Depth of Sampling Samples are usually collected from soil surface layer down to a depth of 15-25 cm in cultivated fields. 30-60 and 60-100 cm. Areas that vary in appearance.2. However. it is advisable to collect separate samples from the 0-15 and 15-30 cm layers. compost or crop residues have been piled should be avoided. A sample taken from such an area would be completely misleading. Consequently. Sampling areas are often traversed in 17 . 0-30. Sampling recently fertilized bands. 2. The purpose of this procedure is to minimize the influence of any local variability in the soil. When fertilizers are broadcast on soil surface. In fruit tree orchards. areas adjacent to roads. These include.. Hence. dead furrows. A good composite sample is made up of a number of soil cores taken at random from 15 – 20 sites in a 1 – 5 ha cultivated field. or where manure. still the samples must be collected all through the plough-depth of 15-25 cm. i.2. the depth of soil sampling should be extended to the depth of root zone. Multiple samples taken systematically on a grid pattern. The multiple sampling method is the best because. 2. band-applied fertilizers are not uniformly applied over the soil surface. In vegetable fields. and areas that cannot be treated or fertilized separately should be omitted. a single sample consisting of the composite of several randomly selected soil cores.e.3. Some farmers plough to a depth of 30 cm. Thus. in addition to providing estimates of nutrient levels. A random distribution of individual sample sites would be ideal. Intensive soil sampling will not be practical unless the economic returns justify the costs. among others: 1. it shows variation in fertility from one part of the field to another. equally reliable information is obtainable with much less effort by reducing the sampling area when the fields are relatively uniform. Figure 1 shows a sampling pattern in a heterogeneous land. Many growers are directing attention to these small spots in their fields and treating them as needed.2. soil type. and then samples should be collected up to this depth. drainage. and previous treatments should be sampled separately. slope. most recommendations call for taking borings at 15-20 locations over the field for each composite sample. it is advisable to take separate samples from these localized areas of poor crop growth. In addition.2. if the root system reaches to about 100 cm of depth. there may be some spots in the field where fertilizers were spilled or plant refuse was buried. A composite sample. or where the topographic conditions are such that high variability is expected.

soil samples should be collected from the root zone of trees. In fruit tree orchards. Figure 1.. 1984) Figure 2. i. Sampling pattern for fertility test in a non-uniform land (Sample numbers refer to composite samples) (Source: Tarzi. around which soil is to be sampled.e. Sampling-sites selection methods for fertility test 18 . the zone moistened by irrigation. Some of these methods are presented in Figure 2. Trees. are selected in a random or systematic pattern. A reasonable number of sites (trees) would range from 520% of total number of trees.a zigzag pattern to provide a uniform distribution of sampling sites. particularly those irrigated by a drip system. reaching to the depth of the root system.

20-30 cm intervals. and delineate these areas on a map. In the laboratory. More important are the survey objectives. In soils having distinguishable genetic horizons. and on a sample card placed inside the bag. pits are dug to about two meters depth or to bed rock if it is shallower than 2 m. geology. Bags should be properly labelled. Information recorded on the data sheet must be accurate. 2. landforms and spatial variability of the land. Bags should be closed tightly. Air-drying is the most accepted procedure of sample preservation and may reduce the rate of possible reactions in the disturbed soil sample. are first studied to collect some basic information about relief and other physical feature of the terrain to be surveyed. rocky soils. placed in wooden or cardboard box. Arial photos taken for the terrain to be surveyed. Questions for which reliable answers cannot be provided should be left unanswered. as in depositional soils. Soil surveyors correlate soil series and mapping units with landform units and land surface features. The methodology will vary in details depending upon the type of terrain. Normally. This is the composite sample to be sent for analysis. Information such as sample number. In areas with complex soil patterns. Soil Sampling for Soil Survey and Classification Studies Soil survey is a type of pedological study the purpose of which is to describe soil characteristics for areas of a few to hundreds or thousands of hectares. e. the average observation density will be one pit per 15-20 hectares. Soil profiles are studied and samples are taken from each horizon.2. and date of sampling should be written on the bag from outside. samples are collected from a sequence of depth intervals. Soil surveyors commence from a convenient point or landmark. the mapping scale. the density will be one per 10-15 hectares. and then shipped or taken to the laboratory. undulating and ridges. The observation density will be lower in areas of poor soils such as shallow soils. After mixing well the gross soil sample. In areas with a relatively simple soil pattern. Where surface soil did not develop from the underlying parent materials. A soil sample should not be allowed to stay moist for extended periods 19 . The dependability of these images serves in approaching and executing soil survey projects.g. and now images taken by remote sensing from satellites. the collected sample is spread thinly on a plastic sheet or tray for air-drying.3. about one kg is transferred into a clean plastic or canvas lined with plastic bag. soil cores are placed in a clean container and clods are crushed. and the complexity of the soil pattern to be surveyed. these surveys are government projects carried out to determine and develop land use and management. It is essential that a Field Data Sheet be filled and sent with the samples to the laboratory (Figure 3). Preparation of Soil Samples Following the sampling process.4. and then select fields or sites for boring or digging of pits. depth.

of cores Purpose of Analysis: Slope: 1-2% 2-5% 5-10% 10-25% > 25% Never Irrigated 1-5 5-15 > 15 Irrigation Method: Flood Furrow Sprinkler Center Pivot Drip Rainfed Never Cultivated 1-5 years 5-15 years >15 years Years of Irrigation: Years of Cultivation: Drainage: Good Moderate Poor Manure/Fertilizer Application History: Manure (type) ________________________ Fertilizers (mineral) ____________________ Rate (kg/ha)_______________________ Rate (kg/ha)_______________________ Note: Questions for which accurate answers cannot be provided should be left unanswered. Soil aggregates should be broken carefully to accelerate the drying process. Figure 3. although these reactions are still possible sources of error. It is generally assumed that chemical and biochemical reactions in airdry soils are reduced to a minimum.of time. _____________ Collector _______________ Address______________________ Date ___________ Area _______________ Location_______________ Owner ___________________ Farm Size ____________________ Vegetative Cover_________________________ Source of Water ____________________ Water Quality ______________________ Sample Depth _____________________ Previous Crop ______________________ Site Selection Method: Random Zig Zag Two Way Diagonal Two Way Cross-Strip Test Plot Capability Assessment Fertility Evaluation Salinity Appraisal Soil Classification Sample Type: Individual Composite No. Field data sheet 20 . FIELD DATA SHEET Sample No.

4. Drying may also result in increased cementation. Other possible results from drying at higher temperatures are chemical changes in the oxidation status of elements. ball mills. clods and large aggregates are crushed and mixed. The analysis in question. steel mortars for smaller aggregates. which may particularly affect particle size distribution analysis. The degree of fineness to be attained. and rocking boards for small aggregates. an agate or boron carbide mortar can be used. Grinding and Sieving of Soil Samples Thorough mixing requires that the sample be crushed and ground to particles of uniform size. 1972). samples may be placed in forced draft of moving air. After drying the sample. Care should be taken not to break the individual soil particles during the grinding process. plate grinders or ball mills or rod mills are used. 21 . rod mills. the measurements are done on moist soil samples as collected from the field. Jaw crushers are used for crushing large aggregates. The degree to which such changes occur varies with temperature and time of drying. This will serve as stock samples for analysis. The sample is mixed with stainless steel rods or balls. 1986) and microbiological reactions. For large amounts of samples.To accelerate the drying process. in a container and the container is rolled over a period of time. For least contamination and for small amounts of samples. agate mortars. 2. and boron carbide mortars. The choice of equipment depends on four factors: 1. The types of grinders used are plate grinders (friction mills). The amount of sample to be crushed or ground. Then the crushed material is further ground to pass 2 mm sieve. rod and ball mills are efficient grinders (Coghill and Devaney. A separate sample is taken to determine soil moisture which is then used to convert results to oven-dry basis. 1937). the soil is sieved through a 2 mm sieve and stored in airtight glass or clean plastic containers as soon as possible to avoid adsorption of gases in the laboratory. The contamination that can be tolerated. variation in the content of available nutrients (Sayegh. Soil aggregates can be crushed by using jaw crushers. 3. like NO3-N and NH4-N. Then. hardened steel mortars or rocking boards (Tan. 2. When properly operated. The purpose of grinding is to reduce heterogeneity and to provide maximum surface area for physical and chemical reactions. Various devices are used for crushing and grinding soils. After grinding. but not in heated air. 1996). For some quick soil analysis. The temperature must not exceed 35°C because drying at elevated temperatures may cause drastic changes in the physical and chemical characteristics of the soil sample (Hesse.5.

Reduction of sample size by quartering 22 . a random and unbiased method of sub-sampling is essential. The sample is spread uniformly over a plastic sheet and divided into four equal portions (Figure 4). and the sub-sample taken for analysis should represent the soil characteristic of the field under investigation. 1972). 1943. Sample splitting can be performed with a mechanical sample splitter. 2. In order to achieve this goal. 1 discard 2 keep Keep 3 4 discard Figure 4. Reduction of Sample Size When a very large sample is collected. Another way for reduction of sample size is by quartering. 1938. such as a riffle sampler. Hesse. Therefore. This process of quartering can be repeated as many times as necessary until the proper size of sample is attained. This process can be repeated as many times as necessary. whereas the remainder is discarded. the sieve size should be reported with the results of analysis.6. The bulk sample must be reduced in size. it is necessary to reduce the size of the sample for ease of storage and handling. Analysis of samples that are passed through sieves of unspecified sizes may produce results that would not be comparable to internationally accepted data. Willard and Dhiel. Portions 2 and 3 are collected and thoroughly mixed. by which the sample is divided in half by a series of chutes (Krumbein and Pettijohn.samples should be stored in a cool and well-ventilated room.

Apparatus Moisture determination cans Analytical balance Drying oven Desiccator Procedure 1. Cohesion is the mutual force of attraction between water molecules. Calculation Weight of water W2 W3 W3 W1 W2 W3 W3 100 W1 Weight of oven dry soil Moisture % (oven dry basis) 23 . or until constant weight is reached.0 (high tension).54). The point at which water is held in soil after excess water has drained out by gravity is called field capacity (pF = 2. Adhesion is the force of attraction between the solid soil particles and water molecules. 2.2). weigh the can accurately with the oven-dry soil in it. After cooling. Compute percent moisture content on oven-dry basis.3. Another force that affects water retention and movement in soil is the capillary force. The pF is the term mostly used to express soil moisture. Place the can with the lid under it in a drying oven at 105°C for 24 – 48 hours. 4. 3. cover it tightly with the lid. although other terms are also used. Water in air dry soil is held with a tension of pF 6.0. Record the weight (W3). Place about 50 g of soil in the can and weigh accurately along with the lid (W2). 5. like atmosphere or bar. is known as wilting point (pF = 4. Weigh accurately a metal can with lid (W1). The point at which water is held in soil at a force that plants cannot extract at a sufficient rate to maintain turgor. Water can exist in soil under a tension varying from pF = 0 (no tension) to pF = 7. which is a function of the size of micropores or capillaries. The amount of water between field capacity and wilting point is called available water. and place in a desiccator to cool. At this point the plants start to wilt. SOIL MOISTURE Water is held in soil by adhesive and cohesive forces. 6. Remove the can from the oven.

soil moisture is expressed on oven-dry basis. the weight of the wet-soil sample (W2 – W1) is used instead of the oven-dry weight (W3 – W1): Weight of water W2 W3 W2 W1 Weight of wet .soil Moisture % (wet soil basis) W2 W2 W3 W1 100 24 . However. moisture content is expressed on wet-soil basis. To do so.The corresponding moisture correction factor (mcf) for analytical results or the multiplication factor for the amount of sample to be weighed in for analysis is: Moisture correction factor = 100 % moisture 100 Normally. for certain purposes.

particles should be moving down freely Determination of the particle size distribution of gypsiferous-calcareous soils is a tedious and time-consuming process. better known as specific surface area. increases. the following can be concluded: 25 . or particle size distribution. As particle size decreases. total surface area. hence the method is known as Bouyoucos Method. which inhibits soil dispersion. Since most of the physical and chemical properties of soil are related to surface activity. As soil particles are freely settling down the water column. Because of their differential settling rate in water. although gypsum has marked effects on the physical properties of soils and it is most desirable to determine the particle size distribution without removing the gypsum fraction.4. they are sorted according to particle size. The estimation of texture under field conditions is misleading because of the presence of gypsum crystals in various sand-sized fractions. The forms and degree of crystallization of gypsum particles influence the feel of the soil and as a result field estimates of texture are generally coarser than indicated by laboratory determinations. is usually removed from soil samples before analysis. the size fractions are sorted into different size ranges.1. Introduction Soil texture. Coarse particles. determination of particle size distribution is a standard procedure for characterizing and classifying soils. move down faster than fine particles. So far. The Bouyoucos Hydrometer is calibrated to read the amount of solid particles remaining in suspension. Based on the experience gained from the analysis of a large number of gypsiferous soil samples. no method for the determination of the particle size distribution of gypsiferous-calcareous soils is entirely satisfactory. Hesse (1974) and Matar and Douleimy (1978) developed methods for the preparation of a stable suspension of gypsiferous soils without removing the gypsum fraction. like sand. Two basic conditions are required in this method: Dispersion of the soil sample into a state of single grain particles During sedimentation. There is a direct relation between particle size and the total surface area of particles in a given weight of soil. SOIL TEXTURE – PARTICLE SIZE DISTRIBUTION 4. Vielliefom (1979) gave a substantially improved method based on that of Hesse. Gypsum. is a rather stable soil characteristic which influences the physical and chemical properties of the soil.

but it increases again as gypsum content goes above 45 percent. Dispersion Individual soil particles must be separated from each other. aggregates breakdown is further facilitated by mechanical stirring.02-2. or at least render them ineffective. but it is mostly present in the coarse and fine sand fractions (0. The distribution of gypsum within the various size-fractions depends on the total amount of gypsum (Vieillefon.2.1. This fraction does not change as gypsum content increases from 25 to 45 percent. 4. The sodium monovalent cation replaces the usual polyvalent cations adsorbed on soils. For most samples with gypsum content between 10 and 25 percent. Once the soil aggregates are separated into individual particles. Since aggregates of solid particles are usually held together by some kind of binding agent. it is first necessary to remove these substances. The mixture of dispersed soil particles in water is called a soil suspension. The polyvalent cations are also reduced in activity as a result of reaction with the phosphorus and consequent precipitation. The adsorbed sodium cations raise the electronegativity of colloids until these particles repel each other and remain dispersed. thereby breaking interparticle linkages. and kept separated during the determination in order to correctly measure particle size distribution. the relationship is not significant. 3. The difference between the weight of such fractions obtained after treatment at 50°C and 105°C shows the following: The fraction less than 20 μm in diameter is greater when the total content of gypsum is about 10 percent. Sodiumhexametaphosphate is an effective chemical dispersing agent for two reasons: 1. The amount of the fractions greater than 20 μm in diameter increases as the total amount of gypsum increases. Gypsum is found in all size fractions. After the binding agents are removed.2H2O during oven drying at 105°C. and decreases with the increase of gypsum content to about 25 percent. they are described as dispersed particles. 26 . 2. 1979). Dispersion is achieved by chemical and mechanical means. The sum of the various size-fractions of gypsiferous horizons may be less than 100 percent due to dehydration of CaSO4. 2.0 mm) followed by the silt fraction.

Bouyoucos determined that after 40 seconds all sand-sized particles (0. the settling rates of dispersed particles in water are measured. with 1 000 ml mark 36 2 cm from bottom Bouyoucos Hydrometer calibrated at 200°C Thermometer C° Reagent Sodium hexametaphosphate. particles settle faster with increased temperature.4. After two hours. 1 litre. d1. and the difference between the densities of the particle. r. is directly proportional to the square of the particle's effective radius. Na6O18P6 solution (examples of commercial names: Calgon. Bouyoucos Method Apparatus Electric mixer (stirrer). g. n. In practice. glassy sodium): Dissolve 50 g of Calgon in water and dilute the solution to a volume of 1 litre 27 . the amount of material remaining in suspension at any time is measured with a hydrometer. Density of water and its viscosity are both affected by temperature. This is why it is necessary to apply correction for temperature. Sedimentation In sedimentation techniques. d2. 4. and thus. with baffled stirring cup Settling cylinder Graduated cylinder.4.3. particles larger than clay (0. but inversely proportional to the viscosity of the liquid. which indicates the density of the suspension at the hydrometer's centre of buoyancy.02 mm and larger) settle out of the suspension and do not influence the hydrometer reading.002 mm) settle out of the suspension and do not affect the hydrometer reading any more. Stocke's law is used to express this relationship: V 2 r 2 g(d1 d2 ) x 9 n The formula shows that settling velocity. and that of the liquid. the acceleration of gravity. Graham’s salt. Large particles are known to settle out of suspension more rapidly than do small particles. V. This is because larger particles have less specific surface area and hence less buoyancy than small particles.

The hydrometer is calibrated to read grams of soil material in suspension.36 to the hydrometer reading. 9. Fill the cup to its half with distilled water and add 10 ml of sodium hexametaphosphate solution. 10. Weigh 50 g oven dried fine textured soil (100 g of coarse textured soil) into a baffled stirring cup. carefully insert the hydrometer and read the hydrometer at the end of 40 seconds. 4. 8. Record the readings on the Data Sheet for Hydrometer Readings (a sample is shown in Figure 5). Remove hydrometer and shake the suspension vigorously in a back and forth manner. After 20 seconds. 28 . Avoid creating circular currents in the liquid. Correct for temperature as described above. Repeat step 4 and 5 to obtain hydrometer readings within 0. silt and clay as calculated on the Data Sheet. Place the cylinder on a table and record the time. From the percentage of sand. Transfer quantitatively the suspension to the settling cylinder by washing the cup with distilled water. fill to the upper mark on the settling cylinder. Place the cup on stirrer and stir until soil aggregates are broken down. Measure the temperature of the suspension. This is the corrected hydrometer reading. This usually requires 3-4 minutes for coarse textured soils and 7-8 minutes for fine textured clay. 6.36 from the hydrometer reading. use the diagram for textural triangle (Figure 6) to determine the textural class of the soil. subtract 0. Take a hydrometer reading exactly two hours later. 3. If 100 g of coarse textured sample was used. 2. and for each degree below 20°C. 7. Fill the cylinder to the lower mark with distilled water after placing the hydrometer in the liquid.5 g differences from each other.Procedure 1. Re-shake the suspension and place the cylinder on a table where it will not be disturbed. For each degree above 20°C add 0. 5. as they will influence the settling rate.

feel it with their fingers when dry. Percent sand (line 9 Percent clay (line 10 line 2) line 2) 100 100 (10) (11) (12) (13) (14) Percent silt (find the silt by difference. Soil class (as per Figure 6) Figure 5. and then they come up with a skilled guess about the textural class of the soil (Figure 7). the 40-second corrected hydrometer reading actually gives the grams of silt and clay in suspension. The weight of sand in the sample is obtained by subtracting line 5 from line 2) Grams of clay (the corrected hydrometer reading at the end of two hours represents grams of clay in the suspension since all sand and silt has already settled by this time). 29 . therefore. Data sheet for recording of hydrometer readings Some experienced field men take a sample of soil in their hand. and then inspect its stickiness after wetting. Subtract the sum of the percent sand and clay from 100).(1) (2) (3) (4) (5) (6) (7) (8) (9) Soil sample identification number Soil weight (g) Forty second hydrometer reading (g) Temperature of suspension (C°) Corrected 40-second hydrometer reading (g) Two hours hydrometer reading (g) Temperature of suspension (C°) Corrected 2-hour hydrometer reading (g) Grams of sand (the sand settles to the bottom of the cylinder within 40 seconds.

32 percent silt and 13 percent sand has a clay texture).Figure 6. Figure 7. Texture triangle showing the percentages of sand.. silt and clay in the textural classes (the intersection of the dotted lines shows that a soil with 55 percent clay. Modified textural triangle for determining soil texture by the feel method (Source: Foth et al. 1977) 30 .

Weigh 25 g of air-dry soil and transfer into an 800 ml Erlenmeyer flask. Wash the content and quantitatively decant into the cylinder. 3. 4. and having an electrical conductivity (EC1:5) >3 mS/cm. add 5 g of ammonium oxalate and boil the mixture for one hour. If the gypsum content is not more than 25 percent (based on preestimation to know the range). follow the same procedure as above. and add to it about 40 ml of distilled water. Add more drops until effervescence stops. but use sodium chloride solution (131. Discard the supernatant. 3. Add 25 ml of 2M HCl to the flask and gently swirl to destroy the CaCO3 content of the soil. then proceed to determine the particle-size fractions. Transfer the content into a 600 ml Erlenmeyer flask. 8. Add 20 ml of sodium-hexametaphosphate solution (40 g/l) and boil the mixture for 3 hours.1. 7. Bring to boiling while stirring. 6.6 g/l) instead of ammonium oxalate. Gypsum Removal by Ammonium Oxalate (Coutinet.2. by repeated washing of the soil with distilled water. 9. Allow to stand for 2-3 minutes. 4.4. Then add 2–3 ml of hydrogen peroxide (H2O2) to destroy the organic matter. The following are the methods that could be used for this purpose.3 is preferred because gypsum is not removed from the sample and the results are closer to the field conditions. Add more distilled water to bring the total volume to about 300 ml. 1. Add 5 drops of H2O2 and gently swirl the flask to destroy organic matter. Method 4. If gypsum content is more than 25 percent. 4. Gypsum Removal by Hydrochloric Acid (Loveday. 2. 1974) This procedure is used for soils containing visible gypsum crystals. Repeat steps 4 and 5 until no more calcium sulphate crystals are seen in solution. Weigh 40 g of soil in an Erlenmeyer flask. 2.5. 1965) 1. Repeat the addition of H2O2 until effervescence stops.5. Gypsum Removal from Soil For certain gypsiferous soils.5. 31 . it is recommended that gypsum be removed from the soil sample prior to its analysis for particle size distribution. 5.5.

Place 10 g of soil in a small funnel fitted with a filter paper. Add 5 ml of 1M NaOH and 10 ml of 10% sodium-hexametaphosphate.4. and shake gently for one hour. allow to settle and decant the clear supernatant. Repeat step 4 until the crystals of gypsum do not show anymore on the sides of the beaker. Add 500 ml distilled water and place on a magnetic stirrer. Pre-treatment of Soil with BaCl2 to Coat Gypsum with BaSO4 (Hesse.3.1M BaCl2 solution. Wash the content and quantitatively decant into the cylinder. 1974) 1.4. 1978) 1. 5. 10 g/l anhydrous sodium carbonate. Stir for one hour. and then add 40 ml of a solution containing 50 g/l barium chloride (BaCl2) and 20 ml of 45 ml/l triethanolamine. Add 40 ml water in the tube. 4. swirl gently and leave for 20 minutes to allow the dispersing of the soil sample. The presence of Ba in the solution can be determined as indicated in 4. 2. Centrifuge and decant the supernatant.4. and proceed as in procedure in section 4.5.3 3.5. Leach the excess Ba ions with pure ethanol until no more Ba is detected in the filtrate. Pre-treatment of Soil with BaCl2 Solution followed by Ethanol (Mater and Douleimy. 4. 4. 3. The presence of Ba can be confirmed if after adding a few drops of potassium chromate solution a yellow precipitate forms. and 10 percent sodium hydroxide to the treated soil. 7. 5. 6.5. Transfer the tube content by several washings with distilled water into the graduated cylinder for particle-size determination. 32 . then shake and decant. Proceed to determine the particle-size fractions. and slowly leach with 0. 4. Add 15 ml of a solution containing 40 g/l sodium hexametaphosphate. Transfer 10 g of soil into a 100 ml centrifuge tube. and disperse by shaking for 30 minutes. 2. Repeat washing the soil with water until no more barium ions can be detected in the supernatant. then proceed to determine the particle-size fractions. Transfer the soil into the suspension cylinder and stir the suspension for 12 minutes after adding distilled water and 10 ml of sodiumhexametaphosphate (40 g/l).

33 . 6. adjust pH to 8. in a centrifuge tube. Shake 10 g soil with 10 ml BaCl2 (50 g/l) and 20 ml triethanolamine [(HOCH2CH2)3N].5.2 and shake. Pre-treatment with BaCl2 Solution (Modified Method by Vieillefon. and discard the supernatant liquid. Add 40 ml distilled water. Add 15 ml of dispersing solution [4% sodium hexametaphosphate + 1% of sodium carbonate (Na2CO3)]. 3. centrifuge. Shake for 1 hour and then centrifuge the suspension.4. 2. 1979) 1. Determine the various particle-size fractions.5. 4. 5. Discard the supernatant liquid.

more interesting.1. It is also required to convert weight-based determinations to a volumebased figure. it is the density of the soil particles. and water storage and movement. the volumetric content of water in a soil layer is obtained by multiplying the gravimetric water content by the product of the bulk density and the volume of the layer.3 g/cm3. If the aggregation of a particular soil is increased. SOIL DENSITY AND TOTAL PORE SPACE 5. This pore space is important for gas exchange (O2 and CO2) between the soil and the atmosphere.65 g/cm3.4 g/cm3. For example. the total pore space will be increased. Soil particle density (PD) is defined as the mass of oven-dried solids divided by the volume of the solid particles alone. is of little practical significance. A medium textured mineral soil that is in good structural condition for plant growth contains about 50% total pore space on volume basis. Bulk density is an indirect measure of the total pore space in the soil and is also affected primarily by texture and structure. The bulk density of fine texture mineral soils ranges from about 1. usually the moisture content at sampling. and to estimate weights of soil volumes too large to weigh. It varies little from soil to soil and. Bulk density and total pore space are readily altered by tillage operations. Bulk density is an extremely useful parameter.0 to 1. The particle density of most mineral soils is about 2.7 g/cm3. and that of sandy soils ranges between 1. Introduction Soil bulk density (BD) is defined as the mass of oven-dried solids divided by the bulk volume of the solids plus pore space at a specified soil water content. texture and structure are the main factors governing the amount of pore space in soil. The magnitude of PD depends on the type of minerals in the particles. The total pore space consists of the pore spaces between adjacent sand. irrespective of the volume of voids between particles. Actually.5. Therefore. The bulk density of organic soils is usually much less than that of mineral soils and may be as low as 0. as it indicates soil structure and void space. silt and clay particles and those between aggregates. It is required to calculate porosity when particle density is known.3 and 1. It is used with bulk density to calculate soil porosity. therefore. to convert weights to volumes. which are often. Organic matter affects pore space indirectly by improving structure. and the weight per unit volume or bulk density of the soil will decrease. and the content of organic matter in the soil. 34 .

Bulk Density of a Disturbed Soil Sample This method is used when it is not possible to take a consolidated sample of soil. and the other uses samples of undisturbed soil. Calculate bulk density. Compact the soil in the cylinder by tapping the cylinder firmly 15 times on the palm of the hand. as in sandy soils and soils of greenhouses and nurseries because they are loose and very friable. and the core method.1.2. 5. Reagent The Clod or Ped Method 35 . 5. On a separate sample.2. like clods and cores. 5. 2. Fill a pre-weighed 100 ml graduated cylinder with air-dry soil. 5. Procedure 1. 3.5. Record the weight of the cylinder and the soil. Measurement of Bulk Density Two methods are commonly used to determine soil bulk density: one uses samples of disturbed soil.dry soil (g) Volume of soil sample (cm3 ) Note: Bulk density is commonly calculated on oven-dry basis. Calculate the weight of the soil. determine the moisture content of the soil sample and calculate the oven-dry weight of the soil in the cylinder.2.2. 6. The second method uses consolidated soil masses.2. Record the volume of the packed soil in the cylinder. Bulk Density of an Undisturbed Soil Sample Two methods are used to determine the bulk density of an undisturbed soil sample: the soil clod or ped method. 7. Calculation BD (g/cm3 ) Weight of oven.3. but for certain uses it is calculated on a wet-soil basis. 4.

could be used as a replacement to the dissolved saran resin.A resin. 7. and detect the change in volume of water in the cylinder (V). 2. this mixture should be prepared in a fume hood and it should be kept in a tightly closed container to prevent volatilization. Note: The clod method may yield higher BD values than other methods. To determine the volume of the clod. This is needed to calculate the oven-dry weight of the soil (Wod). If such a balance is not available. cut them carefully with scissors. The drop in weight (Wa – Ww) is equal to the weight or volume of the water displaced. is dissolved in acetone at a saran:solvent ratio of 1:7. Carefully collect soil clods from a soil profile. hang it to dry for 30 minutes. Break the clod and take a sample for the determination of soil moisture content. 36 . immerse the clod completely in a graduated cylinder half full with water. Calculation BD W od Wa Ww Wod is the mass of solid particles in the clod in grams. 5. such as Dow Saran F 310 (general purpose non-crystalline coplolymer). 6. Dip the clod in the saran solution. Weigh the coated clod and wire in air (Wa). by heating on medium flame. Melted wax. which is the volume of the clod. If the volume of the clod is measured as indicated in step 6: BD = Wod/ V V is the change in volume of water in the graduated cylinder in cm3. Tie and hold the clod with a fine copper wire and weigh it. Additional saran coatings may be applied to make the clod more waterproof. Acetone is flammable. therefore. If roots are present. 4. 3. or volume of the clod in cm3. weigh it while suspended in water with a balance that can accept the clod hanging on the balance beam by the thin copper wire (Ww). Procedure 1. (Wa – Ww) is the weight of the water displaced by the clod in grams.

Be careful to avoid compaction of the soil during collection of the cores. In the first method a graduated cylinder is used.3.3.67 is commonly used as the specific gravity of soils. After careful removal of the soil core. The particle density of most soils varies from 2. Procedure The Core Method 1. Take a portion of this soil for the determination of soil moisture. 5. Knowing the moisture content of the soil core. of soil core (dry basis) (g) Vol. Stir thoroughly with a stirring rod to displace the air. by the volume of the soil core. examine it and trim the ends carefully. calculate the oven-dry weight of the soil sample. which is the volume of the steel tube. and rinse the stirring rod and the inner walls of the cylinder with 10 ml water. 4. Add 50 ml of water to the soil in the cylinder.60 to 2. 3. 5. Measurement of Particle Density Two methods for the determination of particle density (PD) are discussed. 4. 37 .75 g/cm3. 2.5. Both analyses are very simple and rapid.4. Calculate the weight of the soil sample alone by subtracting the weight of the steel tubing. An average particle density value of 2. Procedure The Graduated Cylinder Method 1. 2. BD (g/cm3 ) Wt. Calculate the bulk density in g/cm3 by dividing the weight of soil core. Allow the mixture to stand for 5 minutes and record the volume of the soil plus 60 ml water. Be sure that no soil material is on the inner walls of the cylinder. on oven dry basis.1. Weigh the soil and tubing. of soil core (cm3 ) Values of BD of undisturbed cores are of practical significance as it indicates soil aggregation and structure under field conditions. 5. Weigh 40 g of soil in a 100 ml graduated cylinder. 3.2. in the second method a volumetric flask is employed. Carefully drive a thin-walled steel tubing or pipe (of known weight and volume) into the soil with a block of wood and a hammer.

3. washing down any soil particles adhering to the neck.5. 5. Pipette 50 ml of water into the volumetric flask. Fill a pre-weighed 100 ml volumetric flask to the mark with boiled distilled water cooled to room temperature. 4. The amount of moisture should be added to the amount of added water to obtain the total amount of water used. Calculation Volume of total solids Volume of soil water Volume of added water Volume of (soil + water) = as shown on graduated cylinder Volume of added water = 60 ml + soil moisture (ml) Particle Density (PD). g/cm 3 Oven .3. Procedure The Volumetric Flask Method 1. Weigh the flask plus water (W1). Determine separately the moisture content of the soil sample by the gravimetric method.2.dry wt of soil (g) Volume of total solids (cm3 ) 5. 7. Calculation Volume of soil particles (cm3 ) Ws W1 W2 38 . Weigh accurately 50 g of soil and transfer quantitatively to the volumetric flask (Ws). Heat the flask gently on a hot plate until the water starts to boil in order to drive out air from the soil. and then discard the water and dry the flask thoroughly. 9. 2. Weigh the volumetric flask with its content (W2). Determine on a separate sample the moisture content of the soil by the gravimetric method to find the oven-dry weight of the soil in the flask. Calculate first the volume of soil particles and then particle density (PD). 6. 8. Cool the content and bring up to the 100 ml mark with boiled distilled water cooled to room temperature.

4. Depending on pore size. Calculate BD. There is no sharp line of demarcation between the two pore sizes.6 g/cm3 %PS = 100(2. Calculation % Pore Space (PS) Example PD BD X100 PD A soil sample weighs 110 g and contains 15% moisture.8 ml water.8 = 2.3 g/cm3 36. It is filled with air and water.65 PD = 95.65 g BD = 95. g/cm 3 Ws Ws W1 W2 5.3) / 2. The sample displaced 36.6 = 50 39 .65 75 = 1. pore spaces are given the name macropores (large) or micropores (small). PD and %PS Oven-dry wt = 110 x 100/115 = 95. The volume of the soil sample is 75 ml.Particle density (PD).6-1. Calculation of Percent Pore Space The pore space (voids) is the portion of bulk soil volume not occupied by solid particles.

½H2O is more soluble in water than the fully hydrated gypsum.6. Introduction A good method for estimation of soil salinity is the measurement of the electrical conductivity of the saturation extract because it is related to the field conditions. the soil moisture of the saturation paste is approximately equal to two times soil moisture at field capacity and four times of the wilting point. slides freely off the spatula. For this reason the conductivity of the saturation extract (ECe) can be used for estimating the soil salinity in the field. 3. If the sample hardened. add an additional weighed quantity of air dry soil and mix. flows slightly when the container is tipped. and consolidates easily by tapping the container after a trench is formed in the paste with the flat side of the spatula. The following day. CaSO4. slowly add distilled water to the sample while stirring the soil with a spatula until a condition of saturation is reached. CaSO42H2O to CaSO4½H2O. Recheck again the criteria for saturation. ANALYSIS OF SATURATION PASTE EXTRACT 6. recheck the criteria for saturation as described above. Using a graduated cylinder.2. After the paste is prepared. the soil paste. if more water has been added to the paste. Record the amount of water used to reach the saturation point. 5. Record the total amount of water used to prepare the saturation paste. glistens as it reflects light. This partially hydrated gypsum CaSO4. 6. cover the container with aluminium foil and allow it to stand overnight to permit the soil to imbibe water. Alternatively. Weigh 300 g of air-dry * soil and transfer into an enamelled cup. At saturation point.100 ml Procedure 1. 2.1. add more water and mix it again. or a burette. * Soil samples should not be oven-dried before being used to make a paste because heating to 105°C partially converts gypsum. 40 .2H2O. Preparation of Saturation Paste Apparatus Balance Enamelled cup or 600 ml evaporating dish Spatula Graduated cylinder or burette . 4. Over considerable textural range of soils.

78 = 22.2.78 g of oven .08X 300 g 300 277. Calculation of Saturation Percentage Saturation percentage (SP) is calculated by dividing the total amount of water added (ml) by the oven-dry weight of the soil (g) used and multiplying by 100.2. beside the pH 7 standard buffer solution. Apparatus Determination of Soil pH pH meter with glass electrode Glass beakers . Standardize the pH meter using the standard pH buffers.1.78 6. Procedure 1. What is the saturation percentage? Calculation Let X be the weight of oven-dry soil.25 ml Reagent Standard pH buffer solutions.08 Amount of water in the soil sample is: 300 .22 = 143.6. as determined on a separate sample.2 to calibrate the pH meter.2. X 8%X 300 g X 0. is taken into consideration by adding it to the amount of water used in preparing the saturation paste. Moisture content of the air-dry soil is 8% on oven-dry basis. with ample rinsing of the electrode with distilled water each time it is dipped into a 41 .6 277. and 121 ml of distilled water was required to prepare the saturation paste.8 – 9. another standard solution in the pH range of 8.22 ml Total amount of water in the soil saturation paste is: 121 + 22.dry soil 1.08X 300 g 1.22 X100 51. Since soils of arid and semi-arid regions are alkaline in reaction.22 ml Saturation percentage is: X SP 143. it is recommended to use. Soil moisture.277. Example The weight of a soil sample (air-dry) used is 300 g.

it can also be measured in the filtrate. anions and electrical conductivity. and CO3) as an assessment of their availability. 4. K. Transfer a portion of the already prepared saturated paste to fill about 3/4 of a 25 ml tall beaker.01M) suspension. the electrical conductivity should be determined in extracts obtained when soil water tension is in the range of 0. Mg. SO4. 3. Rinse the electrode carefully with distilled water and immerse into the paste. Transfer the saturated paste into a Buchner funnel fitted with Whatman No. 4. For example. The extract is also used for the determination of some of the soluble constituents (Na. Procedure 1. 6. permanent wilting point (PWP) is about one fourth of SP. Raise and lower the beaker repeatedly to have better contact between the electrode and the paste. 3. Stop the filtration when air starts to pass through the soil cake. pour it on the soil cake in the Buchner funnel and filter again. 2. Preparation of Saturation Extract Determination of electrical conductivity in saturation extract is recommended for soil salinity appraisal because saturation percentage (SP) is directly related to field moisture range.33 – 2. KCl can also be used instead of CaCl2. Ca. Make sure to make adjustment for temperature correction according to instruction usually provided with the buffer. Save the extract for the determination of soluble cations. Record the pH reading. For correlation of soluble salt concentration with plant growth.0 atmospheres. 41 filter paper and connected to a suction system.buffer solution. 42 . 2. If the filtrate is turbid. HCO3. and field capacity (FC) is about one half of SP. In case of saturation paste. Suction system and flasks. Apply suction and collect the filtrate in 50 ml receiving bottles. similar to that at which plants grow.3. Apparatus Extraction unit fitted with Buchner funnel and receiving bottles. NO3. Note: pH can also be measured in the filtrate of 1:2 soil:distilled water or soil:CaCl2 (0. Cl.

thus reflecting the degree of soil salinity. and maize are more sensitive to salinity during early seedling growth than during germination or at advanced stages of growth and grain development (Maas and Hoffman. Or. dissolve 0. or millisiemen per centimeter (mS/cm).1 M: A. and adjust the conductivity meter to read 1. Failure in germination and emergence leads to poor stand and significant reduction in yield (Maas and Hoffman. Wash the electrode. dissolve 7. transfer 100 ml of solution A into a 1 litre volumetric flask. 2. 1977). and store in glass bottles at 4°C. Apparatus Electrical conductivity meter Reagents 1. The EC is reported to a standard temperature of 25°C by adjustment factors according to Appendix F. To inhibit the precipitation of calcium during storage. They also stated that fruit trees are not only sensitive to salinity per se. and dip it in the saturated paste extract. Standard potassium chloride (KCl) solutions.1. 3. For example barley.412 mS/cm. but are particularly susceptible to the toxic effects of sodium and chloride ions. For the 0. Soil salinity is extremely important during germination and emergence of seedlings. For the 0. 6. wheat.1 M solution (12. Determination of Soil Salinity (Electric Conductivity) Electrical conductivity (EC) of a soil solution or extract indicates the concentration of total soluble salts in solution. Salinity affects plants at all stages of development and for some crops sensitivity varies from one growth stage to another. 1977). Procedure 1. B.456 g of KCl in distilled water. The unit of measurement is called millimhos per centimeter (mmhos/cm).9 mS/cm at 25°C). corrected to 25oC.01 and 0.3. Maas and Hoffman further stated that rootstock differences are an important factor in the salt tolerance of fruit trees and grapevine. 0.7456 g KCl in 1 litre distilled water as in A.412 mS/cm at 25°C). add to each 25 ml of the extract one drop of 1 g/l solution of sodium hexametaphosphate. 43 . mix well and bring to volume.5. and then fill the 1 litre volumetric flask to the mark.01 M solution (1. Pour some of solution B into a 25 ml beaker and dip the electrode in the solution. Wash the conductivity electrode with distilled water and rinse with solution B.

4. The readings for samples express the concentration of K or Na as meq/l of the saturation extract. 3.2 mg KCl in a litre of distilled water and for the preparation of 4 meq Na/l.3. Insert the suction tubing in the capsule and record the reading. add 212. Determination of Soluble Calcium and Magnesium Water-soluble calcium and magnesium are measured in the soil saturation extract. Concentration of Ca and of Mg can be determined by atomic absorption spectrophotometric techniques. Switch on the flame photometer and let it warm-up for 15 minutes. dissolve 234 mg NaCl in a litre of distilled water. To use an atomic absorption spectrometer. 6. For better results. Procedure 1. Calibrate the instrument with blank and standard solutions.2. Dip the tubing in distilled water to wash the system. and 0 – 4 meq/l of Na. Determination of Soluble Sodium and Potassium Apparatus Flame photometer Reagents 1. Calculation meq of soluble Na or K/100 g soil meq/litre X SP 1000 6. Usually titration methods are used because these cations are present in high concentrations in arid and semi-arid soils. Record the digital display corrected to 25oC. 4. For the preparation of 2 meq K/l. and then read the sample. Exchangeable Ca and Mg are determined in ammonium acetate extraction solution. Fill the capsules with the soil extracts. Standard K and Na solutions: Prepare a series of K and Na standard solutions in the range of 0 – 2 meq/l of K.5 mg LiCl in each standard to yield a final concentration of about 5 meq/l of LiCl.3. The reading in mS/cm of electrical conductivity is a measure of the soluble salts content in the extract. 2. and an indication of salinity status of the soil. dissolve 149. a number of dilutions are required. 44 .3.

it can be back titrated with the standard 0.5 g of Eriochrome black T and 4. 5. 7.01 N EDTA until a sky-blue end point is obtained. 2. Express the Ca in meq/litre of the saturation extract. Dilute with distilled water to a volume of approximately 25 ml.005 M standard CaCl2 solution Procedure a. Add 2 ml of 4 M NaOH and 2-3 mg of calred indicator. 2-Hydroxy-1-(2-Hydroxy-4 Sulfo-1-Naphthyle 20)-3Naphtholic acid-original salt. 4.01 N: Dissolve 2.Apparatus Microburette . Calculation 45 . Pipette an aliquot (2 to 5 ml) of soil extract in 50 ml white porcelain dish.5 g of pure calcium carbonate crystals in 10 ml of approximately 3 M hydrochloric acid and dilute to 1 litre. Calred indicator. 3. and follow steps 2 to 4. Determination of calcium 1. Sodium hydroxide (NaOH) 4 M: Dissolve 160 g of sodium hydroxide in 1 litre distilled water.5 g of hydroxylamine hydrochloride in 100 ml of 95% ethanol.Ammonium hydroxide buffer solution: Dissolve 67.01 N: Dissolve 0. 6. Titrate the contents slowly with 0. Eriochrome black T indicator: Dissolve 0.01 N calcium chloride solution. Ethylenediaminetetraacetic acid (EDTA) 0. 3. 2. Prepare a blank using 2 – 5 ml distilled water. Ammonium chloride .5 g of ammonium chloride in 570 ml of concentrated ammonium hydroxide and dilute to 1 litre.0 g of EDTA in water and make up to 1 litre. Calcium chloride (CaCl2) standard 0. 5. If the sample is over titrated with EDTA. Standardize the solution against 0. 6.10 ml Reagents 1. 4.

6. Express the amount of Ca + Mg in the sample in meq/l. as meq/l.meq of Ca/litre 1000 X ml EDTA used for soil extract ml EDTA for blank X N of EDTA soln.starts to form as pH rises above 8.4. ml of sample taken aliquot Determination of Magnesium Concentration of Mg. Prepare a blank using 2–5 ml distilled water. Their proportionate content is a function of pH. carbonic acid. ml of sample taken aliquot b.5 ml) into 50 ml porcelain evaporating dish. Calculation Ca Mg meq/litre 1000 X ml EDTA used for soil extract ml EDTA for blank X N of EDTA soln. The CO32. 5. 4. The difference is the concentration of Mg as meq/l.10 ml White Porcelain crucibles 46 . 2. Determination of Calcium and Magnesium 1.ammonium hydroxide buffer solution and 3 to 4 drops of Eriochrome black T indicator. Titrate the contents with 0. Pipette an aliquot (2 .01 N EDTA until a sky-blue end point is obtained.4.3. Determination of Carbonate and Bicarbonate Carbonate and bicarbonate ions are species of the same acid. Dilute with distilled water to a volume of about 25 ml and add 5 ml of ammonium chloride . Apparatus Magnetic stirrer Microburette . and follow steps 2 and 3. is calculated by subtracting meq/l of Ca from meq/l of (Ca + Mg). 3.

Methyl orange indicator: Dissolve 0. Continue the titration. Dilute 0. 4. 5.concentration. For CO32. without refilling the burette. The appearance of a pink colour indicates the presence of carbonates in the sample. Record the total volume of H2SO4 used (Vt). To the colourless solution add 2 or 3 drops of methyl orange indicator. to the pink end point. 3. Place the flask on a magnetic stirrer and titrate the content in the flask with 0. Make a blank correction for the methyl orange titration.01 M H2SO4 by adding one drop every 2-3 seconds until the pink colour disappears.and HCO3. 7. Procedure 1.1 g of methyl orange in 100 ml of water.Reagents 1. Phenophthalein indicator: Dissolve 0. the phenolphthalein end point is considered: meq/litre of CO 3 2 1000 ml X 2 Vph X M of H2 SO 4 5 ml aliquot For HCO3. sulphuric acid in 1 litre distilled water and standardize using a primary standard to determine exact molarity. 3.56 ml of conc.25 g of phenolphthalein in 100 ml of 60% alcohol. 0. Sulphuric acid (H2SO4) standard solution.01 M.in the sample as meq/l. Calculation a. Pipette 5 ml of extract into 50 ml Erlenmeyer flask and dilute with boiled distilled water to a volume of approximately 25 ml. Save the solution for chloride determination. Record the volume of H2SO4 titrant used (Vph).concentration. 2. 6. 2. the methyl orange endpoint is considered: meq/litre of HCO 3 1000 ml X M of H2 SO 4 Vt 5 ml aliquot 2Vph 47 . Add 3 or 4 drops of phenolphthalein indicator. Express the amount of CO32.

2.6. 0. Place the solution in dark for 24 hours.3.5. Estimation by silver nitrate tiration method is described. filter and make the volume to 100 ml. Determination of Chloride Chloride is usually determined in soil saturation extract to assess the concentration of soluble salts. Procedure 1. or start with another 5 ml aliquot of the extract. Titrate the contents under bright light with the standard AgNO3 to a brownish-reddish end point. and (b) to use as a reference for the end point. Prepare a blank in order to (a) correct for the amount of Ag2+ used to form the silver chromate (Ag2CrO4) red precipitate. Add a saturated AgNO3 solution until some brownish red AgCrO4 precipitate forms. Silver nitrate (AgNO3) standard. The volume of solution at the end of titration of the blank should be almost equal to that of the unknown.005 M of AgNO 3 5 ml aliquot 48 . 3. 2.8495 g of AgNO3 in distilled water and dilute to 1 litre. Calculation meq of Cl/litre 1000 ml X ml of AgNO 3 used X 0. Potassium Chromate (K2CrO4) indicator 5%: Dissolve 5 g of K2CrO4 into 90 ml water. Add 5 drops of K2CrO4 indicator to the solution saved after the titration of the carbonate and bicarbonate. Apparatus 10 ml microburette Reagents 1.005 M: Dissolve 0.

a major component of calcareous soils. active CaCO3 was more than 10%. It was found that when total CaCO3 was above 20%. grapes. 49 . But. Tolerant crops: wheat. but. nature of the carbonates was more important in governing retention. watermelons. maize. When total CaCO3 was less than 20%. millets. rice. Calcareous soils with 15% calcium carbonate content have higher water diffusivity and faster water movement than non-calcareous soils of similar texture. 1970. The authors showed that soil retention of P. clover. artichokes. thus reducing the percolation of water. The amount and form of calcium carbonate (total versus active) and its distribution down the soil profile. Mn. Thabet. figs. affect soil physical and chemical characteristics. sugar beet. Effect on plants: Continuous horizons of carbonate accumulation in soil profile may prevent root penetration and thus may retard the degree of plant development and reduce the yield. sugarcane. Moderately tolerant crops: barley.7. banana and potatoes. lettuce. 3. Sensitive crops: citrus. Therefore. CALCIUM CARBONATE Calcium carbonate. beans. 1975). Sys (1975) classified the sensitivity of crops to CaCO3 into three groups as follows: 1. one could give the limit of about 10% active CaCO3. tobacco and onions. The active CaCO3 was more than 10% when the total CaCO3 was above 25% in the studied soils. CaCO3 assists in the formation of stable soil aggregates. which will contribute significantly to the retention of certain essential elements in calcareous soils. ranges from a few percent in slightly calcareous soils to more than 80 percent in some extremely calcareous soils. increased CaCO3 content (25% or more) tends to precipitate within the capillary tubes causing an increase in the proportion of micropores. tomatoes. the retention of those elements was affected mainly by the total amount of carbonates. Evidently. Carter (1981) gave 11 to 30% total carbonate and 7 to 9% active CaCO3 as the critical levels that adversely affected crop growth. cotton. when it was above 20%. Physical effects: The active-CaCO3 portion and the distribution of CaCO3 in the different particle size fraction affects the properties (soil-water relationships) of calcareous soil (Deb and Chadha. alfalfa. olives and dates 2. Zn and Cu was directly related to carbonate content and to the distribution of total and active calcium carbonate between the clay and silt fractions.

Determination of Total Calcium Carbonate Apparatus 25 ml and 100 ml Erlenmeyer flasks Burette.1. cool and dilute to 1 litre. Shake the flask until the crystals dissolve completely. Hydrochloric acid (HCl) Standard 1 M: Add 81 ml HCl to about 500 ml water in a 1 litre volumetric flask. 2. Procedure 1.5 7. Standardize it against a primary standard. 4. Sodium hydroxide (NaOH) Standard 0.0 M HCl. Calculation % CaCO3 %CaCO3 mlHCl 1M 10 1 mlNaOH 0. 3.5M 10 100 100 g Vol. 25 ml Reagents 1. filtrate aliquote ( 10ml) 1000 2 Wt. HCl ( 100ml) Vol. 2. of soil g mlNaOH 0.2.5 M sodium hydroxide. cool and make to volume with distilled water. Standardize it against a primary standard. Weigh 5 g of soil and transfer into a 250 ml Erlenmeyer flask. Filter. and pipette 10 ml of the filtrate into a 100 ml Erlenmeyer flask. Phenolphthalein indicator 1% in 60% ethanol: Weigh 1 g phenolphthalein crystals in 100 ml volumetric flask add 60 ml of ethyl alcohol and dilute to volume with distilled water.5 M: Dissolve 20 g NaOH in 800 ml distilled water in a 1 litre volumetric flask. 3. Add 100 ml of 1. 5.7. Add 2 or 3 drops of phenolphthalein to the content and titrate with 0. Cover the flask with aluminium foil and keep it overnight or heat it to boiling for 5 minutes and let it cool to room temperature. Determination of Active Calcium Carbonate (modified Drouineau method) 50 .

which is dissolved in sulphuric acid to form oxalic acid: 5H2C2O4 + 2MnO4. 7.02 M) to a pink endpoint. and note down the volume used (Vsample). Na2C2O4. Filter the suspension and collect the filtrate (discard the first few ml).1N: Dissolve 3. 4. 2.+6H+ 10CO2 + 2Mn2+ + 8H2O The solution must be heated to 80 – 90oC for rapid reaction. 3. Procedure 1. Sulphuric Acid Concentrated (analytical grade).reacts with 5mg CaCO3 3 NKMnO 4 (V blank 51 . Calculation % Active CaCO Since Therefore.61 g (NH4)2C2O4 in 1 litre of distilled water.1 meq MnO42. Add to it 100 ml of distilled water and 5 ml of concentrated sulphuric acid and heat to a temperature of 60 .Reagents 1.2N: Dissolve 12. Potassium Permanganate (KMnO4) 0. 6.5 g of soil (sieved through a 2 mm sieve) into a 500 ml Erlenmeyer flask. NH 4 2 C 2 O 4 (ml) 5 100 g X X V )X sample filtrate aliquote (ml) 2. 3. Pipette 10 ml of the filtrate into an Erlenmeyer flask. cover and let stand overnight. Add 250 ml of the ammonium oxalate solution and shake for two hours. The reaction is catalyzed by Mn+2 produced and it goes very slowly at first until some Mn+2 is formed.5 g 1000 0. Titrate with KMnO4 (0.70°C. 2. Calculate percent of active calcium carbonate content of the soil. The potassium permanganate can be standardized by titrating with the primary standard sodium oxalate. Filter and store in amber glass bottle. 5. Ammonium Oxalate (NH4)2C2O4 0. Prepare a blank in the same manner using 10 ml of the ammonium oxalate solution. and record the volume of the titrant used (Vblank). The first persistent pink colour (30 sec. Keep the solution at a gentle boil for about 1 hour.16 g KMnO4 in 1 litre of distilled water. Determine a blank by titrating an equal volume of 1 M H2SO4.) should be taken as the end point. Weigh accurately 2. 8.

then the analysis should be repeated with a smaller amount of soil or larger volume of oxalate extractant. 52 . If active CaCO3 content obtained is greater than 17%.5 g 1000 V )X5 sample % Active CaCO 3 Note: The maximum concentration of active calcium carbonate that can be dissolved by the above method is 20%.% Active CaCO 3 NKMnO 4 (V blank NKMnO 4 (V blank 250 ml 100 g 5 V )X X X sample 10 ml 2.

therefore. which is an important parameter for soil fertility and mineralogical characterization. it will be followed in this manual also. The definitions of equivalent and equivalent weight are as follows: Atomic weight: Weight in grams of 6 10 23 atoms of the substance. of Ca 2 20 g/eq 2 eq/mole Equivalent wt. anion. Atomic Wei ght grams per 6 10 23 ions or molecules Equivalent weight: Quantity (mass) of a substance (e. of Al3 27 g/mole 3 eq/mole 9 g/eq 53 . units of equivalent weight are grams per equivalent (g/eq).) that will react with or displace one gram of hydrogen (H+). The exchangeable cations and cation exchange capacity (negative charges on the surface of soil particles) are expressed in terms of milliequivalents of negative charge per 100 g of oven-dried soil (1 meq/100 g soil = 1 cmol/kg in SI system). This is equal to the weight in grams of 6 1023 charges.8. but one equivalent of Ca2+ replaces one equivalent of K+ or one equivalent of any other cation). molecules.1 g/eq 1 eq/mole 40 g/mole Equivalent wt. units of atomic weight are grams per mole (g/mole). compounds and so on. etc.1 g/mole 39. especially in the form of gypsum interferes with the determination of cation exchange capacity. cation. which equals Avogadro’s number of charges (+ or -). Atomic wei ght of X Equivalent weight of X Valence of X Examples: Equivalent wt. compound. The unit meq/100 g has been used in this manual because most of the soil testing laboratories in the Near East still use and are familiar with meq/100g for CEC and exchangeable cations measurements. therefore. ions. of K 39. Thus. CATION EXCHANGE CAPACITY (CEC) Presence of high concentrations of calcium. Equivalent Weight grams per 6 10 23 charges ( or ) The use of equivalents to express concentrations or quantities of nutrients in soil is very convenient and widely used in soil testing laboratories (one Ca2+ cation replaces two K+ cations.g. for clarity. One mole of substance is 6 10 23 atoms.

54 .0 by the addition of more ammonium hydroxide or acetic acid. Procedure 1. acetic acid (analytical grade) to 700800 ml distilled water in 1 litre beaker. ammonium hydroxide.8. Make up to volume with ammonium acetate solution. 4. 2. Add more distilled water to bring the volume close to 1 litre. and adjust pH to 7. Decant the liquid completely and repeat the extraction three more times. 2. Or. 5. Collect the decants in 100 ml volumetric flask fitted with a funnel and filter paper.3.09 g of ammonium acetate in distilled water and dilute to 1 litre.2.0. Sodium acetate (NaOAc) 1.08 g of sodium acetate trihydrate in distilled water and bring volume to 1 litre. stopper and shake in a mechanical shaker for 5 minutes. add 57 ml of conc. Add 30 ml of 1. Adjust the pH to 8. with constant stirring. Adjust pH to 7. Ethanol 95% 3. Ammonium acetate (NH4OAc) 1. 4. Then. 6. 3.2. Discard the decants. Repeat steps 2 – 4 with ethanol or isopropyl alcohol until the EC of the decant reads less than 40 mS/cm (usually it takes 4 to 5 washings). add 68 ml of conc.0 M sodium acetate solution to the tube. Na standard solution: Refer 6.1. repeat steps 2 – 4 using the ammonium acetate solution. Centrifuge at 2000 rpm for 5 minutes or until the supernatant liquid is clear. Determination of Cation Exchange Capacity (CEC) Apparatus Centrifuge 50 ml round bottom centrifuge tubes Mechanical shaker Flame photometer Reagents 1. To displace the adsorbed Na.0 M: Dissolve 77.0 M: Dissolve 136. Weigh accurately about 5 g soil and transfer the sample to a 50 ml centrifuge tube.

Or. 2. add 68 ml of conc. Calculation meq of Na/100 g soil R X 10 Wt. To determine sodium concentration by flame photometry (see section 6. 4. So.2. Mg. Ammonium acetate (NH4OAc) 1. with constant stirring. Bring the volume close to 1 litre. 55 . Let it settle until clear or filter.3. Sodium oxalate (Na2C2O4) saturated solution: Add 10 g sodium oxalate crystals to 100 ml distilled water.2). add LiCl in each standard to yield a final concentration of about 5 meq/l of LiCl. dissolve 77.0 by the addition of more ammonium hydroxide or acetic acid.0. of soil (g) Emission Reading (R meq/l) X 100 g 100 ml X 1000 ml Wt. acetic acid (reagent grade) to 700-800 ml distilled water in a 1 litre beaker. the meq/100 g of Na is actually meq/100 g exchangeable cations (Ca.2.0 M solution: Add 57 ml of conc. For better results. Determination of CEC in Gypsiferous and Calcareous Soils Apparatus Centrifuge 50 ml round bottom centrifuge tubes Mechanical shaker Flame photometer Reagents 1. ammonium hydroxide. Allow to stand with occasional shaking for 8 hrs or longer. prepare a series of Na standard solutions in the range of 0 – 4 meq/l of Na. 8.09 g of ammonium acetate in distilled water and dilute to 1 litre.3. Then.7. of soil (g) Where. Adjust pH to 7. Na standard solution: Refer 6. and adjust pH to 7. Ethanol 95% or isopropyl alcohol 3. Na and K). R is the meq/l of Na as determined by the flame photometer. The displaced Na is actually a measure of the Cation Exchange Capacity (CEC) of the soil.

is the single grain structure of the predominantly 56 . Mg and K. Decant the liquid completely and repeat the extraction three more times. of soil (g) Where R is the meq/l of Na as determined by the flame photometer.3. 5.Procedure 1. repeat steps 2 – 4 using ammonium acetate solution. 6. However. Na and K) or the CEC of the soil. and in the Fezzan province of Libya. Centrifuge at 2000 rpm for 5 minutes or until the supernatant liquid is clear. 8. As more and more of the cation exchange capacity of soil becomes satisfied with Na on the expense of Ca. 2.2. To displace adsorbed sodium. that ESP may be as high as 50 percent or more.3. 3. 4. Some critical values were internationally given to ESP for the classification of sodium-affected soils and its effect on soil structure and plant growth. Repeat steps 2 – 4 with ethanol 95% or isopropyl alcohol until the EC of the decant reads less than 40 mS/cm (takes 4 to 5 washings). Add 30 ml of saturated sodium oxalate solution to the tube. is actually the meq/100 g of exchangeable cations (Ca. As was explained above (section 8. Weigh accurately 4 g of soil and transfer to a 50 ml centrifuge tube. probably. The reason.1). it is a common observation in the sandy soils of the Persian Gulf Countries. Collect the decants in a 100 ml volumetric flask fitted with a funnel and filter paper. Make up to volume with ammonium acetate solution. the clay fraction become dispersed and deflocculated causing the destruction of soil structure. stopper and shake for two hours. or CEC. Exchangeable Sodium Percentage Exchangeable Sodium Percentage (ESP) is the relative amount of exchangeable Na to the sum of exchangeable cations. Mg. Calculation meq of Na/100 g soil R X 10 Wt. of soil (g) Emission Reading (R meq/l) X 100 g 100 ml X 1000 ml Wt. meq/100 g of Na displaced by NH4. but soil structure is not impaired and so is plant growth and yield. Determine sodium concentration as in section 6. Discard the decants. 7.

Accordingly. In contrast. soil structure of clayey soils in Sudan would be seriously impaired at ESP values of only 8 percent due to de-flocculation of the clay fraction. ESP values that are critical in clayey soils are tolerated in sandy soils. Calculation ESP Exchangeab le Na (meq/100 g) X 100 CEC (meq/100 g) 57 .sandy soils.

SOIL GYPSUM Precise determination of gypsum in soils is difficult. The factors. Figure 8 shows the higher values obtained for gypsum content with increasing water to soil ratio. Effect of soil:water ratio and particle size on total gypsum extraction Apparatus Centrifuge Centrifuge tubes – 50 ml Mechanical shaker 58 . Results are. (2) exchange reactions in which soluble calcium replaces other cations. Determination of soil gypsum by precipitation with acetone is described here. lower than the real amounts present.053 mm) instead of 100 (2. (1978) improved gypsum determination by grinding the soil sample to 270 mesh (0. such as sodium and magnesium.9. Conventional standard methods for the determination of gypsum in soils do not extract the total amount. 20 Mesh10 Mesh 50 Mesh 100 Mesh 170 Mesh 270 % GYPSUM 10 0 1:50 1:100 1:200 1:300 1:400 1:500 SOIL:WATER RATIO Figure 8. and also with increased mesh size. therefore.0 mm). and by using a larger volume of water. that may influence the amount of Calcium and Sulphate extracted from gypsiferous soils are (1) the solution of calcium and sulphate from sources other than gypsum. because of inherent errors involved in the extraction of this mineral with water. Sayegh et al. other than the solubility of gypsum.

Procedure 1. 41 filter paper.500 0. Determine the gypsum concentration in solution from Table 2. Transfer 20 ml aliquot of the filtered extract into a 50 ml centrifuge tube. Centrifuge the content at 2000 rpm for 3 minutes. Filter the content through Whatman No. Add 20 ml of acetone.121 0. in an Erlenmeyer flask.584 2. then invert the tube on a clean filter paper and let it drain for 5 minutes. stopper the flask.5 Source: Richards. Add 40 ml of distilled water to the tube. 9. 8. 0. mix and allow to stand for 15 minutes or until the precipitate flocculates. 11. and shake for 20 minutes on a mechanical shaker. Place 1 g of air-dried soil. Measure the EC of the solution and correct conductivity reading to 25°C.Reagent Acetone (analytical grade). 7. Table 2. stopper and shake until the precipitate is completely dissolved. 5. which shows a direct relationship between the EC of the extract and its gypsum content. 6. Repeat step 6.205 59 . carefully decant the supernatant. Wash the sides of the tube with 10 ml acetone and disperse the precipitate. ground to pass through a 270 mesh (0.900 1. 3. 4.226 0. 10. 2. Add 500 ml of distilled water.053 mm) sieve. Electrical conductivity values for different CaSO4 concentrations in water CaSO4 concentration (meq/l) EC at 25°C (mS/cm) 1 2 5 10 20 30. 1954.

Calculation Gypsum content per 100 g soil is calculated as follows: meq of CaSO 4 in aliquot meq/l of CaSO 4 from EC reading X ml of water used 1000 ml meq of gypsum/100 g soil 100 X meq of CaSO 4 in aliquot Soil : water ratio X ml of water extract used 100 X meq of CaSO 4 in aliquot X 500 20 60 .

SOIL ORGANIC MATTER 10. 500 ml Magnetic stirrer Burettes. In the following procedure the factor 1. The wet combustion analysis of soils by chromic acid digestion has been accepted as a standard method for determining total C. 0. as it gives acceptable results.025 M): Dissolve 14. Organic matter can be estimated in soils by determination of the change in weight of a soil sample resulting from destruction of organic compounds by H2O2 treatment or by ignition at high temperature. a value of 1. Ferrous sulphate (FeSO4. while the ignition method gives an overestimate because inorganic fractions may also be lost during ignition. 3. Walkley – Black Wet Combustion Method Soil organic matter is defined as the organic fraction of soil including plant. as given in the procedure below.95 g ferrous sulphate in water and dilute to 1 litre. The H2O2 method does not quantitatively remove all organic matters. Published organic C to total organic matter conversion factors for surface soils vary from 1. In the soils of arid and semi-arid regions. 200°C Reagents 1.04 g of potassium dichromate in water and dilute to 1 litre. 61 . cool to room temperature.10.724 is an acceptable factor and is commonly used. Standardize this solution daily against 10 ml of 0. 4. The organic matter content of a soil may be estimated by multiplying the organic carbon concentration by a constant factor based on the percentage of Carbon (C) in organic matter. 2. Ferroin indicator (ortho-phenanthroline ferrous sulphate. and dilute to 1 litre.7H2O in water. 0. although whenever possible the appropriate factor must be determined experimentally for each type of soil. containing silver sulphate: Dissolve 25 g silver sulphate in a litre of sulphuric acid (96%.0. 0. Potassium dichromate (K2Cr2O7) solution.1667 M: Dissolve 49.1667 M potassium dichromate. add 15 ml of concentrated sulphuric acid.85 g o-phenanthroline monohydrate and 6. animal and microbial residues at all stages of decomposition including fresh and humus fractions.1.724 to 2. reagent grade). 10 ml Thermometer. Sulphuric acid concentrated.5 M: Dissolve 140 g of FeSO4. Apparatus Erlenmeyer flasks.7H2O).724 is used for calculation.

Add 200 ml of water and 4 to 5 drops of Ferroin indicator.003. and heat gently to a temperature of 150°C. but without soil. Since some soils adsorb the o-phenanthroline indicator.Black method for the determination of organic carbon in soils has been found to give approximately 89% recovery of carbon as compared to the dry combustion method.5 M ferrous sulphate until colour changes from green to red.724 Remarks: The Walkley . Transfer a weighed sample.meq of FeSO 4 ) X 0. Make a blank determination in the same manner. Add 10 ml of 0. avoiding contact with iron or steel. The presence of nitrates and carbonates up to 5 percent and 50 percent. Swirl the flask. the titration may be improved by a prior filtration. 10. insert a thermometer. then the analysis should be repeated with a smaller amount of soil or larger volume of dichromate. 3. In that case. H2SO4. 2. using a rapid filter paper in a Buchner funnel. 4. it was found that recovery of organic 62 . 9. 5. then add 20 ml of conc.1667 M potassium dichromate.dry soil (g) Organic matter % Organic C % X 1. the milliequivalent weight of carbon. which results in error caused by thermal decomposition of dichromate. Keep contents of flask in motion in order to prevent local overheating. Calculation Organic C % (meq of K 2 Cr2 O 7 .0 g for clay soil and 2-3 g for sandy soil). do not interfere. and allow to cool to room temperature slowly. Place the flask on an asbestos pad. Swirl to disperse the soil. 8.5 mm screen. 7. by 89 and multiplying by 100 to convert to percent. Grind the soil to pass through 0. Titrate with 0.336 Oven . 6. in a study by Sayegh and Salib (1969) on calcareous Lebanese soils collected from the Beka'a Valley. respectively.Procedure 1. The conversion factor 0.336 was obtained by dividing 0. Chloride interference is eliminated by the addition of the silver sulphate to the digesting acid as indicated. However. filter after the addition of water and add the indicator to the filtrate. If more than 80% of the dichromate solution is reduced. not exceeding 5 g and containing from 10 to 25 mg of organic carbon (always a few trial samples are to be done in an unknown situation) to a 500 ml wide mouth Erlenmeyer flask (1. to standardize the reagents.

63 .carbon when measured by the wet combustion method was 78% of the dry combustion method.

Boric acid 4% solution: Dissolve 40 g of boric acid in 1 litre of distilled water. 64 . 0.11. Sodium hydroxide (NaOH) 45% solution: Dissolve 450 g NaOH in 1 litre of distilled water. Sulphate mixture: Mix 10 parts of potassium sulphate. 5. 4. SOIL NITROGEN 11. 4.05 M: Dissolve 2.1. Digest further at full heat. 3. Procedure 1. Sodium thiosulphate (Na2S2O3. 1 part of ferrous sulphate and 1/2 part of copper sulphate. Cool the flask.red methyl mixed indicator: Mix both indicators at a ratio of 1:1 in powder form. add 10 g of the sulphate mixture and digest on the Kjeldahl apparatus gradually raising the temperature until the digest becomes clear. 8. Bromocresol green . grind the mixture and pass through a 40-mesh screen. 6. Sulphuric acid (H2SO4) standard solution. 3. Add 5 g of sodium thiosulphate and heat gently for about 5 minutes. Add 50 ml of sulphuric-salicylic acid mixture to the flask and swirl to bring the sample quickly into intimate contact.8 ml H2SO4 in 1 litre of distilled water and standardize using a primary standard. 7.5H2O): Twenty-mesh dried powdered crystals. 2. taking care to avoid frothing. Sulphuric . Weigh 10 g of soil (which has been passed through a 20 mesh sieve) and transfer into an 800 ml Kjeldahl flask. Total Nitrogen (Kjeldahl method) Apparatus Kjeldahl digestion unit Ammonium-N distillation unit Reagents 1.salicylic acid: Dissolve 1 g of salicylic acid in 30 ml of concentrated sulphuric acid. Mossy Zinc pieces. 2. Allow it to stand overnight.

5. Nitrite is seldom present in detectable amounts.1 M KCl. 0. connect the flask to the distillation unit.01 M CuSO4. 0. These range from specific ion electrode to manual colorimetric techniques.5.35% CaSO4. 0. however. and 2. 1. 8. turn on heat. 7.0 M KCl. micro-diffusion. for routine analysis automated colorimetric techniques and phenoldisulfonic acid colorimetric methods are commonly used.015 M H2SO4.8 S T = ml of standard acid with sample titration B = ml of standard acid with blank titration M = molarity of sulphuric acid S = weight of soil sample in g 11. These include. 0. shake by swirling. Various extractants at different molarities have been used. and flow injection analysis. Determination of Mineral Nitrogen Inorganic N in soil is present predominantly as nitrates NO3.0 M KCl.2H2O solution.03 M NH4F. 65 .5 M NaHCO3 pH 8. Exchangeable NH4 is defined as NH4 that can be extracted at room temperature with a neutral K salt solution. 0. Cool. Nitrate is highly soluble in water. steam distillation.and ammonium ions NH4+.0 M KCl.and NH4+-N are even more diverse than the methods of extraction (Keeney and Nelson. and its determination is normally unwarranted except in neutral to alkaline soils following the application of NH4 or NH4-forming fertilizers (Keeney and Nelson. saturated 0. Steam distillation is still a preferred method when using N15.01 M CaCl2. Calculation Kjeldahl N (%) (T B) X M X 2. add 300 ml of distilled water and mix. 0. and a number of solutions including water have been used as extractants. Add a large piece of mossy zinc and a spoon of glass beads. Titrate a blank prepared in the same manner but without adding a soil sample.05 M standard sulphuric acid solution to the first faint pink. 0. such as 0. Slowly add 100 ml of concentrated sodium hydroxide by letting it run down the neck and settle in the bottom of the flask.01 M CuSO4 containing Ag2SO4 and 2.2. 6. Add 10 drops of bromocresol green-methyl red indicator and titrate with the 0. The methods for the determination of NO3.05 M K2SO4. 1982). 1982). and distil 150 ml into an Erlenmeyer flask containing 50 ml of 4 percent boric acid solution.

5 M copper sulphate solution and 1 litre of a 0. 3. 66 .6% silver sulphate solution and dilute to 10 litres with water.11. which interferes with colour development of the phenoldisulfonic acid method. Copper sulphate (CuSO4) solution. it should be removed before analysis by the use of Ag2SO4 to precipitate chloride as AgCl. Dissolve 125 g CuSO4. Add 450 ml concentrated H2SO4 while shaking. Mix well. Determination of Nitrate by the Phenoldisulfonic Acid Method One of the major difficulties in estimating NO3 in soils by colorimetric methods is obtaining a clear colourless extract with low contents of organic and inorganic substances. which interfere with the colorimetric method. Store the resulting phenoldisulfonic acid [C6H3OH(HSO3)2] solution in a glass-stoppered bottle.7221 g KNO3 (oven dried at 105°C) in water and dilute to 1 litre. The Ag2SO4 is added to the extract or to the reagent used for extraction.5H2O per 1 litre of distilled water. Nitrate-extracting solution: Mix 200 ml of a 0. 4.2. 2. if the chloride concentration is more than 15 μg/g. 0. Standard nitrate solution (100 μg NO3-N/ml stock solution): Dissolve 0. 0.6%): Dissolve 6. chloride (Cl) is the major anion.5 M: Mix one part NH4OH (sp. Therefore. Heat or shake well until all the salt is dissolved. In arid and salt affected soils. Place the Kjeldahl flask (loosely stoppered) in boiling water in a beaker and heat for 2 hours. about 7. Phenoldisulfonic acid (phenol 2. Apparatus Reciprocating shaker Heavy-duty hot plate Spectrophotometer Dispenser Reagents 1. and the AgCl is removed by filtration or centrifugation after precipitation of the excess Ag2SO4 by an alkaline reagent such as Ca(OH)2 or MgCO3. gr. 5. Silver sulphate (Ag2SO4) solution (0.90) with one part H2O. Add 225 ml fuming H2SO4 (13-15% SO3).1. It is necessary to remove the excess silver ions before analysis of the extract because they interfere with the phenoldisulfonic acid method of determining NO3.4-disulfonic acid): Transfer 70 ml of pure liquid phenol (carbolic acid) to an 800 ml Kjeldahl flask.0 g Ag2SO4 per 1 litre of distilled water. 6. Mix well. Dilute ammonium hydroxide solution (NH4OH).5 M:. Mix thoroughly.

Add 0. 13. Allow to settle for a few minutes.00. Calcium hydroxide. After beakers are cool. Pipette 10 ml of the clear filtrate into a 100 ml beaker. and 2. 9. as indicated by the development of a stable yellow colour (15 ml).2 g Ca(OH)2 and shake for 5 minutes. 0. reagent-grade powder (free of NO3).60. Evaporate to dryness on a hot plate at low heat in a fume hood free of HNO3 fumes. Rotate the beaker to dissolve the residue (stir with a glass rod until the entire residue is in solution). Allow to stand for 10-15 minutes. Standard nitrate solution (10 μg NO3-N/ml working solution): Dilute 100 ml of 100 μg NO3-N/ml stock solution to 1 litre with water.00 μg NO3-N per ml.7. Add 16. Rotate the beaker so that the reagent comes in contact with all the residual salt. Procedure 1. 7. Add 0. Add 25 ml 2M KCl solution and shake for 10 minutes. reagent-grade powder (free of NO3). Standards: evaporate 0.40. Magnesium carbonate. Filter through a Whatman filter paper No. 2. 42. add 16. 8. 14. 6. 10. Read the concentration of NO3-N at 415 nm. These standard solutions have 0.5 ml of cold water.5 g MgCO3 and shake for 10-15 minutes. 2. 11. 12. Mix well. 9. Mix thoroughly. 1. 5. Follow steps 9 to 13. (Caution: the phenoldisulfonic acid is very corrosive). and 10 ml of the 10 μg NO3-N/ml working solution after adding 10 ml NO3-extracting solution in 100 ml beakers and evaporate to dryness. 8. Let the beaker cool and add 2 ml phenoldisulfonic acid rapidly (from a burette having the tip cut off or a dispensette) covering the residue quickly.5 ml of water (volume becomes = 50 ml). 1. 5. Do not continue heating beyond dryness. 67 . 8. 3. Cool the beaker to room temperature and add dilute NH4OH slowly until the solution is distinctly alkaline. 4. Place about 5 g soil in an Erlenmeyer flask.

Cl. 2.N in test soln. Note: Manufacturer instructions should be consulted for details of electrode assembling. after colour developmen t (ml) Vol. the analysis must be made before the NO3. with specific nitrate electrode and reference electrode. or read the concentration directly (if using a specific ion meter calibrated to take into account the 1:2 dilution). specific treatment of the extract may be required. of oven dried soil (g) NO . Place the beaker on a magnetic stirrer. If NH4+-N is to be determined by an electrode on the same sample. 2 M (for ionic strength adjustment): Dissolve 264 g of reagent grade (NH4)2SO4 in 1 litre of water. 2. Apparatus pH – millivolt meter or specific ion meter.. evaporated (ml) Wt.2.analysis. Determination of Nitrate by the Specific Ion Electrode The concentration of nitrate-nitrogen (NO3-N) is estimated by comparison of the electromotive force (emf in millivolts) in the unknown with that in the NO3--N standards prepared by the same method. Add 20 g of soil and 40 ml of distilled water to a 100 ml beaker.N in soil ( g/g) Vol. The presence of soil solids does not markedly affect NO3.2. Stir the mixture intermittently for an hour (two to three times). insert the electrodes into the suspension and start the stirring. If interference are suspected (high soluble salts. storage and standardization. Reagents 1. Record the millivolt reading (if using a calibration curve standardization method). 68 . of extracting soln. Procedure 1. because significant sample contamination by the external filling solution of the reference electrode may occur.electrode determinations. Ammonium sulphate [(NH4)2SO4].Calculation NO 3 . ( g/ml) X 3 11. Standard nitrate-nitrogen (NO3-N) solutions: Prepare a series of standards in water ranging from 1 to 100 mg NO3--N per litre. (ml) X Vol.or NO2-).

Aliquots from this extract will be used for the following assays. If the KCl extract cannot be analyzed soon after its preparation (within 24 hours). Extraction of Exchangeable Ammonium and Nitrate Apparatus Erlenmeyer flasks Pipettes Mechanical shaker Reagent Potassium chloride (KCl) solution. it forms a precipitate at the pH of 11. Otherwise. 3.3. 11. The addition of EDTA is necessary to complex divalent and trivalent cations present in the extract. equipped with 1 cm light path and capable of measuring absorbance at 636 nm. filter the soil-KCl suspension (Whatman no.4–12 used for colour development.1. also known as sodium nitroprusside as a catalyst in the reaction between phenol and NH3 increases the sensitivity of the method several folds. and add 100 ml of 2 M KCl. Place 10 g of soil in a 250 ml. Stopper and shake the flasks on a mechanical shaker for 1 hour. The addition of sodium nitroferricyanide dihydrate. wide mouth Erlenmeyer. Procedure 1. 42 filter paper) and store in a refrigerator. approximately 2 M: Dissolve 150 g of reagent-grade KCl in 1 litre of distilled water.3. Determination of Ammonium by Indophenol Blue Method The phenol reacts with NH3 in the presence of an oxidizing agent such as hypochlorite to form a coloured complex in alkaline conditions.11. and this turbidity would interfere with the formation of the phenol-NH3 complex. Allow the soil-KCl suspension to settle and for the supernatant to clear (usually about 30 min). Reagents 69 . 4. Apparatus Variable wavelength spectrophotometer. 5. 2.

Ethylenediaminetetraacetic acid (EDTA) reagent: Dissolve 6 g of ethylenediaminetetraacetic acid disodium salt (EDTA disodium) in 80 ml of deionised water. and dilute to 100 ml. add 4. and immediately make up to volume with deionised water and mix well. Allow the flask contents to stand for 1 minute. 2 M: Dissolve 150 g reagent-grade KCl in 1 litre of distilled water. 3. Add a small amount of additional NaOH if required to adjust the pH. Remove the flask from the bath. 4. and determine the absorbance of the coloured complex at a wavelength of 636 nm against a reagent blank solution. dilute 4 ml of the stock NH4+ solution to 200 ml. then add 2 ml of the phenolnitroprusside reagent. Pipette an aliquot (not more than 5 ml) of the filtered 2 M KCl extract (see 11. Procedure 1. and dilute to a final volume of 100 ml. 6. Na2Fe(CN)5NO. adjust to pH 7. 5. Potassium chloride (KCl) solution. 70 . and mix the contents of the flask.480 g of sodium hydroxide NaOH in 70 ml of deionised water.2.1. mix well. 2. Immediately before use. Buffered hypochlorite reagent: Dissolve 1. the solution contains 100 μg of NH4+-N/ml.98 g of sodium monohydrogen phosphate (Na2HPO4) and 20 ml of sodium hypochlorite (NaOCl) solution (5-5. Use less or more hypochlorite solution if the NaOCl concentration is higher or lower than that indicated. cool to room temperature. If pure.25% NaOCl). Aliquots of 3 ml normally contain sufficient NH4+-N for measurement. Standard ammonium (NH4+) solution: Dissolve 0. The resulting working solution contains 2 μg of NH4+-N/ml.4717 g of ammonium sulphate (NH4)2SO4 in distilled water and dilute to a volume of 1 litre. 3.4 and 12. Store the solution in a refrigerator. Add 1 ml of the EDTA reagent. dry (NH4)2SO4 is used. Place the flask in a water bath at 40°C for 30 min. Check the pH to ensure a value between 11.5 and 12 μg of NH4+-N into a 25 ml volumetric flask. 5. 2. Phenol-nitroprusside reagent: Dissolve 7 g of phenol and 34 mg of sodium nitroprusside [disodium pentacyanonitrosylferrate.2H2O] in 80 ml of deionised water.3) containing between 0. Determine the NH4+-N concentration of the sample by reference to a calibration curve plotted from the results obtained from the measurement of known concentrations of NH4+-N. followed by 4 ml of the buffered hypochlorite reagent. Mix well and store in a dark-coloured bottle in a refrigerator. 4. Dilute to a final volume of 100 ml.

Iodide forms complexes with Hg+.3.1).1 mV 1. 3. Add an appropriate amount of 2 M KCl solution (same volume as that used for aliquots of soil extract) to the 25 ml volumetric flasks. If an extract other than 2 M KCl is used. Care must be taken to prevent air bubble entrapment under the electrode. Place a 20 ml aliquot of the soil extract in a 50 ml beaker containing a Teflon-coated stirring bar.3. Procedure 1. The meter should be calibrated immediately before each series of analysis. Sodium hydroxide (NaOH). in millivolts) in the unknown with that obtained by analysis of NH4+-N standards by the same method.2. 2. 2. Standard NH4+-N solutions: Prepare a series of standards in 2 M potassium chloride (KCl) ranging from 0. because the electrode responds only to NH3 activity. Measure the intensity of blue colour developed with these standards by the procedure described for the analysis of unknown extracts. as described under 11. 5. If Hg+ is present in the sample. To prepare a standard curve. Place the beaker on a magnetic stirrer. 2. 1. Apparatus Ammonia electrode pH-millivolt meter with sensitivity of Reagents 0. 11. add 2 ml of 0. 8.25 M: Dissolve 10 g of NaOH in 800 ml of distilled water and dilute to 1 litre. sodium Iodide (15 g of NaI/l) can be added to the 0.7. and 6 ml of the 2 μg/ml NH4+-N solution to the series of 25 ml flasks.25 M NaOH. 9. The sample or standard is made alkaline by the addition of NaOH (pH 11-12). prepare the standards in this solution.25 M NaOH and insert the NH3 electrode connected to a pH-millivolt meter. This is easily accomplished by inserting the electrode at about a 20° angle with respect to vertical.1 to 10 μg of NH4+-N/ml (using NH4 working solution. add 0. 0. Measurements should be made within 1-2 minutes after the addition of NaOH to ensure no loss of NH3. 71 . 4. Determination of Ammonium by Specific Ion Electrode Ammonium-N concentration is also estimated by comparison of the electromotive force (emf.

3. record the electrode potential value and calculate NH4+-N in the sample by comparison of this value to a calibration curve (as described under 11. Stir the solution for 1 min.3..1). 72 .

reductant soluble Fe-P. while Fe-P amounted to 19 percent of the total phosphorus suggesting a comparatively high iron content which is supported by the soil analysis and by the dark reddish brown colour. The amounts of the various discrete chemical fractions of P. In the alkaline low calcareous soils Ca-P was the least. SOIL PHOSPHOROUS In general. Most of the remaining 1/3 was converted into organicP and NaHCO3 extractable-P. arid and semi-arid soils are low in available phosphorus and plants respond to application of phosphatic fertilizers. amounting to 88 percent of the total phosphorus in highly calcareous soils. 12. the considerable differences in the proportions of the various P fractions were associated with the degree of calcareousness. the distribution of the applied P was mainly in the forms of Ca-P and Al-P followed by water soluble P. Bashour and Al-Jaloud (2000) studied the fate of applied phosphorus in arid calcareous soils of Saudi Arabia and found that 1/3 of the applied P fertilizers was taken up by plants and about 1/3 was retained in the soil as calcium phosphate.2.12. Sayegh and Abdul Majid (1969) studied phosphorus fractionation and retention in soils of the semi-arid region. and the results are briefly indicated below. and are related to the genesis of soils (Westin and Buntley (1966). water soluble P and easily replaceable P in the highly calcareous soils. 73 . Thus. Applied fertilizer phosphate quickly reverts to insoluble forms. the applied P was distributed in a variety of forms decreasing in the following order: residual-P > FeP > Al-P > Ca-P> organic P. 1961). The retention of phosphorus in soils is the result of chemical precipitation and physico-chemical sorption (Hemwall.1. Fe-P. and occluded Al-Fe-P decreased with an increase of CaCO3 content. Fractionation of Soil Phosphorous Phosphorus characterization indicated that the water-soluble and easily replaceable P increased while Al-P. 12. in the alkaline non-calcareous soils with iron and aluminium oxides. The Ca-P in the soils increased with the increase of CaCO3 content. amounting to 5 percent. Fate of Applied Phosphatic Fertilizer The applied phosphorus was mainly converted to the forms of Ca-P. which are formed in soil determine the relative effectiveness of phosphatic fertilizers on crop growth (Lindsay and De Ment. In contrast to the calcareous soils. In the slightly calcareous soils. 1957).

In contrast. reductant soluble Fe-P. 12. resulted in less P retention. and occluded Al-Fe-P. The retention of P was more rapid in the alkaline noncalcareous soils. thus the removal of amorphous materials resulted in increased effective surface area and more retention reaction. The soil derived from hard siliceous calcareous beds contained intermediate amounts of P fractions. removal of the amorphous materials from the clay fractions of the non-calcareous soils. calcium phosphate is present where conditions are favourable for the presence of calcium.12. which contained larger amounts of iron and aluminium oxides than in the low and high calcareous soils. therefore. Tisdale and Nelson (1993) reported that in general the inorganic phosphorus content in arid soils is higher than the organic phosphorous content. which coat the clays. 74 . This was attributed to the presence of comparatively high amounts of iron and aluminium in the amorphous materials. 12.4. The slower retention in the calcareous soils might be due to the continued slow precipitation of calcium phosphates in the course of time. Phosphorous Retention Phosphorus retention of the soils increased with the increase of iron and aluminium oxides. While in neutral to alkaline soils. But they fail to mention the importance of iron and aluminium amorphous materials on phosphorus retention. in the highly calcareous soils. silt and sand fractions in the neutral and alkaline soils (Sayegh and Abdul Majid. the soil developed from the hard Eocene calcareous rock had a greater percentage of all the P fractions except for the Ca-P. 1969). On the other hand. Iron and Aluminium Amorphous Phosphate in Calcareous Soils Most text books state that iron phosphates and aluminium phosphates and their intergrades are found in acidic soils where conditions are favourable for the presence of Al and Fe. The slight difference in the cation exchange capacity between the clays without any amorphous material or clays containing little quantity of amorphous material (partially clean and clean clays) did not appear to provide an adequate explanation for the large difference in phosphorus retention.5.3. postulated that the retention capacity of the Ca-saturated samples was due to a surface reaction. Influence of Soil Parent Materials on the Distribution of the Inorganic P-fractions The highly calcareous soils had the highest percentage of Ca-P. The removal of the amorphous materials from the clay fractions of the low and high calcareous soils increased P retention from 2 to 70 percent upon the addition of 250 μg/g of P. It was. and no Fe-P. which are rich in iron and aluminium oxides.

Sulphuric Acid (H2SO4). the NaHCO3 solution (Watanabe and Olsen. 4. make the volume to 2000 ml. 12.4393 g of KH2PO4 (dried at 40°C) in distilled water and make the volume to 1 litre. Sodium bicarbonate (NaHCO3) solution. Prepare only as much as needed. It can be stored up to 1 month if kept in glass bottle and more than 1 month if stored in polyethylene containers. Standard phosphate solution: Dissolve 0.0 g NaHCO3 in 1 litre of distilled water. When cool.6. as this solution is not stable for more than 24 hours. 6. make the volume to 1 litre. 1965) is the most commonly used in calcareous soils. Before bringing it to volume. adjust pH to 8. Procedure 1. This solution contains 100 μg of P/ml. 2. Avoid exposure of the solution to air. Ammonium molybdate solution: Dissolve 12 g of ammonium molybdate in 250 ml of distilled water.5 M: Add 140 ml of conc. Determination of Available Phosphorous (Olsen’s method) Of the many extractants proposed for estimating available soil P. respectively.056 g of ascorbic acid in 200 ml of ammonium molybdate solution and mix. 3. This may need about 20 ml/l. 2. (1988) have reported that the Aridisols and Andisols have 64% and 63% of inorganic phosphorus. Store in a Pyrex bottle in the refrigerator. Add both solutions to 1 litre of 2. and 0. Ammonium molybdate . Weigh 5. However.0 g soil sample in 250 ml Erlenmeyer flask. 0.5 M H2SO4 (140 ml conc. H2SO4 per litre). 75 . 5.Brady (1990) and Soltanpour et al.5 M: Dissolve 42.ascorbic acid solution: Dissolve 1. Working standard (dilute) phosphate solution: Dilute 50 ml of the standard phosphate solution to one litre. 2.5 with 1 M NaOH. Add 100 ml of NaHCO3 extracting solution to it. Apparatus Mechanical Shaker Spectrophotometer Funnels and filter papers Reagents 1. (18 M) H2SO4 to 800 ml of distilled water. mix. This solution contains 5 μg of P/ml.2908 g of antimony potassium tartrate in 100 ml distilled water. the pH needs to be checked before use.

and develop colour as described above Calculation P g/g soil P g/ml X 50 ml 100 ml X 10 ml 5 g soil 76 . 0. acidify to pH 5 by adding 1. 8. add 8 ml of the ammonium molybdate – ascorbic acid solution. (sources of error: the amount of P extracted increases with time and intensity of shaking.0 ml of 2. and let stand for 10 minutes. 9. 5. 10. 7. Shake on a mechanical shaker for 30 minutes. Make volume to 40 ml with distilled water. Swirl carefully in the beginning. and with temperature. Shake the suspension by hand immediately before pouring it into the funnel and discard the first 5 to 10 ml of filtrate if turbid. Determine P concentration of the sample from a calibration curve relating the readings of absorption units to concentration in μg P/ml. 5. The colour is stable for 24 hours and maximum intensity is obtained in 10 minutes.0 ml of filtrate to a 50 ml volumetric flask. 6. Filter the suspension through Whatman No. Bring the volume to 50 ml.5 M H2SO4. Preparation of the standard curve: i) add 0. Read absorbance at 882 nm on the spectrophotometer. Transfer 10. ii) add 10 ml of the NaHCO3 extracting solution. mix well. 40 filter paper into clean and dry 125 ml Erlenmeyer flask.5 M H2SO4. 4.3. 2. 15 and 20 ml of 5 μg P/ml standard stock solution to a series of labelled 50 ml volumetric flasks.4 μg P/g per degree °C). 1 ml of 2. then vigorously to remove residual carbonates.

it includes part of the exchangeable K.50 ml Mechanical shaker Flame photometer Reagents 1. dissolve 77. add 68 ml of conc. with constant stirring.09 g of ammonium acetate in distilled water and dilute to 1 litre. Or. Potassium chloride (KCl) 0. Lithium Chloride (LiCl). 2.0 M solution: Add 57 ml of conc. SOIL POTASSIUM 13. like K-feldspars and micas. Weigh accurately 5 g of soil and transfer into a 50 ml centrifuge tube. in addition to K soluble in water. 1. In general. 77 . Adjust pH to 7.491 g of potassium chloride in one litre of 1. Plants in the field do not benefit from this form of K. Bring the volume close to 1 litre.12 g of lithium chloride in distilled water and dilute to 1 litre. 3.0 M ammonium acetate: Dissolve 1.02 M in 1.0. 0.05 M: Dissolve 2. and the manner of drying the sample also affects K extractability. and adjust pH to 7. Procedure 1. because of the variation in the clay mineralogy of the soils.0 by the addition of more ammonium hydroxide or acetic acid. The following procedure is suggested for determining plant available K in soils of the arid and semi-arid regions. Ammonium acetate (NH4OAc). ammonium hydroxide. Moreover. Then.1. acetic acid to 700-800 ml distilled water in a 1-litre beaker.0 M NH4OAc solution to be used for preparing standard curve. Apparatus Centrifuge Round bottom centrifuge tubes . moisture content of the soil sample. routine laboratory tests for determining plant available K do not reflect the true situation under field conditions. Another factor which complicates the determination of plant available K in arid and semi-arid regions is that extracting solutions used for exchangeable K may also extract part of the nonexchangeable K from K-aluminium silicate clay minerals.13. Determination of Available Potassium The determination of plant available K is complicated as. and it may also apply to Ca and Mg.

Potassium standard solutions in the working linear range of the instrument. Decant the supernatant into a 100 ml volumetric flask. 0.5 – 10 μg K/ml.1 M: Dilute 6. HNO3 to a volume of 1 litre.2 and 8.5 g of finely ground soil (70 mesh) and transfer into a 200 ml beaker.05 M: Dissolve 2. 3. stopper and shake in a reciprocal shaker for 5 minutes. 1. of soil (g) 13. HNO3 to a volume of 1 litre. 5. 7. Weigh accurately 2. add LiCl in each standard to yield a final concentration of about 5 meq/l of LiCl. Calculation meq of K/100 g soil R X 10 Wt. 0.2 ml of conc. For better results.0 M: Dilute approximately 62 ml of conc.12 g of lithium chloride in distilled water and dilute to 1 litre. 3.0 M ammonium acetate solution to the tube. Lithium Chloride (LiCl). Centrifuge at 2000 rpm for 5 minutes or until the supernatant is clear. Make up the supernatant volume to 100 ml by adding ammonium acetate solution. Nitric acid (HNO3). like 0. Repeat steps 2 – 4 three more times. Nitric acid (HNO3).2. Determination of Fixed Potassium Apparatus Flame photometer or atomic absorption spectrophotometer. 8. 4. Determine K concentration in the extract by flame photometer as in section 6. of soil (g) Reading (meq/l) X 100 ml 100 g X 1000 ml Wt. Add 20 ml of 1. 6. 4. Prepare a series of working K standard solutions in the range of 0 – 2 meq/l of K from stock solution of 0. 2. Add 40 ml of 1.0 M nitric acid to the beaker and place it in 78 .2.02 M KCl already prepared.1.3. Procedure 1. Reagents 1.

an oil bath at 113°C for about 25 minutes. Remove the beaker and wipe oil from outside. 2. Filter the contents into a 100 ml volumetric flask and wash the soil four times with 10 ml portions of 0.1 M nitric acid, each time filtering into a 100 ml flask. Cool the solution, dilute to volume and mix thoroughly. 3. Prepare K standard solutions in the recommended range of the instrument, like 0, 0.5, 1, 2, 3, 5, 7 and 10 μg K/ml. Add the same volumes of nitric acid solutions that were added in the samples. To suppress ionization and interference, add LiCl solution to yield a final concentration of about 5 meq/l (in case AAS is used, LaCl3 (Lanthanum Chloride) is added as the suppressing agent). 4. Refer to section 6.3.2 for the flame-photometry determination of K.
Calculation

Fixed K ( g/g soil) K ( g/ml) in solution X

100 ml 2.5 g soil

Note: This is in case no dilution was made on the sample prior to K measurement.

79

14. SOIL SULPHUR
Sulphur (S) is present in soils in organic and inorganic forms. Organic S is an important constituent of proteins and amino acids. The major inorganic sources of S include gypsum (CaSO4), and pyrite (Fe2S). Sulphur is also added to soil as a result of the use of fertilizers containing S, such as K2SO4, and some pesticides. It exists in soil and soil solution mainly as the SO42- anion in combination with the cations, Ca2+, Mg2+, K+, Na+ or NH4+. When present in the form of elemental sulphur (S), it will be oxidized under aerobic condition to form SO42-. Under anaerobic condition, SO42- will be reduced by microorganisms into SO32- and S2-. Hydrogen sulphide (H2S) is formed especially in swamps and other areas with stagnant water. Waterlogged and paddy soils provide a suitable environment for the formation of H2S. In soils rich in iron, H2S usually precipitates as FeS, which imparts to soils a black colour. When H2S is allowed to accumulate, it is not only toxic to soil organisms, but also it creates environmental problems. A group of bacteria present in soils is capable of oxidizing the H2S into elemental S and SO42-. Away from arid and semi-arid regions, probably in some acid soils, further formation of sulphuric acid (H2SO4) will lower soil pH to about 2, resulting in the formation of acid sulphate soils, sometimes called cat-clays. In addition to the toxicity created by the extremely low pH, the acidity will liberate very high levels of Al and Fe, which may reach toxic levels to plant growth. The total S content in soils varies widely from soil to soil. Sandy soils in the humid regions are generally low in S (0.002%). In contrast, soils in arid regions may contain 5% SO42--S. Plants absorb S mostly in the sulphate SO42form, which is the available form of S. Sulphate is extractable by water, NaCl, CaCl2, NH4OAC, NaHCO3 and Ca(H2PO4)2 solutions. Concentration of SO42- is determined as follows:
Apparatus

Spectrophotometer Mechanical shaker Volumetric flask
Reagents

1. Mono-Calcium Phosphate (Ca(H2PO4)2.H2O) solution: Weigh 2.03 g of Ca(H2PO4)2.H2O and dissolve it in 800 ml distilled water with constant stirring. Transfer to a 1-litre volumetric flask and make up to volume with distilled water. This solution contains 100 mg P/l. 2. Acetic acid (CH3COOH), 50%: Add 50 ml acetic acid to 50 ml distilled water.

80

3. Concentrated. Ortho-Phosphoric acid (H3PO4). 4. Barium chloride crystals, BaCl2: The crystals are ground to pass a 0.5 mm sieve, and retained on a 0.25 mm sieve. 5. Gum acacia solution, 0.25% (w/v) in water. 6. Standard sulphate solution: Dissolve 147.9 mg anhydrous Na2SO4 in distilled water and dilute to 1 litre. This solution contains 100 μg SO4/ml.
Procedure

1. Weigh 5 g of soil into a 100 ml polyethylene centrifuge tube, add 50 ml Ca(H2PO4)2 solution, and shake the mixture for 30 minutes on a mechanical shaker. Filter into 50 ml volumetric flask. 2. Pipette 5 ml of the extract into a 50 ml volumetric flask, add 5 ml of acetic acid, 1 ml of H3PO4 and 1 g of BaCl2 crystals. The phosphoric acid will decolourise any Fe present in solution. Mix gently by inverting the flask several times. Add 2 ml of gum acacia solution and make up to volume with distilled water. 3. Mix gently again and at 5 +/- 0.5 minutes, measure BaSO4 turbidity with a spectrophotometer at 420 nm. 4. Estimate SO42- concentration in sample by comparing turbidity with a calibration curve prepared by carrying sulphate standards through the entire procedure.
Calculation

mg SO 4 /100 g soil g SO 4 /ml in sample X 50 ml X 50 ml 50 ml 100 g 1 mg X X X 5 ml 5 ml Wt. of soil (g) 1000 g/mg 10 g SO 4 /ml in sample X Wt. of soil (g)

81

15. GYPSUM REQUIREMENT
Although gypsum is sparingly soluble in water, it is one of the most suitable chemicals used in reclaiming sodic and saline-sodic soils. Its solubility never exceeds 2.4 mg/litre. However, the problem is not mainly concerned with the degree of solubility of calcium sulphate, but to a great extent on the difficulty in replacing sodium by calcium in the colloidal complex. This difficulty is the main problem in the use of gypsum in reclaiming sodic soils, especially in calculating the actual amount of gypsum which should be added to such soils in order to react with Na2CO3 and sodium clay so as to bring its pH to about 8, i.e. to reclaim them. This difficulty increases when these soils are rich in soluble salts, i.e. saline-sodic soils. The common procedure in such cases is to determine the soil content of Na2CO3, and then calculate the equivalent amount of calcium sulphate needed to affect the transfer of Na2CO3 to Na2SO4. This calculation is essentially theoretical and the amount of gypsum thus calculated varies greatly from the actual amount needed to reclaim such soils under field conditions. This is mainly due to the fact that the following factors are usually not taken into consideration: 1. The soluble sodium salts which accumulate in the soil during the process of salinization, eventually leading to alkalinization of such soils. 2. The percentage of exchangeable sodium in the colloidal complex of the soil. 3. The amount of colloidal material in the soil. 4. The calcium carbonate content of the soil. Therefore, in general, it is recommended to multiply the theoretical quantity of gypsum by three or four to obtain the practical amount of gypsum actually required. A practical method was developed by Schoonover, 1953 to determine gypsum requirement, which is given below.
Apparatus

Erlenmeyer flasks Pipettes Filter papers
Reagents

1. Ammonium chloride – ammonium hydroxide buffer solution: Dissolve 6.75 g of ammonium chloride in 57 ml of concentrated ammonium hydroxide and dilute to 100 ml. 2. Saturated gypsum solution: Add about 40 g gypsum (CaSO42H2O) to 10 litres of water. Allow to stand with occasional shaking for 8 hours or

82

5 ml of ammonium chloride-ammonium hydroxide buffer solution. Procedure 1. 4. Let settle until clear or filter. and copper in concentrations greater than several tenths of mg/kg. Record the ml of titrant used (B).03 N 0. interfere with the performance of the Eriochrome black T indicator. Add 50 ml distilled water. If interference is encountered. Filter and pipette 10 ml of the filtrate to 200 ml Erlenmeyer flask. then Ca and Mg should be determined by atomic absorption spectrophotometer. 3. Add 100 ml saturated gypsum solution.5 g hydroxylamine hydrochloride in 100 ml of 95 percent ethanol. aluminium. the solution will have a distinct blue colour with no trace of pink or violet). 2.03 N 382 = tonnes gypsum/ha (15 cm soil depth) 764 = tonnes gypsum/ha (30 cm soil depth) Note: Iron. stopper flask.V) 0. 83 . Trisodium versenate solution (EDTA). 6. Titrate 10. commonly known as trisodium versenate) titration method. Record the ml of titrant used (V).V) (B . Usually the concentrations of these metals in water and ammonium acetate extracts of soils of arid regions are insufficient to cause interference.03 N: Dissolve 6. Standardize this solution against standard CaCl2 solution.longer.5 g Eriochrome black T and 4. 0.0 g of analytical reagent disodium dihydrogen ethylenediaminetetraacetic acid in 1 litre of distilled H2O. and 4 to 5 drops of Eriochrome black T indicator. 3.03 N trisodium versenate solution (at the end point. 5. and manganese when present in concentrations greater than 20 mg/kg. Weigh 5 g of soil into a 200 ml Erlenmeyer flask. 0. Calculation Gypsum meq/100g = (Ca meq/l in gypsum solution) – (Ca + Mg meq/l in filtrate) X 2 (B . 4. and shake at intervals for 10 minutes. Determine calcium concentration (meq/l) using EDTA trisodium salt (C10H13N2Na3O8. Determine calcium plus magnesium in solution by titration with 0. Eriochrome black T indicator: Dissolve 0.0 ml of saturated gypsum solution.

The concentration of soluble Fe in river water and ground water is estimated to range from 0. It is needed for chlorophyll formation. In soil solution iron exists in two oxidation states. which occurs in soils as yellow crystals with a metallic luster similar to gold.1. 1973. ferrous Fe2+ and ferric Fe3+. Iron occurs in soils in an amorphous form coating soil particles and. frequently manifested as yellow stripes on young leaves. Ilmenite (FeTiO3) is another important iron mineral. The most important iron minerals in soil are hematite (Fe2O3) and magnetite (Fe3O4).1. SOIL MICRONUTRIENTS 16. The major inorganic sources of Zn are sphalerite. The hydrated form of hematite is often called limonite (2Fe2O3. The concentration of Fe2+ and/or Fe3+ in soil solution is very low. due to the highly insoluble nature of Fe2O3 minerals. The normal iron concentration in plant tissue varies considerably with plant species from 100 μg/g dry matter of grasses to 1000 μg/g in alfalfa dry matter. Another iron mineral is pyrite (FeS2). Iron is an essential micronutrient for plant growth. and the presence of high amounts of phosphates. Fe2+ is the dominant species. It has strong magnetic properties. Iron deficiency in soils can be induced by overliming. Therefore. which acts as a carrier of oxygen. and hemimorphite [Zn4(Si2O7)(OH)2.1. In animals. Zinc. but 84 . Zinc Zinc (Zn) is present in small quantities in igneous and sedimentary rocks. Tan. Iron Iron (Fe) is the third most abundant element in earth crust. hence the name fool's gold. as organic complexes.1.2. ZnS. Iron concentration of <20 μg/g in plant tissue is considered deficient. also. and may result in development of chlorosis.16. 16.1 to 10 mg/l (Krauskoph. Hematite is red in colour and its presence gives the soils a red colour. iron deficiency is most likely a problem in the calcareous soils of arid and semiarid regions. ZnCO3.H2O]. 1994). such as granite. Iron deficiency often occurs on plants growing in alkaline calcareous soils. and is a valuable source for the production of many industrial products. iron is present in the blood hemoglobin. Hydrozincite [Zn5(CO3)2(OH)6] is another Zn mineral frequently mentioned. In addition. The granular soil structure in Oxisols is believed to be stabilized by iron coatings around the structural units. such as basalt. Under anaerobic conditions. Magnetite is black in colour and crystalline in nature. Concentration of Zn is usually higher in basic igneous rocks. Iron.3H2O). smithsonite. than in acid igneous rocks. whereas under aerobic conditions Fe3+ is the dominant species. Manganese and Copper 16.

and is then called exchangeable Zn.5. Because of its cationic nature. whereas at high pH. Mn3+. On maize plants. Zinc is also essential for seed and grain production. dehydrogenase. Zn is present as the divalent Zn2+ ion. The concentration of Zn ions is dependent upon pH. For example. On the other hand. In soil solution. Zn concentration of < 15 μg/g of leaf dry matter cause Zn deficiency. Therefore. high soluble Zn contents occur in acid soils. high amounts of manganese may be present in highly 85 . Zn deficiency is found in alkaline calcareous soils. It is then called exchangeable manganese. and occur only in large amounts as Zn ore deposits. The total Mn content in soils varies considerably from 20 μg/g to 6000 μg/g (Krauskoph. and decreases at high pH values. Its concentration increases at low pH values. the concentration of Zn2+ ions in neutral and alkaline calcareous soils is in the range of 1 10-8 to 1 10-10 M (Norvell. The element functions as a catalyst. Zn deficiency produces white to yellow leaves with bleached stripes. Most Zn compounds are sparingly soluble in water. The trivalent form usually exists as Mn2O3. The concentration of Mn2+ in soil solution is very low.this mineral is considered similar to smithsonite (Hurlbut and Klein. e. whereas low soluble Zn contents are found more in basic soils. The tetravalent form (MnO2). the Zn ion is adsorbed by the negatively charged surfaces of soil colloids. 1977). The trivalent ion itself is unstable in soil solution. The concentration of total Zn in soils is approximately in the range of 10 μg to 300 μg/g. 1990). Therefore. All the minerals stated above are very rare in soils. especially in reduced soil environment. and is needed only in very small amounts. especially in Aridisols. Zinc is a micronutrient to plants. 1973). It is released into the soil by rock weathering and is re-deposited in various forms of Mn oxides. Mn2+ is usually adsorbed on the negatively charged surfaces of soil colloids. It is present in several plant enzymes. The divalent manganese ion is the main form of Mn in soil solution. and peptidase. 16. 1973). Consequently. Zn2+ exhibits minimum solubility and precipitates as Zn(OH)2. as is the case with all the other microelements. At pH 9. The average Zn content in normal agricultural soils is 50 μg/g (Brady.3.g. seldom exceeding 0. a symptom known as white bud of maize. proteinase.1. Zn2+ concentration is very high in soils. Zn2+ concentration is low. At low pH. and Mn4+. and development of growth hormones. The normal concentration of Zn in most plants ranges on the average from 15 to 125 μg/g. Because of its cationic nature. Manganese Manganese (Mn) is present in small quantities in many rocks. which is manifested as stunted growth. Zinc deficiency is common in the calcareous soils of arid and semiarid regions. Zn concentration of > 400 μg/g of leaf dry matter is considered excessive and may induce Zn toxicity.05 mg/l. which can be found in substantial amounts in acid soils. is perhaps the most stable and inert form of manganese. The element can exist in three oxidation states: Mn2+.

Present at concentration < 3 μg/g dry matter. However. and in nitrogen fixation. In the soil solution. which is manifested by yellowing and curling of leaves. Cu deficiency is more likely to occur in basic soils.1.chelate (Krauskoph. whereas above this pH. It is essential in enzyme reactions. such as Ultisols and Oxisols. Copper Copper (Cu). copper exists as Cu+ (cuprous). The concentration of free and exchangeable Cu ions is high in acid soils. or Cu2+ (cupric) ions. hence Cu affects photosynthesis.3. 16.4. However. 1973). Cu(OH)+ is the major copper ion. and grey specks in oat leaves. is classified as a native element. sulphates. The most common Cu mineral in soils is perhaps chalcopyrite (CuFeS2).g.30 μg Cu/g. Therefore. Because of its cationic nature. Cuprous ions are so unstable in aqueous solution that they will be automatically affected by the soil redox process. Soybean and oats are especially sensitive to Mn deficiency. Copper is a micronutrient. 1973). Therefore. low amounts of manganese usually occur in Aridisols. oxides. stunted growth and development of short 86 .g. Manganese is required for plant growth only in very small amounts.500 μg/g dry matter. A Mn concentration of < 20 μg/g dry matter is considered deficient and is usually manifested by development of necrotic spots. The concentration of soluble Cu ions in soils is on the average 20 mg/l. The total Cu content in soils is in the range of 10 μg/g to 80 μg/g (Krauskoph. The normal Mn content in plant tissue is 20 . in the forms of sulphides. Cu deficiency will occur. Manganese deficiency is likely to occur in calcareous soils of arid and semiarid regions. 1973). At concentrations > 10-7 mol/l Cu+ ions are unstable at ordinary temperature. The normal concentration in plant tissue is approximately 4 .g. whereas Cu toxicity may be displayed more by highly weathered acid soils. and low in basic soils. Manganese is an essential micronutrient and is needed by plants to activate a number of enzymes. Cu is noted to be needed in protein and carbohydrate metabolism. meaning that it can occur as a native element in the earth crust in contrast to such elements as Al. It also plays an essential role in photochemistry and in N-metabolism and assimilation.weathered acid soils. e. and are then called exchangeable Cu. and is needed only in small amounts by plants. known as marsh spots in pea leaves. it can exist at these conditions as a CuCl2. which exist only in the form of a compound. called auto-reductionoxidation reaction. e. Aridisols. The Cu2+ concentrations in many neutral and calcareous soils are reported to amount only 1 10-12 M (Norvell. e. The element is required for chlorophyll formation. cupric ions are more stable and are the major copper ions in the soil solution. and converted into Cu and Cu2+. Ultisols and Oxisols. Lindsay (1973) noted that Cu2+ is the dominant ion in soils at pH values < 7. The most common form of Cu in soils is in the form of minerals. and silicates. On the other hand. Cu2+ will be adsorbed by negatively charged surfaces of soil colloids. carbonates. and in the reproductive stages.

2H2O. EDDHA and DTPA.2.7 g CaCl2. Standard solutions of Fe. These elements can also be determined in the soil solution extracted by centrifugation of a moist soil sample collected directly from the field. 2.internodes. Weigh separately 149. Diethylenetriaminepentaacetic acid (DTPA) solution: Weigh 19. and shake for 30 minutes on a mechanical shaker. dilute the extract so that the reading is in the linear working range of the atomic absorption spectrophotometer. Centrifuge. and make up the volume to 10 litres with distilled water. Measurement of Element Concentration Using Atomic Absorption Spectroscopy Atomic absorption spectrophotometry has become a common practice in almost all laboratories. 16.2. which is manifested by yellowing of leaves. 16. especially for the measurement of trace elements (Te) concentration in solution. Determination of Available Micronutrients Available Fe.2. 2. and decant into a sample bottle fitted with funnel and filter paper. Zn.67 g DTPA and with constant stirring. Cu concentration in leaf tissue of >20 μg/g may result in Cu toxicity. Weigh 5 g of air-dried soil (<2 mm) in a 100 ml polyethylene centrifuge tube. 16. If needed. add 20 ml DTPA solution. On the other hand.3 with 1:1 HCl (approximately 42 ml required).2H2O mixture. Procedure 1. dissolve in 1 litre of distilled water. Cu and Mn: Stock standard solutions containing 1000 mg/l of the metals. AA spectrophotometer.2. After the DTPA has dissolved completely. Zn. DTPA Extraction Method Reagents 1. Adjust the pH to 7. Lindsay and Norvell (1978) developed the DTPA (diethylenetriaminepentaacetic acid) method and reported good correlations between DTPA-extractable micronutrients and plant growth. and poorly developed roots with frequently discoloration. and dissolve in 1 litre of distilled water. has its 87 . 3. dilute the solution to 9 litres. including EDTA. Pour under constant stirring the DTPA solution to the TEA-CaCl2. Each instrument.2 g TEA (triethanol amine) and 14.1. Cu and Mn in soils are extracted with several chelating agents.

The furnace AAS is a much more efficient atomizer than the flame and can directly accept very small quantities of sample. Flame AAS uses a slot type burner to increase the path length. The light source is usually a hollow-cathode lamp of the element that is being measured. 88 . Atomic absorption spectroscopy requires that the analyte atoms be in the gas phase. While flame AAS measures concentration of analyte in μg/ml. Atomic absorption spectroscopy (AAS) uses absorption of light to measure the concentration of analyte atoms in a flame or graphite furnace. 5. Samples are placed directly in the graphite tube and the furnace is electrically heated in several steps to dry the sample. 4. Sample solutions are usually aspirated with the gas flow into a nebulizing/mixing chamber to form small droplets before entering the flame. Prepare standard solutions in the working range. Lamps convert electrical energy into radiation. but it is essential to have a general knowledge of the basic principles of the technology. Concentration measurements are determined from a working curve after calibrating the instrument with standards of known concentration. Measure the signals from the series of working standards of known concentration. and dilute to the volume with DTPA solution. Atoms absorb the radiation and make transitions to higher energy levels. 3. and therefore to increase the total absorbance. Light absorption is proportional to the amount of analyte atoms in the path of light. Procedure 1. and plot the analytical signals (the instrument or detector response) as a function of analyte concentration. Ions or atoms in a sample must undergo vaporization or atomization in a high-temperature source such as a flame or graphite furnace. 10 μg/ml of the trace metal. ash organic matter. A calibration curve is a plot of the analytical signal (the instrument or detector response) as a function of analyte concentration. 2. and vaporize the analyte atoms. The calibration curves are then used to determine the concentration of an unknown sample. Prepare an intermediate standard solution by pipetting 10 ml from the 1000 μg/ml Stock solution of the analyte Te into a 200 ml volumetric flask. These calibration curves are obtained by measuring the signal from a series of standards of known concentration. 2. 1. or to calibrate the linearity of an analytical instrument. like 0. Always dilute with the DTPA solution. furnace AAS detects concentrations in μg/l.instruction manual that guide the user to the adjustment and operation of the instrument. Now follow the step by step procedure given in the instruction manual to optimize the working condition of the instrument.

0 0 – 0.0 – 4.0 0 – 2.0 3.5 – 6.0 89 .Calculation g Te/g soil g Te/ml sample X 20 ml 5 g soil 16.5 – 1.3.0 4.2 – 3.0 – 3.0 >6.2 1.1 0.0 >6.0 2.0 1.8 – 3.1 – 0.5 0.5 3.5 0.0 – 10.3 – 0.0 6.3 0.0 – 6.6 – 1.0 – 6.8 0.0 >3.0 >10 0 0 – 0. DTPA Extractability and Availability for Plant Uptake Lindsay and Norvell (1978) suggested some critical levels for DTPA extractable micronutrients as a guide to deficiency and availability of these trace elements for plant uptake and growth: Micronutrients (μg/g soil) Availability Zn Mn Fe Cu Very Low Low Medium High Very High 0 – 0.

It is released by weathering of the minerals in the form of H3BO3 and its concentration is usually <1 10-4 M. In areas with geothermal activity. The normal B concentration in plant tissue is reported to be between 20 and 100 μg/mg dry matter of mature leaves. where an average concentration of 4. gases flowing from inner earth contain B. Since highly leached soils usually exhibit low soil pH. and are.units polymerize and form a variety of borate crystals. It is essential in sugar translocation and in the synthesis of hormones and protein in plants. whereas B toxicity could be noted in Aridisols. Borax is the most common among borate minerals. hence for the growth of young shoots. On the other hand. In sugar beets. sedimentary and metamorphic rocks. The BO32. 1973). Because of its anionic character. Borate minerals occur mostly in arid regions. whereas a B concentration >200 μg/mg indicates B toxicity. Total Boron by Na2CO3 Fusion Apparatus 90 .6 μg/ml has been reported (Krauskoph. In soil solution. 1973). BO32. Therefore. It is needed for cell division. However. in contrast to the other micronutrient elements. which equals 0. Therefore. Concentration of 1–2 mg B/kg soil is perhaps more representative for surface soils. B can exist both as H3BO3 and H2BO3-. they may contain excessive amounts of B for plant growth.1 mg/l (Krauskoph. In humid regions borate ions may tend to leach from soils.will not be attracted by the negatively charged soil colloids. it results in rotting of the shoots. They are formed by the evaporation of water in enclosed salt-water lakes and basins in arid regions. a nutritional disease called heart rot. This is in contrast with the other micronutrients. acid soils are deficient in B. Methods for determination of total B and available B are described here. the major inorganic sources of B are borate and boron-silicate minerals. Total B content in soils is between 7 and 80 μg/mg soil.1. It is present in small amounts in igneous. Since arid region soils are usually not affected by leaching. A boron content of <15 μg/mg indicates B deficiency. therefore. B deficiency is more likely to occur in Ultisols and Oxisols. soil genesis and classification. 17. soluble B concentrations are low in highly leached soils. SOIL BORON Boron (B) is a non-metal. a very small amount. Boron is an essential micronutrient element for plant growth. When dissolved in hot springs the element becomes boric acid (H3BO3). Boron deficiency is usually manifested in formation of white and rolled leaves. High concentrations of B are found only in seawater. soluble B concentrations are expected to be high in soils not affected by leaching. Boron in soils is primarily of importance in soil fertility and plant nutrition but is not used as a significant parameter in soil characterization. strongly basic in reaction.17.

0 mg phenolphthalein in a 100 ml volumetric flask. 6. 5. Sodium Carbonate (Na2CO3) anhydrous. 95%. 0. and dilute to volume. cool. 91 . HCl to 500 ml distilled water in a 1 litre volumetric flask. 0. Store in a polyethylene vial.1 M: Add 8. Phenolphthalein solution: Weigh 50. and add 4 ml increments of 2 M H2SO4 until the solution pH is 6. and dilute to volume. 5. 3.Platinum crucible Bunsen burner Beakers. contains 350 μg B/ml. Procedure 1.02 M: Dissolve 800 mg NaOH in a 500 ml distilled water in a one litre volumetric flask. Sodium Carbonate (Na2CO3). allow the solution to cool and dilute to volume with distilled water. 2. Weigh 1. add 80 ml of distilled water. Standard B solution: Pipette 35 ml of a stock solution containing 1000 μg B/ml into a 100 ml volumetric flask. called standard solution. solid crystal powder. flasks and funnels Filter papers Reagents 1. Cool to room temperature.1 ml conc. This solution. Add 6 g of Na2CO3 powder. and wash the contents of the beaker and the crucible with distilled water into the flask. Sodium Hydroxide (NaOH).0 g of 100 mesh (2 mm) soil in a platinum crucible. 8.0-6. Hydrochloric Acid (HCl).5. Ethyl alcohol. collecting about 150 ml. 4. H2SO4 to 800 ml distilled water into a 1 litre volumetric flask. add 10 ml of H2SO4 to disintegrate and dissolve the melt. 7. Place the crucible on its side in a 250 ml Pyrex beaker. 30% solution: Weigh 30 g of Na2CO3 in a 100 ml volumetric flask. mix and heat on a Bunsen burner until the sample is completely fused with the Na2CO3. Sulphuric Acid (H2SO4). 2 M: Add 12 ml of conc. Filter the solution into a 500 ml volumetric flask fitted with funnel and filter paper. 3. 4. allow the solution to cool and dilute to volume with distilled water. Shake the flask until the phenolphthalein crystals have dissolved completely. 2. add 50 ml ethyl alcohol and dilute to the volume with distilled water. and dilute to volume with ethyl alcohol.

atomic emission spectrometry or inductive coupled plasma (ICP) is used for boron measurement in laboratories where such equipment is available.4 M) into a 1 litre volumetric flask. add 800 ml of distilled water and allow the solution to cool to room temperature. and dilute to volume with distilled water.6. Apparatus Boron-free.1 ml of conc.0 mg Ca(OH)2 into a 100 ml volumetric flask. For the measurement of B concentration in the digestion solution. Recently. add a few drops of phenolphthalein and Na2CO3 solution (30%) to attain a slightly alkaline reaction. dilute 0. alkali-resistant glassware or stainless steel Water bath Rubber policeman Reagents 1. 0. 2. Weigh 20 g of air-dry soil into a 250 ml Erlenmeyer flask. Extracted B can then be determined by colorimetric methods using reagents such as carmine or azomethine-H. Dilute with ethyl alcohol to a volume of 400 ml. Calcium hydroxide (Ca(OH)2) suspension: Weigh 400. add 900 ml distilled water to dissolve under constant stirring. 17. refer to section 17. and reflux the suspension for 5 min. Place a refluxing funnel on the Erlenmeyer flask.2.01 M: Weigh 1.11 g anhydrous CaCl2 into a 1 litre volumetric flask. Dilute to volume with distilled water. and add 40 ml of hot deionised water (in calcareous soils. 2. HCl (12.1 M: Measure 8. and dilute to volume with distilled water. 7. 3. 0. 3.3.01 M CaCl2 is used instead of hot deionised water). Hydrochloric Acid (HCl). 92 . Procedure 1. then bring to volume (500 ml) with ethyl alcohol. and heat the mixture to the boiling point. Available Boron by Hot Water Extraction This is the most commonly used method for available B in soil. Prepare a blank by following the same fusion procedure but without soil. Calcium Chloride (CaCl2). and dilute to volume with distilled water. Cool and filter the suspension into a 50 ml volumetric flask.

depending on concentration of B in solution. Prepare a series of B standard solutions (1. 7.3. 2.02 mg B. Apparatus Spectrophotometer Boron-free. 6. beakers. 93 .1 mg (100 μg) of boron. Filter the digest into a 10 ml volumetric flask.5. which should contain not more than 0. 3.1. add 2 ml of the Ca(OH)2 suspension and evaporate to dryness on a water bath. 2. Shake until completely dissolved. etc. add 5 ml of HCl (0. each one of them uses a different compound for colour development. colorimetric methods are followed. 17. 4. Pipette 2 ml of the sample (digestion solution or water extract). 17. 5. Measurement of Concentration by Colorimetric Methods For the measurement of B concentration in the digestion solution for total boron. 5. One ml of this solution contains 0. Pipette 25 ml of the filtrate into an evaporating dish. Pipettes. and 10 μg B/ml) with distilled water using standard boric acid stock solution.5716 g of recrystallized H3BO3 in distilled water and dilute to 1 litre. Cool to room temperature. a solution of carmine in concentrated sulphuric acid changes colour from a bright red to a blue.5.0.3. Carmine solution: Dissolve 920 mg carmine in 1 litre concentrated sulphuric acid. 2. Sulphuric acid (H2SO4) concentrated. The following are two procedures. Hydrochloric acid (HCl) concentrated. Heat the evaporating dish gently over a flame to destroy organic matter. Standard boric acid stock solution: Dissolve 0. alkali-resistant glassware (flasks.1 M) and dissolve the digest by rubbing with a rubber policeman. Colour Development – Carmine Method In the presence of B. burettes. or in the hot water extract for available B. and dilute to volume with distilled water.4. Reagents 1. into a 25 ml volumetric flask. 7. Procedure 1.0.

carefully introduce 10.3.0 ml conc. Treat the blank and the calibration standards exactly as the sample. and allow to stand for 45 to 60 minutes for colour development. Prepare a standard curve using the blank as a reference and observe absorbance at 585 nm in a cell of 1 cm or longer light path against each standard sample containing known amount of B (expressed as μg B/ml). mix. make to volume (25 ml) with deionised water. Note: Bubbles may form as a result of incomplete mixing. Colour Development – Azomethine-H Method Apparatus Analytical balance Flask or beaker Volumetric flask Funnels 94 . Add 2 drops (0. Add 10.1ml) conc. taken for estimation = 25 ml (this was reduced to 10 ml) B content in the reduced sample (μg/ml) = X B content in the 10 ml reduced sample (μg) = X x 10 (quantity present in the original 25 ml extract) B content in 50 ml original extract (quantity in μg present in 20 g soil) = X x 10 x 2 B content in 100 g soil (μg) = X x 10 x 2 x 100/20 17. which is bluish or blue depending on the concentration of B in the sample. mix well. 5.0 ml of Carmine reagent. of the extract = 50 ml Vol. 6. Calculation B content in g/100 g soil Where. 4. Check the calibration daily because the carmine reagent deteriorates.2. HCl. X x 10 x 2 x 100 20 X x 100 X = Reading in μg/ml from the standard curve Note: Weight of the soil taken = 20 g Vol.3. H2SO4. Make sure that there are no bubbles in the optical cell when absorbance readings are being made. and allow to cool to room temperature. Determine the B content (as μg B/ml) in the unknown sample from the standard curve.

If solution is not clear. 0.025 M): Dissolve 9.40 and 0. it should be heated gently in a water bath or under a hot water tap at about 300 C till it dissolves.0 g L-ascorbic acid in about 100 ml deionised or double-distilled water.42 filter paper Spectrophotometer Reagents Azomethine-H: Dissolve 0.05.10. Procedure 1. 0. 2. Take 5 ml of the clear filtered extract in a 25 ml volumetric flask and add 2 ml buffer solution. with constant stirring. Make the volume to 25 ml with deionised or double-distilled water and measure absorbance at 420 nm. Buffer solution: Dissolve 250 g ammonium acetate in 500 ml deionised or double-distilled water and adjust the pH to about 5. 0.Whatman No. Mix the contents thoroughly after the addition of each reagent. Then. Intensity of colour is measured at 420 nm. Standard stock solution: Dissolve 0. This will give reading for standard solution having B concentration 0.8819g Na2 B4O710H2O AR grade in a small volume of deionised water and make volume to 1 000 ml to obtain a stock solution of 100 g B/ml.0 ml of 5 g B/ml solution (working standard) to a series of 25 ml volumetric flasks. 0.0 and 4.80 g B/ml. 6.25. 2. 1. Let the solution stand for 1 hour to allow colour development. EDTA solution and azomethine-H solution. the volume is made to the mark. 2 ml EDTA solution and 2 ml azomethine-H solution.0.20. 5. Add 2 ml each of buffer reagent. This solution contains 5 g B/ml. Preparation of standard curve: Take 0. 3.45 g azomethine-H and 1.3 g EDTA in deionised or doubledistilled water and make the volume up to 1 litre. The colour thus developed has been found to be stable up to 3-4 hours. EDTA solution (0. 0. 95 .50. Mix the contents after each addition and allow to stand at room temperature for 30 minutes. 4.5 by slowly adding approximately 100 ml glacial acetic acid. 0. Every week a fresh solution should be prepared and kept in a refrigerator. Working standard solution: Take 5 ml of stock solution in a 100 ml volumetric flask and dilute it to the mark.

Apparatus Centrifuge and 50 ml centrifuge tubes 96 . 18. The amount of charcoal added may vary with the organic matter content of the soil and should be just sufficient to produce a colourless extract after 5 min. and therefore. of boiling on a hot plate. since the procedure involving this chemical does not require the use of concentrated acid. Molybdenum toxicity (molybdenosis) is common when cattle graze forage plants with 10-20 g Mo/g. and is reported to range between 0. tend to be leached from the soils in humid region.1 g/g soil or less.ion under neutral to alkaline conditions. The total Mo content in soils is perhaps the lowest of all the micronutrient elements. Because of the anionic nature of Mo. 2. In plants a deficiency of Mo is common at levels of 0.2 g/g and 10 g/g. quinalizarin and curcumin. Excess amounts of charcoal can result in loss of extractable B from soils. Mo exists mainly as HMoO4 ion under acidic condition. and as MoO42. Molybdenum can be toxic due to greater solubility in alkaline soils of the arid and semi-arid regions. SOIL MOLYBDENUM Molybdenum (Mo) is a rare element in soils. Determination of available Mo by ammonium acetate extraction is described here.Calculations Weight of the soil taken = 25 g Volume of extractant (water) added = 50 ml First dilution =2 Volume of the filtrate taken = 5 ml Final volume of filtrate after colour development = 25 ml Second dilution =5 Total dilution = 2x5 = 10 times Absorbance of the soil solution as read from the spectrophotometer = X Concentration of B as read from the standard curve against X = C g/ml Content of B in the soil ( g /g or mg/kg) = C x 10 Note: 1. its anions will not be attracted much by the negatively charged colloids. and is present only in very small amounts in igneous and sedimentary rocks. The major inorganic source of Mo is molybdenite (MoS2). The use of azomethine-H is an improvement over that of carmine. In the soil solution. and deficient in acid soils of the humid regions.

0 M ammonium acetate solution to the tube. 2. 5. as described under 16. Repeat steps 2 – 4. 1. Add 33 ml of 1. Centrifuge at 2000 rpm for 5 minutes or until the supernatant is clear.Automatic shaker Atomic Absorption Spectrophotometer Reagents 1.09 g of ammonium acetate in 1 litre of distilled water and adjust pH to 7. 3. 97 .2. Procedure 1. stopper and shake in a mechanical shaker for 5 minutes.0 M: Dissolve 77.2. 7. 6. Decant the solution into a 100 ml volumetric flask. Weigh accurately 5 g soil and transfer it into a 50 ml centrifuge tube. Ammonium acetate solution (NH4OAc). 4.0. Make up the volume to 100 ml with ammonium acetate. Determine Mo concentration in the extract by the atomic absorption spectrophotometer.

19. SOIL SELENIUM
Determination of total selenium (Se) in soils is of little value in predicting Se uptake. Cary and Allaway (1969) have shown that plant uptake of Se is closely correlated to the water-soluble Se fraction in soils high in Se content. This correlation has not been demonstrated for soils low in Se content. The most commonly used extractants are: Ammonium Bicarbonate – DTPA, hot water, saturated paste extract, DTPA (2 hrs), and 0.5 M Na2CO3. The above five extractants, when tested on soils high in Se, showed high correlation with Se in wheat plant (Jump and Sabey, 1989). However, Se in saturated paste extract expressed as mg Se/l of extract was found to be the best indicator of Se uptake in Se-accumulating plants. The data of Jump and Sabey (1989) suggested that soil or mine-spoil materials that have more than 0.1 mg Se/l of saturated extract might cause Se toxicity in plants. The ammonium bicarbonate-DTPA method showed that Se in extract correlates better with Se in wheat grain, better when soil samples were taken from the 0 – 90 cm depth as opposed to 0 – 30 cm depth (Soltanpour et al., 1982b). This was found to be particularly useful to screen soils and overburden material for potential toxicity of Se. Concentration of 0.05 μg Se/g or less in feed and forage plants is in the deficient range and-4 – 5 μg Se/g or more are in the toxic range.
Procedure

The ratio of soil to any of the extractant listed above varies from 1:2 to 1:5, and the extraction time from 15 min to 2 hrs. The filtered extract can be analyzed for Se using a hydride generating system attached to an ICP emission spectrometer (Soltanpour et al., 1982 a) or hydride generating system attached to atomic absorption spectrophotometer.
Note:

1. The extracting methods developed for Se have been found to be suitable for predicting the availability of Se in areas where plants suffer Se toxicity. Because of rather small quantities of available Se in Se-deficient areas, no reliable extractant has yet been developed. Therefore, plant Se and total soil Se will continue to serve as the best tools available for testing the Se status of Se-deficient soils. 2. Selenium deficiency has implications with respect to livestock and human nutrition, but not to plant nutrition. So far, there is no known yield response to Se addition on cultivated crops, and its essentiality to plants is not established yet.

98

20. POTENTIALLY TOXIC ELEMENTS - CD, CR, NI AND PB
As a result of on-land application of certain waste products, like digested sewage sludge contaminated with industrial wastes, soils could become seriously contaminated with certain potentially hazardous products of the industry, like cadmium (Cd), chromium (Cr), nikel (Ni) and lead (Pb). In addition to analysis for plant essential elements, like Fe, Zn, Mn and Cu, soil laboratories are now charged with a new list of metals considered to be potentially toxic elements. A total elemental analysis of soil for these elements is not necessary for the assessment of risk of soil contamination with potentially toxic elements and its consequent availability for plant uptake. Instead, extraction of a fraction that would indicate the availability of the metal for plant uptake and consequent ecotoxicology should be practised. The DTPA extraction procedure used for Fe, Zn, Mn and Cu is also valid for the assessment of soil contamination with the potentially hazardous heavy elements. In recent publications the EPA methods have also been used to determine these elements, and are described below. Cationic metals are metallic elements that occur predominantly in the soil solution as cations. Examples are Cd2+, Cr3+, Ni2+ Pb2+. Oxianions are elements that are combined with oxygen in molecules with overall negative charge such as Chromate (CrO4-2), which is negatively charged and leachable in the soil solution causing risk to human health and environment (Pierzynski et al., 2000).
The EPA Method (3050)

The United States Environmental Protection Agency (EPA) in 1986 adopted the following acid digestion procedure for total sorbed metals.
Apparatus

AAS Hotplate Beakers Watch glass Filter papers
Reagents

1. Nitric acid (HNO3) concentrated, and 1:1 dilution in deionised water. 2. 30% hydrogen peroxide (H2O2).

99

3. Hydrochloric acid (HCl) concentrated.
Procedure

1. Add 10 ml of 1:1 HNO3 to 2 g of air-dried soil (<1 mm) in a 150 ml beaker. 2. Place the sample on a hot plate, cover with a watch glass, and heat (reflux) at 95°C for 15 minutes. 3. Cool the digest and add 5 ml of concentrated HNO3. Reflux for an additional 30 minutes at 95°C. 4. Repeat the last step, and reduce the solution to about 5 ml without boiling (by only partially covering the beaker). 5. Cool the digest again and add 2 ml of deionised water and 3 ml of 30% H2O2. 6. With the beaker covered, heat the sample gently to start the peroxide reaction. If effervescence becomes excessively vigorous, remove the sample from the hot plate. Continue to add 30% H2O2 in 1 ml increments, followed by gentle heating until the effervescence subsides. 7. Add 5 ml of concentrated HCl and 10 ml of deionised water and reflux the sample for an additional 15 minutes without boiling. 8. Cool and filter through a Whatman No. 42 filter paper. Dilute to 50 ml with deionised water. Analyze for Cd, Cr, Ni, and Pb by atomic absorption spectrophotometer or inductively coupled plasma (ICP) spectroscopy.
The EPA Method (3052)

The United States Environmental Protection Agency adopted the EPA method No. 3052 for the acid digestion of siliceous and organically based matrices in a closed vessel device using temperature control microwave heating.
Apparatus

AAS Microwave oven Flasks
Reagents

1. Nitric Acid (HNO3), 65% 2. Hydroflouric Acid (HF), 40%
Procedure

1. Weigh 0.5 g of sample in a microwave vessel.

100

Analyze for Cd. Ni. Cool the rotor by air or by water until the solution reaches room temperature. Step 1 2 Time 5 min 10 min Temperature 180 C 180oC o Microwave power Up to 1000 watt Up to 1000 watt The EPA Method (3060A) . then gently swirl the solution to homogenize it. Add 9 ml HNO3 and 3 ml HF acids. 3. 5.Alkaline Digestion for Hexavalent Chromium For the extraction of Cr (VI) the sample is digested using 0. Open the vessel and transfer the solution to a marked flask. 101 .28 M Na2CO3 and 0.95oC for 60 minutes to dissolve the Cr(VI) and stabilize it against reduction to Cr(III). Cr. Close the vessel and introduce it into the rotor segment 4. 6.5 M NaOH solutions and heating at 90 .2. Cr (VI) can be measured in the extract by Atomic Absorption Spectrophotometer or ICPMS or other validated analytical techniques (EPA methods 7196 or 7199). and Pb by atomic absorption spectrophotometer or inductively coupled plasma (ICP) spectroscopy. Run the microwave programme to completion as suggested by the microwave manual.

1956). 1962. x-rays are scattered. 1969. A crystal plane is composed of a systematic and/or periodic arrangement of atoms in space. a number of XRD runs are made on pre-treated samples. Amorphous and free iron may be present as coatings. Mg or Mg plus glycolation. 1972). 1980 and Carson and Dixon. and 1.1 nm). The coherently scattered waves may constructively interfere with each other. This kind of arrangement of atoms is called a crystal lattice.4 nm for vermicullite. depending on pre-treatment. Saturation with K will normally effect a collapse of 102 . Potassium saturation and glycolation of Mgsamples are used to distinguish between expanding and nonminerals. Clay minerals are crystalline in structure and built of several planes. These phenomena influence the physico-chemical properties of the soil clay fraction. and management practices. The removal of these compounds is usually performed by the dithionite-citrate-bicarbonate (DCB) method (Jackson. 1. organic matter is removed by treating the clay samples with H2O2. For differently saturated expanding the identification of minerals. during its formation. which corresponds to the unit of x-ray wavelength.2 nm for montmorillonite. and in order to enhance the diffraction peaks. like saturation of the mineral with K. Mineralogical analysis is based on the principle that x-rays will be diffracted by these planes. fertility status. The common unit for the measurement of the distance between planes. Schwertmann.S. system of soil taxonomy includes the identification of clay minerals. The diffraction pattern serves as a fingerprint of each mineral. Sayegh and Rehman. This is why the U. Type of clay minerals can then be identified by measuring this diffraction at different angles. 1969. and heating at 5000C. effects certain shifts in spacing that are characteristic of the type of mineral. known as lattice spacing or intermicellar spacing.715 nm is characteristic for kaolinite. producing diffraction maxima. For example. Prior to running an XRD. Removal of CaCO3 is done by an acid treatment. Besides. The nature and relative presence of clay minerals determine to a great extent soil properties and characteristics. Pre-treatment of the clay sample. is the angstrom unit (1Å = 0.21. Bajwa. Each mineral type is characterized. When a beam of x-rays hits a crystal. potassium and ammonium retention showed a direct relationship with the type of clay minerals present in soil (Sayegh and Abdul Majed. Each atom in the lattice serves as a scattering point. A spacing of 0.0–1. by a certain pattern of spacing between planes. and clay particles attain negatively charged surfaces. substitution of certain elements for some higher valence positively charged elements (isomorphous replacement) occur. IDENTIFICATION OF CLAY MINERALS BY X-RAY DIFFRACTION (XRD) The very fine size (<2 microns) of the clay particles give rise to very high specific surface area. phosphorous.

0 0.g. and radiation counts or peak intensities in 103 .4 1. Effect of pre-treatments on the d-spacing of selected clay minerals d-spacing nm Clay minerals K-saturated samples 1.intermicellar spacing.2 0.0-1.4 1. smectite and illite Illite. and the value for d-spacing of 2.0-1. Reconstitution of the d-spacing to 1. Table 3 presents the intermicellar spacing for some common clay minerals under different conditions of pre-treatment.7-1. chlorite Mg-saturated + glycolation 1.72-0.7 nm is achieved by the glycolation procedure. Table 3..72-0.2 0.715 Smectite Vermiculite Illite.0 nm. chlorite Mg-saturated samples 1. e. halloysite Kaolinite.4 1.2 0.0-1.70 Chlorites Vermiculites Chlorites (kaolinite and sesquioxides become amorphous) The diffractogram is composed of a series of diffraction peaks printed with the beam angles (2 ) on the abscissa. chlorite.7 nm exhibited by smectite collapse to 1. halloysite Kaolinite Heat at 500 °C 1.0-1. metahalloysite Kaolinite.715 Vermiculite.75 0.4 1. kaolinite. illite Halloysite.75 Vermiculite. chlorite Smectite.8 1. None of these treatments will have any effect on the d-spacing of non-expanding minerals.

Saturation with K produces a shift of the peak to 1. 1995) Smectite or montmorillonite mineral type is characterized by a first-order xray diffraction peak of 1. 1995). Peaks serve as fingerprints for the identification of the mineral species. 104 . which does not change with pre-treatment.the y-axis. Figure 9. The following illustrations serve as examples (Tan.0 nm (Figure 10). Identification of kaolinite using its characteristic XRD patterns (Source: Tan.23 nm that shifts to 1.713 nm. Figure 9. The position of the diffraction peaks corresponds directly to the dspacing. exhibits a diffractogram characteristic of kaolinite clay mineral characterized by a first-order x-ray diffraction peak of 0.73 nm after solvation or glycolation of the sample.

1995) 105 .Figure 10. Identification of smectite using its characteristic XRD patterns (Source: Tan.

I. J. Contribution à l'étude des sols gypseux de la partie sud du golfe de Gabès. 9:65-75. Es 33.S. I. 1962. 1980. Miller. Quantitative x-ray mineral analysis of clays. 15(6):90-100. In Rural Integrated Development of the Mountains of Northern Lebanon. XL11-2. Macmillan Publ. 1974. Bashour. Abrukova. Bashour.. Soil Sci. Brady. University of Ghent. G. 5.1. The Nature and Properties of Soils: Macmillan Publ. England. W. Bashour. 1920. A.. pp. Anal.Y. I. Assoc. A. M. A. and Roederer.. Mineralogy of Al-Hasa Desert soils (Saudi Arabia). Mineralogical Society.. monograph No. 1933. Section spéc.H. Arid Zones Res. M. Jodhpur.171-182. Vol.M. G. and Isayev.C.F. New York. Boyadgiev. and McClure. USA Brindley. Soil Sci. Prasad. G. P. and Sayegh. Mineral. 141-438. A. Classification of gypsum-bearing soils in the transcaucasus.P. N. Management of Problem Soils in Arid Ecosystem. A. 1990. NY. Co. 2000. Akhvlediani.I. 3. 8:145-149. In: Crystal structures of clays Minerals and their x-ray identification.. CRC.. Forms of evolution of gypsum in arid soils and soil parent materials. Vol. NY. 11:1019-1027.M. Fertility and fertilizer requirements. Beirut. and Mazroa. 29:327-340.. 1992.D. Thesis.A. 532-534. Co. London. Structural mechanical properties of greybrown gypsiferous soils. Belgium. USA. 1995. The Land Journal. Soc. Plant. P. France Etude Sol. 1960. New York. pp. Bureau. Pedologie. and Al-Jaloud. Soviet Soil Science. Ph. New York. Gypsiferous soils of Iraq. 1980. and Sayegh. Soil clay mineralogies in relation to fertility management . L.I. N.E. Boyadgiev.References Aba-Husayn. Comm. Salty soils of arid and semi-arid regions Sci. Bajwa. T.L. FAO Report to Ministry of Agriculture. Morphology and composition of some soils under cultivation in Saudi Arabia. Al-Mashhady. d'Etudes de pédologie et d'Hydrologie. 1973. Lebanon. 1983. The crystalline state. 25(2):138-147. Geoderma. Bear. Balba. 106 . I. Phosphorus fractionation in calcareous arid soils in Saudi Arabia. 3:1-47. 1985. T.effect of soil clay mineral compositions on potassium fixation under conditions of wetland rice culture. Sampling soil plots.W. Soviet Soil Science.M. T. Lewis Publishers.I. V. Rev. Scientific Publisher.H. Bull. Clays and clay minerals. 2001. 1983.D.K. Bragg. F. Barzangi. A.

pp. 1965. and Sayegh. Am. Agronomie Tropicale. Carstea. 1957.P. M.R. F. M. 1972. 1944.H. W. Soil Sci. Sanchez Conde. R and Bohor..S. U. 22:322-337. 58:275-288. Paper No... 1965.. Techn. Chem. 107 . 7:519-525. Canadian J..E. L. Drouineau. H.. New York.G. Coghill. Matrix-flushing method for quantitative multicomponent analysis. 1974. Soil Sci. Soil Sci. Sanchez Conde. P.Carson. M. Deb.H. 1969. 12:441-450. Potassium selectivity in certain montmorillonitic soil clays. 12:1242-1253. Laboratory manual for introductory soil science. Cary. Carter. Paris.P. 398-411.M. AGON/SF/SYR/67/522. Hughes. W.P. The Euphrates pilot irrigation project. 18:227-232. S. Soil Sci. Méthodes d'analyse utilisables pour les sols salés. Hesse. F. Chang. Proc. Cryst.E. Soc. J. The fixation of phosphorus by soils. Am.B. B. NY. and Thien.D. Iowa. Random clay powders prepared by spray drying. A. V.G. Mineral. E. Hemwall. Co. 95-112. 1937. C. 1942. D.G. S.J. J. B. Publ. Hernando. W.R. 33:571-574. The stability of different forms of selenium applied to low-selenium soils. Methods of soil analysis-texture analysis of gypsic soils. 16:437-447. Hesse. Quantitative interpretation of x-ray diffraction patterns of mixtures. Ball-mill grinding. 61:173175.S. V. Dubuque. G. Study of the mineral nutrition of maize on soils rich in gypsum. Brown Company Publishers. 1970. 1969. J. Proc. Journal of Indian Society of Soil Science. and Contreras. J. Coutinet.B. 36:838-843.G. J. 1981. Appl. S. Bureau Mines.D. and Allaway. Anales de Edafologia y Agrobiologia. 1963. Properties of vermiculites and smectites: expansion and collapse. Dosage rapide du calcaire actif.D. 1977. P. 55:1780-1786. Principles of soil sampling. Association of total CaCO3 and active CaCO3 with growth of fine tree species on chernozemic soils. Palermo 1964. Annales Agronomiques.H.D. 1974. Am. A Textbook of Soil Chemical Analysis. Mechanical analysis of calcareous soils and distribution of CaCO3 in various fractions. M. Foth H. Harward. Withee. M. Advances in Agronomy 1957. and Devaney.H. calcaires et gypseux..V.. I. Soc.. Influencia de los niveles de yeso y de humedad en la fertilidad de un svelo yesoso.. Clays and Clay Minerals. Hernando.R. Jacobs. pp. Zolfo in Agricultura. and Chadha. and Contreras.. FAO. Cline. 1970. and Dixon. 581. 1972.

103:115-134. Giordano.A. John Wiley & Sons.. 643-698.B. In: Micronutrients in Agriculture.. SSSA Spec. Note on a proposed method for the mechanical analyses of gypsiferous soils. Univ. Appleton-Century Co. 1973. Soc. Soil Chemical Analysis . Am.J.J. and Nelson. P. Marcuse. iron... Mortvedt. W. Soil Sci. K. pp. Commonwealth Bureau of Soils Technical Communication N: 5H. Publ. preparation and analysis. M. 1978. J. F. Jump. Sayegh. Equilibria of metal chelates in soil solution.. J. Mordvedt. P. Soil Sampling. Inc. 1973. 5:189-206. Part 2. of Wisconsin. Krauskoph.J. Madison.Advanced Course.M. 1956. A. 1938. Syria. In: Micronutrients in Agriculture. Mortvedt (ed).R. Lindsay. WI. 1949. WI. J. N. Ed: Selenium in agriculture and the environment. Jackson. Soc. W.L. 1989. D. G.7-40. Geochemistry of micronutrients. 108 .. Effectiveness of some iron phosphate as sources of phosphorus for plants. Inc. and Sabey. Plant and Soil. Am. Am. pp. Jacobs.R. 1973. S. W.L. NY. Madison. Damascus. of irrigation and drainage division ASCE.D.T. R. 1978. J.A. Pages 95-105 in L. Pettijohn. 1982.C.K. Methods for analysis of irrigated soils.M. Am.Hurlbut (Jr. Krumbein. 1977. 1977. Inorganic phase equilibria of micronutrients in soils. W. and Norvell. In: Methods of Soil Analysis.L.S. Am. New York. Lindsay (eds). and De Ment. In: Micronutrient in Agriculture. J. J. 1996. Nitrogen .H. 4157.. J. Matar. Lindsay W.Z. manganese and copper. and W.V. Soil Sci. 23 Chapter 5. USA. Optimum allocation and variance components in nested sampling with an application to chemical analysis.J. NY. Development of DTPA soil test for zinc.J. Soc.. and Hoffman. 14:118.L. Lindsay. C. Aust. C. Biometrics. Crop salt tolerance current assessment. H.W. Soc. A.L. New York. T. B. pp.L. 1978. WI. 1974.115-138. Dept. ACSAD publication. Madison. Marcel Dekker Inc. Soc. Soils.. Loveday. Giordano. Manual of Sedimentary Petrology. New York. Agr. and Atallah. pp.K.inorganic forms. Manual of Mineralogy.W.E. Keeney. Maas. 29:277-81. Norvell. and Klein. Soil Sci. 10016. Soil Res. Soil test extractants for predicting selenium in plants. Inc. Kim. D.L. The effect of soil conditioners on pore size distribution and water retention of a calcareous soil. NY. Madison. E. Marwan. Soil Sci. Lindsay (eds). II: Particle size analysis. H. A.). 1961. and W. and Douleimy. J. WI. 42:421-428. The Arab Center for the Studies of Arid Zones and Dry Lands. W.

A. and Chamblee. 17:343-357. Soc. Sayegh. J. Handbook No.. Agrochimica. Sayegh. 1986.G. 125(5):194-300. 20(1):167-175. Khan. Sayegh. Soils and Environmental Quality. University of Calif. R. Rome. Agron. International symposium on new developments in the field of salt affected soils (December 4-9. Lebanon. 1969. 39:26-40.J. Sayegh. Soil Sci. 47:20-23. 1969. United State Salinity Laboratory Staff. N. 1955. 109 . J. Pierzynski. Harward. FAO Soils Bulletin 62. 108:202-208. Schwertmann. Sims. A. Cairo. Soil Sci. Government Printing Office. U.S.M. and Rigney.H. Proc. and Ryan. USA. J. Sayegh. D. USA.Petersen. Dung.F.H.. M..H.E.. Service. P. 1975. Soil Science. (ed.. American Mineralogist. Bodenkunde.. A. 1978. Soil sampling from fields of uniform and no uniform appearance and soil types. A.H.A.A. In: Management of gypsiferous soil. A. 60. Sayegh. 1947. A. J. Some physical and chemical properties of soils in the Beqa'a plain.A. 1965. A. 1924. 97:9-25. R. A. CRC Press Washington DC. G. L. Alban. Washington D. Soil Sci.H. Diagnosis and improvement of Saline and Sodic Soils. Sayegh A.H. Calif (mimeo).H.T. The Journal of Soil Science. Amer. General Organization for Government printing offices. J. Soil variability as determined by statistical methods. 2000. 1969.F. and Vance. A. A.S. E. Z.. Khan. 1962. Optimum size of sample for hand separation of forage crop mixtures into their component species in small plot experiments. Die selective kationensorption der Tonfraktion einiger Boden aus Sedimenten..H.C. G. Schoonover. Soc.H.. Humidity and temperature interaction with respect to K-saturated expanding clay minerals. Sayegh. Examination of soils for alkali-quick tests. U. and Petersen. 1954. Pflan. Agron. J. 50:490-495. Ammonium fixation in alkaline Lebanese soils. H. A. Arab Republic of Egypt. 22:252-254. Berkeley. Suggestion of criteria for sampling and classifying salt affected soils of the Middle East... and Salib. and Knox.). United State Department of Agriculture. L. 1972). and Abdul Majid. 1958. 1953. and Rehman. Factors affecting gypsum and cation exchange capacity determinations in gypsiferous soils. Am. Italy. Reed. Post. Ext. Phosphorus fractionation and retention in alkaline Lebanese soils. Richards. A sampling study in a saline and alkali area.G. XIII(3):265-276.G.

J. Olsen S. Thesis. Randomly oriented powders for quantitative identification by x-ray diffraction. Cahiers/ORSTOM. New York. Ministry of Agriculture and Water. Vieillefon. 110 . 1993. Serie Pedologie. Soc. Marcel Dekker Inc. 1996.. Jones. R.J. American University of Beirut. D.M. Effect of nitrogen fertilization on dryland wheat on grain selenium concentration.J. Van Schuylenborgh.L. Page et al. Soc. Preparation.D. Soil Sampling.M. of Agronomy. The effect of manganese sulfate on several crops growing on organic soil when applied as a stream or spray on the crop. Wisconsin. Soc. Soltanpour.R. 1995. Effect of variations in digestion conditions and inorganic soil constituents.. Tisdale.G. Rome. Part 2. Soltanpour. and Nelson. D. N. Land evaluation in Europe. Soil Sci. FAO Soils Bulletin 29.. Soil Fertility and Fertilizers. G. and Workman. 63:251-263. 8:334-340. 2:50-57. Soltanpour.. 1994. J. Environmental Soil Science. The effect of air-drying of soil samples upon some physical soil properties. and Wilson. S. pp. ASA. Italy. 1943. 1988. A.L.. SSSAJ.Sherman.J. Sys. Neth. Optical emission spectrometry.L. Proc. Chemical Methods. and Jones.B. Marcel Dekker Inc. Fox. Am. Thabet. Amer..Y. Directorate of Agricultural Research. Sparks. and Goos.. A. A quick method to extract organic phosphorus from soils. 1979. Soil Sci.M. Wageningen. Macmillan Co. Gypsiferous soils. 1972. Methods of Soil Analysis. G. Walkley.C.. Lebanon. 113.N. P.Y. Eds. R. Madison. USA. 1982a. A critical examination of a rapid method for determining organic carbon in soils. (ed). Tan. Tan. 9:345-348. J.L.. M. 1947. NY. Pages 29-65 in A. W. the Netherlands. Tarzi. 1975. 1954. P. Contribution to the improvement of analysis of gypsiferous soils. J. 1971. and Rios Romero. and Analysis. Kingdom of Saudi Arabia. N. R.. Part three. 2nd ed.N. Sci. P. 1984.L.H. New York. WI. F. Clay Mineral. Riyadh. 9. 1975. Beirut. Duthie. Madison. C. Soil Sci. 51:255-256. J. New York. P. Thomson. A. K. Am.H. Van Alphen. Bulletin 12.L.. 1982b. Procedures for collecting soil samples for different purposes. and Harmer. S. J. USA . Active and total CaCO3 in soils. 17:195-223. Method of Soil Analysis. K.P. Agronomy No. International Institute for Land Reclamation and Improvement. 46:430-433.N. Agri.

). Test of an ascorbic acid method for determining phosphorus in water and NaHCO3 extracts from soil. NY.. 1943.Watanabe. Amer. and Diehl. Soc.. X-ray diffraction techniques. Univ. Klute (ed. Soc.R. Am. A. 1966. Proc. 1918. Westin F.331-362. 9. in Agr. In: Methods of Soil Analysis. and Allardice. Whittig. Variability in soils and its significance to past and future soil investigations. Waynick. Van Nostrad. Soil phosphorus in South Dakota I: inorganic phosphorus fixation of some soil series. 30:245.S. pp. 29:677-678. H. Agronomy and Soil Sci.. Proc.H. Advanced Qualitative Analysis. New York. of California Pub. WI. L. Soil Sci. Am. Sci. G. W.C. S. Inc. 3:243-269. Soc.D. Agronomy series No. 1986.J. 111 . H. Soil Sci. 1965. Am. and Buntley.D. Willard.R. and Olsen. F.. Madison. Part 1. D..

49 4.09 (242) (210) 39. List of the atomic weights of the elements Element Actinium Aluminium Americium Antimony Argon Arsenic Astatine Barium Berkelium Beryllium Bismuth Boron Bromine Cadmium Calcium Californium Carbon Cerium Cesium Chlorine Chromium Cobalt Copper Curium Dysprosium Einsteinium Erbium Europium Fermium Fluorine Francium Gadolinium Gallium Germanium Gold Hafnium Helium Holmium Hydrogen Indium Iodine Iridium Iron Krypton Lanthanum Lawrencium Lead Lithium Lutetium Magnesium Manganese Symbol Ac Al Am Sb Ar As At Ba Bk Be Bi B Br Cd Ca Cf C Ce Cs Cl Cr Co Cu Cm Dy Es Er Eu Fm F Fr Gd Ga Ge Au Hf He Ho H In I Ir Fe Kr La Lw Pb Li Lu Mg Mn Atomic Number 89 13 95 51 18 33 85 56 97 4 83 5 35 48 20 98 6 58 55 17 24 27 29 96 66 99 68 63 100 9 87 64 31 32 79 72 2 67 1 49 53 77 26 36 57 103 82 3 71 12 25 Atomic Weight (227) 26.35 44.72 72.91 (147) (231) (226) (222) 186.34 (249) 9.183 (237) 58.59 95.00 58. 112 .96 (253) 19.08 (251) 12.30 173.93 118.94 Element Mercury Molybdenum Neodymium Neon Neptunium Nickel Niobium Nitrogen Nobelium Osmium Oxygen Palladium Phosphorus Platinum Plutonium Polonium Potassium Praseodymium Promethium Protactinium Radium Radon Rhenium Rhodium Rubidium Ruthenium Samarium Scandium Selenium Silicon Silver Sodium Strontium Sulfur Tantalum Technetium Tellurium Terbium Thallium Thorium Thulium Tin Titanium Tungsten Uranium Vanadium Xenon Ytterbium Yttrium Zinc Zirconium Symbol Hg Mo Nd Ne Np Ni Nb N No Os O Pd P Pt Pu Po K Pr Pm Pa Ra Rn Re Rh Rb Ru Sm Sc Se Si Ag Na Sr S Ta Tc Te Tb Tl Th Tm Sn Ti W U V Xe Yb Y Zn Zr Atomic Number 80 42 60 10 93 28 41 7 102 76 8 46 15 78 94 84 19 59 61 91 88 86 75 45 37 44 62 21 34 14 47 11 38 16 73 43 52 65 81 90 69 50 22 74 92 23 54 70 39 30 40 Atomic Weight 200.90 192.26 151.60 158.312 54.94 144.Appendix A.93 63.40 40.011 140.12 132.03 50.37 91.54 (247) 162.24 20.9994 106.80 138.0080 114.00 (223) 157.939 174.47 101.92 204.69 47.04 88.2 15.85 238.91 35.09 107.25 69.92 (210) 137.9898 87.453 52.91 65.91 85.85 83.50 (254) 167.59 196.1 150.81 79.909 112.003 164.91 (257) 207.4 30.97 24.012 208.22 Mendelevium Md 101 (256) Numbers in parentheses indicate mass of most stable known isotopes.37 232.96 78.974 195.870 22.94 131.71 92.97 178.102 140.91 14.82 126.948 74.064 180.75 39.04 168.93 1.19 6.007 (253) 190.98 10.23 102.96 28.98 (243) 121.90 183.95 (99) 127.2 55.62 32.

8 4.7 4.4 7.6 8.8 8.4 5.6 9.6 1.0 8.1 13.6 8.0 8.4 5.8 2.8 5.2 5.2 5.0 9.2 1.4 4.5.4 7.0 4.8 10.2 4.0 6.0 5.4-Dinitrophenol 4-Dimethylaminoazobenzene Bromochlorophenol blue Bromophenol blue Methyl orange Bromocresol green 2. 113 .8 7.0 8.9 3.2 6.2 8.7 5.1 7.0 yellow yellow yellow yellow Colourless Yellow Yellow-orange Purple Purple Yellow-orange Blue Yellow Violet Yellow-orange Yellow-orange Purple Violet Blue Purple Purple Yellow Blue Red Blue Red Yellow-orange Orange-yellow Purple Purple Blue-green Purple Blue Blue Red-violet Blue Brownish-yellow Violet 1 Adapted from pH Indicators.8 6.0 5.0 6.5-Dinitrophenol Alizarinsulfonic acid sodium salt Methyl red Methyl red sodium salt Chlorophenol red Hematoxylin Litmus extra pure Bromophenol red Bromocresol purple 4-Nitrophenol Bromoxylenol blue Alizarin Bromothymol blue Phenol red 3-Nitrophenol Neutral red 4.4 4.6 6.0 3.2 7.8 6.6 4.2 9.2 1.8 2. pH indicators1 pH Indicators Name Colour pH transition intervals pH pH Colour Cresol red m-Cresol purple Thymol blue p-Xylenol blue Triphenylcarbinol 2.4 6.3 10.2 1. Merck and Co.2 8.3 4.0 7.7-Tetrabromophenolphthalein Cresol red 1-Naphtholphthalein m-Cresol purple Thymol blue P-Xylenol blue Phenolphthalein Thymolphthalein Alizarin yellow GG Epsilon blue pink red red red red Colourless Red Yellow Yellow Red Yellow Colourless Yellow Red Red Yellow Yellow Red Orange-yellow Yellow Colourless Yellow Yellow Yellow Yellow Colourless Bluish-red Colourless Orange Brownish Yellow Yellow Yellow Colourless Colourless Light yellow Orange 0.8 2.8 7.0 8.0 7.1 3.2 6.6 9.4 8.0 4.8 6.Appendix B.2 1.5 7.6.3 9.4 5.2 11.5 12.0 3.2 2.3 6. E.6 4.8 3.8 2.

Alloys with gold. fused nitrates. Shock °C Chemical Inertness Notes Trademarks: pyrex (Corning Glass Works) Kimax (Owens-Illinois) Borosilicate glass 200 Soft glass Alkali-resistant glass Fused quartz High-silica glass Porcelain 1050 1000 Attacked to certain 150°C change degree by OK alkali solutions while heating Attacked by alkali Low solutions More sensitive than borosilicate Resistant to most acids. Properties of laboratory materials Material Max. molten salts. Attacked by many organic solvents (acetone. H2SO4. Trademark: Corning Quartz crucibles used for fusions Similar to fused quartz More resistant to alkalis Trademark: Vycor than borosilicate (Corning) 1100 (glazed) High 1400 (unglazed) High Resistant to most acids. Attacked by many organic solvents Inert to most chemicals Usually alloyed with iridium or rhodium to increase hardness. chlorides at >1000°C. and boiling conc. ethanol OK) Not attacked by HF. HCI. Platinum crucibles for fusions and treatment with HF Ni and Fe crucibles used for peroxide fusions Platinum 1500 Nickel and iron Stainless steel 400-500 High Polyethylene 115 Flexible plastic Polystyrene 70 Somewhat brittle Useful for storage of solutions and reagents for trace metal analysis Teflon 250 114 . HNO3 Not attacked by alkali solutions or HF. silver. Working Sensitivity to Thermal Temperature. Attacked by aqua regia. Very High halogens Very High Boron-free.Appendix C. dil. and other metals Fused samples contaminated with the metal Not attacked by alkalis and acids except conc. cyanides.

08 0. but still unknown quality Meets minimum purity standards High purity Highest purity Conforms to tolerance set by the United States Pharmacopoeia for contaminants dangerous to health Conforms to minimum specifications set by the Reagent Chemicals Committee of the American Chemical Society Required for accurate volumetric analysis (for standard solutions) Notes May be used in preparation of cleaning solution only Concentrations of Commercial Reagent-Grade Acids and basesa Reagent H2SO4 HClO4 HCl HNO3 H3PO4 HC2H3O2 NH3 a b c F. ml Transfer Pipettes Burettes 0.P. Molarity.C.02 0.0 38.051 0.898 These are approximate concentrations and cannot be used for preparing standard solutions.01 98. A.4 14.01 0.8 % by Wt.10 0.00 60. Class Aa Capacity.b 98.P.0 Density (20°).831 1.0 69. (Chemically pure) U.05 0.0 99.5 36.02 0.03 0.15 0.S. Wt. reagent Reagent grade Primary standard Analytical grade Purity Indeterminate quality More refined.5 28.689 1.4 15.0 70.02 0.46 63. NBS Tolerances for Volumetric Glassware.6 11. Grades of chemicals Grade Technical or commercial C.0 85. ml (Less than and Including) 1000 500 100 50 25 10 5 2 a Volumetric Flasks 0. conform to these tolerances.01 Corning Pyrex glassware and Kimball KIMAX.03 0. 115 .30 0.Appendix D.006 0.05 0.6 12. Class A.S.03 Mc 17.02 Tolerances.188 1.7 17.08 100.05 0.668 1. g/cm3 1.05 17.08 0.4 14. Formula weight.409 1. 94.03 0.

NO3-N Phosphorus Olson method 0–5 0–3 5 – 15 3–8 15 – 30 8 – 14 30 – 40 4 – 20 >40 >20 Potassium 0 – 85 NH4OAC. mg/kg (Bashour. Nutrient range in soils.extractable Magnesium Exchangeable Calcium Exchangeable Sulphur Water soluble Sodium Water Soluble 0 – 85 0 – 500 0 – 10 0 – 300 85 – 150 150 – 250 250 – 450 >450 85 – 180 500 – 1200 10 – 20 180 – 300 300 – 500 >500 1200 – 2500 2500 – 3500 >3500 20 – 35 35 – 45 >45 >300 116 .Appendix E. 2001) Nutrient Very Low Low Medium High Very High Nitrate.

9 67.8 44.7 82.4 32.2 41.960 0.152 1.0 24.0 68.375 1.4 57.2 32. R25 = Rt/ft ft 1.2 26.117 1.867 0.4 19.877 0.4 30.0 °F.0 25.918 0.4 87.087 28.247 1.6 31.097 1.8 83.2 95.6 86.9 85.2 29.4 22.861 0.0 13.2 22.Appendix F.996 0.694 0.8 71.157 1.6 18.0 60.147 1.921 0.4 ft 1.4 70.1 74.0 45.4 93.2 20.2 1.8 88.2 27.2 59.0 ft.043 1.801 0.907 0.4 73.3 67.964 0.0 36.6 32.8 °F.7 73.0 81.8 107.843 0.9 1.2 82.0 32.0 15.102 1.716 0.7 87.4 83.6 64.3 85.8 27.2 84.4 111.2 23.911 0.0 31.6 55.5 88.092 ft.6 70.122 1.038 1.3 90.6 81.0 40.0 4.613 1.2 19.0 91. Dept of Agriculture 117 .082 28. 71.763 0.5 78.0 22. 84.6 75.829 0.064 1.2 104.528 1.142 1.029 1.3 81.2 75.0 41.277 1.0 34.8 1.6 72.055 1.8 116.815 0.4 20.0 19.1 69.012 1.0 77.0 6.897 0.0 105.992 0.884 0.914 0.858 0.047 1.2 113.4 29.0 12.9 89.4 0.0 96.947 °C 29.8 25.971 0.2 31.8 30.0 16.4 26.004 1.8 33.950 0.8 31.2 30.887 0.218 1.8 0.309 1.8 75.488 1.0 8.873 0.8 74.8 26.S.6 100.0 37.0 7.0 30.940 21.0 27.8 66.6 26.8 32.956 0.4 23.2 18.2 66.0 35.6 83.788 0.8 20.020 1.0 39.8 53.5 1.683 21.2 24.8 °F.4 48.988 0.2 89.6 27.6 84.008 1.3 76.6 30.0 42. EC25 = (k/Rt) °C 22.936 21.0 44.0 11.0 18.078 28.8 0.8 23. 37.488 1.727 0.2 80.4 27.953 0.127 1.1 87.8 19.8 62.4 64.7 78.705 0.4 18.880 0.0 17.073 28. Temperature factors (ft) for correcting resistance and conductivity data on soil extracts to the standard temperature of 25°C EC25 = ECt °C 3.9 76.016 1.660 1.6 29.2 102.189 1.5 65.0 69. U.051 1.904 0.0 20.4 86.932 21.0 72.979 0.894 0.000 0.107 1.943 21.3 72.136 1.925 0.5 74.864 0.6 25.0 86.025 1.2 25.068 28.1 65.0 73.7 69.112 1.2 50.2 70.6 77.4 25.8 24.131 1.8 65.6 90.4 68.967 0.1 0.983 0.6 19.0 46.901 0.4 31.6 ft 0.8 98.0 82.0 51.6 22.6 20.8 79.929 Source: Agricultural Handbook 60.2 79.163 1.6 46.870 0.739 0.6 109.0 38.0 23.6 68.0 18.341 1.569 1.975 0.9 80.0 114.034 1.890 0.4 39.5 79.0 29.0 42.0 10.0 14.1 78.411 1.2 88.6 24.7 91.0 47.2 1.5 0.6 23.0 9.775 0.0 90.750 0.0 43.4 24.6 66.709 1.0 5.4 77.0 26.060 1.

20 10 3.102 -3 gram. oz pound.49 1.3 3.24 0. ton ton (U.77 1.057 3.78 acre-inch cubic foot.914 0.).47 247 0.55 10-3 10-3 104 10-2 10-2 hectare.3 6. kg ha-1 liter per hectare.78 0.47 10-4 10. in3 bushel. t ha-1 megagram per hectare. km2 (103 m)2 square kilometer. L (10-3 m3) liter.10 2.Appendix G.946 28. Mg ha-1 meter per second. kg megagram. lb acre-1 pound per acre.907 0.).84 1. m3 cubic meter.386 2. g (10-3 kg) kilogram.609 0. pt Mass 102.29 10-2 645 9.454 100 907 0. μm (10-6 m) millimeter. km (103 m) meter.53 0.265 33.64 10-5 35.102 1. m2 square meter. km2 (103 m)2 square meter. yd foot. in2 Volume 0.94 10-2 10 kilometer.0 25.87 67.893 7.S. L (10-3 m3) -3 1. mi yard. m3 liter.52 10-2 2. Conversion factors for SI and non-SI units (Soil Science Society of America Journal) To convert Column 1 into Column 2.05 10-3 2. mi2 acre square foot. mm2 (10-3 m)2 cubic meter. qt cubic foot. m s-1 1.4 0.405 4. ton ton (U.107 893 893 0. kg ha-2 kilogram per hectare.4 0.19 62.24 0. nm (19-9 m) mile. Mg (tonne) tonne. ft micron.71 53.304 1. bu quart (liquid).59 1. multiply by Column 1 SI Unit Column 2 Non-SI Unit To convert Column 2 into Column 1 multiply by Length 0.590 4. lb acre-1 pound per bushel. ft2 square inch.0 3.24 10-2 10-2 10-2 10-2 kilogram per hectare.907 0. 56 lb bushel per acre. μ inch. ft3 cubic inch. L ha-1 tonnes per hectare. lb bu-1 bushel per acre.12 10-3 2.76 1.10 10-3 1. L (10-3 m3) liter. å Area 2. lb ounce (avdp).35 1.621 1. mm (10-3 m) nanometer.473 2.05 103 9. m micrometer.01 1. ha square kilometer. L (10-3 m3) liter.75 9. in angstrom.447 118 . kg kilogram. kg ha kilogram per cubic meter. Mg ha-1 megagram per hectare.094 3. 60 lb bushel per acre. ton acre-1 mile per hour 454 28. kg kilogram. ft3 gallon pint (fluid).S. lb quintal (metric). t -1 pound.28 1. kg m-3 kilogram per hectare. q ton (2000 lb).12 10-3 1. ton Yield and Rate pound per acre. g (10 kg) gram. m2 square millimeter.446 2. m3 cubic meter. m meter.205 0.73 35.8 2.1 acre acre square mile.83 10-2 1.86 0.12 12. lb acre-1 ton (2000 lb) per acre. kg ha-1 kilogram per hectare. 48 lb gallon per acre pound per acre. L (10-3 m3) liter.

90 10 1. ppm milligram per kilogram. % parts per million. rd rem (roentgen equivalent man) Plant Nutrient Conversion 2. Ci picocurie per gram. acre-in hectare-centimeters. G Water Measurement cubic meter. gallons per minutes.7 10-2 100 100 Electrical Conductivity. S m-1 mmho cm-1 tesla. g kg percent. cm2 g-1 square meter per kilogram.32) 1.1 10-4 102. (continued) To convert Column 1 into Column 2. Pa pound per square foot. and Magnetism millimho per centimeter. Sv (equivalent dose) curie.00 47.273) (9/5 °C) + 32 57.01 10-2 10-2 10-4 1.28 8. Pa pound per square inch. ° 2 -1 2 -1 0.123 1. ft3 s-1 U. Gy (absorbed dose) sievert.73 10-3 9. m3 h-1 hectare-meters. ha-cm acre-feet. K Celsius.40 8.1 1. m3 h-1 cubic feet per second.09 1.101 0. rad Celsius.9 6.3 10 104 9. m kg square millimeter per gram. Mg m-3 gram per cubic centimeter.39 1.8 101.33 1 10 1 3.001 0.03 10-2 12. ha-m acre-inches. acre-in cubic meter per hour. acre-ft hectare-meters.830 0. m2 kg-1 square centimeter per gram.75 0. °F Plane Angle degrees (angle). MPa (106 Pa) megagram per cubic meter. lb in-2 Temperature Kelvin. pCi g-1 rad.45 Specific Surface square meter per kilogram.81 10-3 4.1 10-2 1 0. (ion exchange capacity) meq 100 g-1 -1 gram per kilogram. mg kg-1 Radioactivity becquerel. ha-m acre-feet. cmol kg-1 milliequivalents per 100 grams. lb ft-2 pascal.7 1010 37 0.90 103 1.11 97. °C Fahrenheit. Bq becquerel per kilogram.715 0.1 0.1 1 2.00 (K . siemen per meter. T gauss. Electricity.APPENDIX G. multiply by Column 1 SI Unit Column 2 Non-SI Unit To convert Column 2 into Column 1 multiply by 10 1000 9.437 0.602 119 . m3 acre-inches.00 2. °C radian. MPa (106 Pa) bar megapascal. Bq kg-1 gray. acre-ft Concentrations centimole per kilogram.9 0.29 1.66 Element P K Ca Mg Oxide P2O5 K 2O CaO MgO 0. mm g Pressure atmosphere megapascal. g cm-3 pascal.00 (°C + 273) 5/9 (°F .01 0. gal min-1 cubic meter per hour.227 0.7 10-11 2.20 1.S.

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