An Evaluation of Chicken Litter Ash, Wood Ash and Slag for Use as Lime and Phosphate Soil Amendments Baiq Emielda Yusiharni SP (B.Sc-Hon) in Soil Science University of Mataram, Indonesia 2001 This thesis is presented for the degree of Master of Science of The University of Western Australia School of Earth and Geographical Sciences Faculty of Natural and Agricultural Sciences 2007
85
Embed
An Evaluation of Chicken Litter Ash, Wood Ash and …research-repository.uwa.edu.au/files/3231623/Yusiharni...An Evaluation of Chicken Litter Ash, Wood Ash and Slag for Use as Lime
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
An Evaluation of Chicken Litter Ash, Wood
Ash and Slag for Use as Lime and Phosphate
Soil Amendments
Baiq Emielda Yusiharni SP (B.Sc-Hon) in Soil Science
University of Mataram, Indonesia 2001
This thesis is presented for the degree of
Master of Science of
The University of Western Australia
School of Earth and Geographical Sciences
Faculty of Natural and Agricultural Sciences 2007
ABSTRACT
Standard AOAC methods of chemical analysis have been used to characterize and
chicken litter ash (CLAT), wood ash (WA) and iron smelting slag for use as a
combined liming agent and phosphate fertilizer. Rock phosphate has this function and
was included for comparison purposes. All the byproducts had pH values above 9 and
a liming capacity above 90% of pure lime, as a result, these materials will be effective
as liming agents. Total P concentrations for CLA, CLAT, slag, and WA were 3.6%,
4.75%, 0.26%, and 0.44% respectively indicating that they could be used as P
fertilizers when applied at the high rates required for liming soils. For all the
byproducts, citric acid (CA) dissolved phosphorus at faster rate than did neutral
ammonium citrate (NAC) and alkaline ammonium citrate (AAC). For long extraction
times total P dissolved mostly increased in the sequence CA>NAC>AAC. For no
extraction time was the P soluble in the three extractants a reliable predictor of the
effectiveness of these materials as P fertilizers which was established by plant growth
measurements. XRD and SEM analyses identified the P containing compounds and
provided explanations for the chemical analyses and dissolution behaviour. CLA,
CLAT and WA consist mostly of mixtures of apatite, calcite, and quartz although
CLA also contains much carbonised litter, which contains a low concentration of P.
Calcium magnesium silicate (akermanite) and calcium aluminium silicate (gehlenite)
were the main constituents of slag. For all apatitic materials little apatite persisted in
CA residues after 120 hours extraction but considerable apatite remained in NAC and
AAC residues.
A glasshouse experiment was carried out to identify the effectiveness of the wastes as
phosphate fertilizers for a highly P-deficient acid lateritic soil. Treatments included
various types and rates of industrial byproducts and included monocalcium phosphate,
dicalcium phosphate and rock phosphate as reference materials. Various levels of
phosphate were applied, ryegrass was planted and harvested after 8 weeks and at 4
week intervals thereafter. Dry matter yield ranged from 0.025 g to 2.3 g/pot for the
first harvest, from 0.03 g to 2.3 g/pot for the second harvest and many plants died of P
deficiency before the third harvest. The agronomic effectiveness of the materials as
phosphate fertilizers was calculated by comparing the various amounts of phosphate
i
required to produce the same yield for the various materials and relating these values
to the performance of monocalcium phosphate. This is the “horizontal comparison” or
“substitution value” procedure that gives values of Relative Effectiveness (RE) that
are independent of the rate of application of the fertilizers. The RE values for all the
materials relative to monocalcium phosphate (100%) for the first harvest are as
follows, 50% for dicalcium phosphate, 31% for rock phosphate, 7% for partly burnt
chicken litter ash, 7% for totally burnt chicken litter ash and 1% for wood ash and
slag. The RE values for the second harvest were 100% for monocalcium phosphate,
80% for dicalcium phosphate, 40% for rock phosphate, 10% for partly burnt chicken
litter ash, 8% for totally burnt chicken litter ash and 2% for wood ash and slag. Data
for subsequent harvests are not reported due to the death of many plants. Clearly
chicken litter ash has appreciable value as a phosphate fertilizer whereas wood ash
and slag are ineffective. Explanations for these differences in effectiveness are
discussed in the text.
An evaluation of the liming effect of the byproducts indicates that they may be used
as a soil amendment on acid soils and are nearly as effective as standard lime
(CaCO3). Byproducts are also sources of other plant nutrients so they may be regarded
as a form of compound fertilizer and liming agent.
ii
ACKNOWLEDGEMENTS
I would like to give my deepest thanks and appreciation to my supervisor Prof.
Bob Gilkes for his help, encouragement, and great attention during supervising my
study. I also thank Dr. Andrew Rate as my cosupervisor.
I acknowledged Australian Government (AusAID) for providing financial
support for my postgraduate research. Special thanks to Rhonda Haskell and Cathy
Tang (AusAID Liaison Officers) for being friendly and helpful in many things.
I would like to express my great appreciation to my husband, Husnan Ziadi for
helping me with laboratory and glasshouse work and especially for all his support so
that I can finish my study. Special thank to my lovely daughters, Lula and Fadila.
I also thank Michael Smirk for his assistance in solving chemical analysis
problems. Special thanks to Gary Cass and Elizabeth Halladin for lending me
laboratory equipment. Thanks to Rick Roberts and family, Cameron Duggin, Than
Hai Ngo, Geoff Kew, Georgie Holbeche, Matt Landers, Yamin Ma and Rina Barus
for being friendly and helpful.
Finally, thanks to all mineralogy group members for your friendship and for
sharing knowledge, experiences, thoughts, and laboratory equipment.
iii
LISTS OF CONTENTS
ABSTRACT i AKNOWLEDGEMENTS iii LISTS OF CONTENTS iv LIST OF TABLES vi LIST OF FIGURES vii LIST OF APPENDICES ix Chapter 1. INTRODUCTION
1.1. General Introduction 1 1.2. Objectives of the Study 2 1.3. Structure of the Thesis 2
Chapter 2. LITERATURE REVIEW 2.1. Acid Soils 3 2.2. Effect of Soil Acidity on Plants 4 2.3. Acid Soils in Australia 5 2.4. Liming Resources and Lime Requirement 7 2.5. Industrial Byproducts as Liming agents
2.5.1 Slag 9 2.5.1.1 The Nature of Industrial slag 9 2.5.1.2 Application of Slag in Agriculture 12
2.5.2 Wood Ash 13 2.5.2.1 The Nature of Industrial Wood Ash 13 2.5.2.2 Application of Wood Ash in Agriculture 16
2.5.3 Chicken Litter Ash 16 2.5.3.1 The Nature of Industrial Chicken Litter Ash 16 2.5.3.2 The Use of Chicken Litter Ash in
Agriculture 18
Chapter 3. A Laboratory Evaluation Of The Industrial Byproducts: Chicken Litter Ash, Wood Ash And Iron Smelting Slag For Use As Combined Liming Agent And Phosphorus Fertilizer
3.1. Introduction 20 3.2. Materials and Methods
3.2.1. Calcination of Chicken Litter 21 3.2.2. Industrial Byproducts 22 3.2.3. Characterisation of the Materials 22 3.2.4. Chemical Extraction of the Materials (AOAC Method) 23 3.2.5. Chemical Analysis of the Extracts 23 3.2.6. Glasshouse Experiment 24
3.3. Results and Discussion 24 3.3.1 Calcination of Chicken Litter 24
3.3.2 Dissolution of Industrial Byproducts 31 3.3.3 Relationship of Relative Agronomic Effectiveness (RE) of
CLA and CLAT with P Availability Determined by Chemical Extraction 39
3.4. Conclusions 41
iv
Chapter 4. Plant response to the byproducts: Chicken Litter Ash, Iron Smelting Slag and Wood Ash as Phosphorus Fertilizers 4.1. Introduction 42 4.2. Materials and Methods 42 4.2.1. Soil 42
4.2.2. Industrial Byproducts and Reference Fertilizers 42 4.2.3. Analysis of Industrial Byproducts and Soil 43 4.2.4. Glasshouse Experiment 43 4.2.5. Relative Agronomic Effectiveness 44
4.3. Results and Discussion 45 4.3.1. Byproduct Characterization 45 4.3.2. Soil pH, EC and Bicarbonate P 45
4.3.3. Plant Composition and Yield Response Data 47 4.3.4. Relative Effectiveness (RE) 51 4.4. Conclusions 52 Chapter 5. General Summaries, Limitation and Future Work 54 5.1. General Summary 54
5.2. Limitations and Future Works 55 Chapter 6. Publications from this thesis: 57 REFERENCES 58 APPENDICES 65
v
LIST OF TABLES
Table Page2.1.
2.2.
2.3.
2.4.
2.5.
2.6.
2.7.
2.8.
2.9.
2.10
3.1.
3.2.
3.3.
4.1. 4.2.
National and State areas (million hectares) of surface soil (0 - 10 cm) pH (measured in calcium chloride) based on information fromAustralian Soil Resources Information System (first number) andcommercial laboratories (second number).
Calcium carbonate equivalence values of some liming materials Chemical constituents of blast furnace slag (Lee 1974). Major element composition of slags (Li and Gilkes 2002). Chemical compositions of slag products used in New Zealand (Bolan2004). Mineralogical compositions of slags (Li and Gilkes 2002) Concentration of total and water-soluble plant nutrients in wood ash The chemical composition of plant ash derived from diverse species Characterisation of the chemical properties of chicken litter ash Nutrients present in Fibrophos based on the grades for Southern andCentral England/Wales The nomenclature for calcined chicken litter samples produced bycalcination at various temperatures and their pH measured in water Properties of industrial byproducts. Percentages of total phosphorus, calcium, magnesium, potassium and sodium dissolved after 1hour extraction in citrate solutions for chicken litter ash calcined at various temperatures and for Sechura rock phosphate (RP), wood ash (WA) and slag. Chemical properties of industrial byproducts and rock phosphate. Levels of P added to soil for the plant growth experiment Basal fertilizer and dose per pot used in the glasshouse experiment
6 8
10
11
11
12
14
15
17
18
21
27
32
43
44
vi
LIST OF FIGURES
Figure Page2.1.
2.2.
3.1.
3.2.
3.3.
3.4.
3.5.
3.6.
3.7.
3.8.
3.9
4.1
4.2.
4.3.
Soil pH ranges Interpolated top soil pH (1990-1999) Percentages of total P extracted from chicken litter ash produced atvarious temperatures for various durations of extraction in citric acid (A), neutral ammonium citrate (B) and alkaline ammonium citrate (C) XRD patterns of chicken litter ash calcined at various temperaturesbefore (A) and after extraction for 120 hours in citric acid (B), neutralammonium citrate (C) and alkaline ammonium citrate (C). Q = quartz (d = 3.43Ǻ), A = apatite (d = 2.84 Ǻ) Cu Kα radiation Scanning electron micrograph (SEM) and X-ray spectra of the indicated particles for 500oC calcined chicken litter (C500) before and after extraction for 120 hours in citrate solutions Percentage of P extracted from five phosphatic byproducts by threecitrate extractants for various durations of extraction XRD patterns of byproducts (A) and their residues after extraction for120 hours in citric acid (B), neutral ammonium citrate (C) and alkalineammonium citrate (D) Scanning electron micrographs (SEM) and X-ray spectra of indicated particles for original CLA and residues after extraction for 120 hours in three citrate solutions. X-ray spectrum of a carbon grain in partly burnt chicken litter ash showing that it contains minor amounts of Si, P, S, Cl, K, and Ca (A) and a silicate grain (feldspars) in totally burnt chicken litter ash containing much Si, Al, K and Ca (B). Scanning electron micrographs (SEM) and spectra of indicated grains for CLAT and residues after extraction for 120 hours in three citrate solutions. The relationship of relative agronomic effectiveness (RE) and thesolubility of P in CA for 6 hours extraction. Plots of log P applied (mg/kg) versus pH, EC, and Bic P for soil samples taken after the last harvest Yield (g/pot) versus log rate of P applied (mg/kg) for each harvest for the seven fertilizers Internal efficiency of P utilization curves for each harvest
4 6
25
28
30
33
35
36
37 38 40 46 48 49
vii
4.4. 4.5.
P content versus log P applied for all harvests RE values for the byproducts based on yield and P content for the fourharvests
50 52
viii
LIST OF APPENDICES
Appendix Page4.1.1
XRF Analysis of Plant Dry Tops for Harvest I 65
4.1.2
XRF Analysis of Plant Dry Tops for Harvest II 66
4.1.3
XRF Analysis of Plant Dry Tops for Harvest III 67
4.1.4
XRF Analysis of Plant Dry Tops for Harvest IV 68
4.2.1 Photograph showing the growth of ryegrass before the first harvest for the highest (a) and lowest (b) rates of all the fertilizers, including zero rate of application (control)
69
4.2.2 Photograph showing the growth of ryegrass before the second harvest for the highest (a) and lowest (b) rates of all the fertilizers, including zero rate of application (control).
70
4.2.3 Photograph showing the growth of ryegrass before the third harvest for the highest (a) and lowest (b) rates of all the fertilizers, including zero rate of application (control).
71
4.3
Concentration of Phosphorus in Plants Tissue 72
4.4.1
RE Values Based on P Applied and Yield for Each Harvest 73
4.4.2 RE Values Based on P Content and P Applied for Each Harvest
74
4.4.3
RE Values Based on Soil Bic P and P Applied for Each Harvest 75
ix
Chapter 1
1.0 Introduction
1.1. General Introduction
Soil acidity is a major problem worldwide as it decreases plant growth by affecting
the availability of nutrients and causes various toxicities. Acid soils may also suffer
from phosphorus, nitrogen, calcium, magnesium, potassium and other deficiencies
(Ritchie 1989; Samac and Tesfaye 2003). Acid conditions in soils cause aluminium
(Al) and manganese (Mn) to become more soluble (Slattery et al. 1999) and these
elements can be toxic to plants. Soil acidity also affects the activity of
microorganisms in soil (Robson and Abbott 1989). Acid soils are commonly deficient
in phosphate so that both conditions require correction, which can be carried out by
application of a single mineral ameliorant, which is the focus of this thesis.
Australia faces a serious problem with soil acidification. Acid soil has caused major
land degradation and has decreased plant production over several million hectares of
agricultural land in Australia (Evans, 1991). Approximately 35 million hectares of
agriculturally productive land presently have strongly acid soils (pHCa < 4.8) and 55
million hectares are fairly or slightly acid (pHCa 4.8-6.0) (Slattery et al. 1999).
Liming is the most common way to ameliorate acid soils. At some locations sources
of natural lime are inadequate or expensive. Alkaline industrial byproducts such as
metal smelting slag, wood ash and chicken litter ash may be used as replacements for
lime under these circumstances. Such byproduct materials are commonly dumped
however they may be used to ameliorate soils with consequential environmental
benefits. Some alkaline byproducts contain phosphate so that two adverse soil
conditions can be overcome by a single application of byproduct.
In contrast to the wealth of knowledge available on the nature and effectiveness of
alternative liming agent in Europe and USA, little is known of their nature,
effectiveness and availability in Australia. In particular the possibility of using lime
from industrial byproducts and mineral processing activities as soil amendments has
received little attention. Li and Gilkes (2002) mention that in 2001, almost 1 million
1
tons of lime was applied to soils in Western Australia, most of which was supplied to
farmers as natural lime, mostly as limesand and limestone from coastal areas. The
sources of those limes are likely to be inadequate in the long term and lime is
expensive in some locations. Therefore Western Australian agricultural soils might
potentially receive lime from other sources that are available locally including iron-
smelting slags, wood ash and chicken litter ash.
1.2 Objectives of this study
This study focused on the use of iron-smelting slags, wood ash and chicken litter ash,
which might be used as liming agents and to increase soil fertility on agricultural land
in Western Australia. These materials are readily available from present and planned
industrial activities in Western Australia. The study has been conducted under
laboratory, and glasshouse conditions to identify the properties of these industrial
byproducts, the effects of the addition of industrial byproducts as liming agents and
phosphate fertilizers to acid soils, together with effects on nutrient uptake, and growth
of plants.
1.3. Structure of the thesis
The organisation of this thesis consists of 5 chapters in which each chapter specifies
and discusses different aspects of the research and also discusses the related literature.
Chapter 3 and 4 have been written in journal format and these manuscripts are
currently under reviews. Justification and objectives of this research are introduced in
Chapter 1. A general literature review is given in Chapter 2. An evaluation as
phosphorus fertilizers of the byproducts: chicken litter ash, iron smelting slag and
wood ash is presented in Chapter 3. Plant response to the byproducts: chicken litter
ash, iron smelting slag and wood ash as phosphorus fertilizers is presented in Chapter
4. General discussion and conclusions, limitations of this work and suggestions for
further work are presented in Chapter 5. Tables and figures are placed within the text
and all the references cited are listed at the end of the thesis followed by the
appendices.
2
Chapter 2
2.0 Literature Review
2.1 Acid Soils
Soils become acid because of several factors. Many soils have become acid through
slow, natural processes and agricultural development can accelerate these processes
(Porter 1981; Whitney and Lamond 1993). Some soils are formed from parent
materials that are intrinsically acid and have low abundances of the alkali elements;
Ca, Mg, K and Na (Samac and Tesfaye 2003; Foy 1984). Soils containing sulphide
become very acid when drained as H2SO4 is produced (Thomas and Hargrove, 1984).
Whitney and Lamond (1993) point out that soil development processes under moist
condition generally include leaching, which together with consequences of soil
management cause soils to become acidic.
Major mechanisms of acidification of soil according to Helyar and Porter (1989)
relate to the carbon (C), and nitrogen (N) cycles. Carbonic acid results from
dissolution in soil solution of CO2 in the soil air. As water percolates through the soil,
acidification occurs as bicarbonates are leached and the hydrogen ion adsorbed and
remains. Soil can become more acid as an effect of nitrogen movement into and out of
the soil, depending on the nitrogen form that is added and on the form of nitrogen that
is removed, or accumulates (Porter 1981). The application of nitrogen fertilizers to
soils may cause a large acidifying effect. Nitrogen fertilizers contain ammonium and
soil bacteria convert ammonium (NH4+) to nitrate (NO3
+) through the nitrification
process. Hydrogen (H+) is released in this process, and free hydrogen ions cause an
increase in acidity. An important consequence of acidification is the replacement of
calcium, magnesium, potassium, and sodium (basic cations) on the soil cation
exchange complex by hydrogen, manganese, and aluminium (acidic cations) (Spies
and Harms 2004).
The acidity of a soil can be measured through its pH value, which may be taken to be
the pH of water in equilibrium with the soil (i.e. the soil solution). Soil pH is a
measure of the activity of the hydrogen ion (H+) in soil solution (Slattery et al. 1999).
Soil pH is defined as the negative log 10 of the hydrogen-ion activity (pH = - log (H+)
3
of soil solution (Evans 1991; Tan 1998). Soils can be separated into a several acidity
and alkalinity categories (Slattery et al. 1999), as shown in Figure 2.1.
NEUTRALITY
3
Slight
Moderate Very strong
Very strong
Strong
Very strong
Moderate
Slight
Very strong
Strong
4 5 6 7 8 9 10
Range in pH common for humid region mineral soils
Range in pH common for most mineral soils
Range in pH common for arid region mineral soils
Extreme pH for acid peat soils
11
ACIDITY ALKALINITY
Attained only by alkali mineral soils
Figure 2.1. Soil pH ranges (Slattery et al. 1999)
2.2 Effect of soil acidity on plants
Soil acidity affects plant growth partially through direct effects of pH on root function
and partly through its effects on soil properties (Russell 1988). Extreme subsoil
acidity may be harmful for plant growth because it can cause shallow rooting, drought
susceptibility, and poor use of nutrients in subsoil (Kauffman 1977). The cause of
poor plant growth on acid soils may vary with soil pH, types and amounts of clay
minerals, contents and types of organic matter, salts levels, and plant species or
genotype (Clark 1982).
In acid soils and mine spoils, the most important factor limiting plant growth is
aluminium toxicity (Foy 1984; Samac and Tesfaye 2003). The problem mainly occurs
below pH 5.0, but it may arise at values as high as pH 5.5 in kaolinite dominant soils.
The poor root development, which occurs in acid soils at pH 5.0 and below, is
probably due mostly to aluminium toxicity that limits both rooting depth and degree
4
of root branching (Foy 1984). Aluminium in solution in acid soils occurs inter alia as
Al3+, Al(OH2)2+, Al(OH)2+, and Al(H2O)3+ (Kinraide 1991). For most plants,
aluminium ions rapidly reduce root growth at micromolar concentrations. The most
toxic ion for the wheat plant is Al3+, while in dicotils the more toxic ions appear to be
Al(OH)2+ and Al(OH)2+ (Samac and Tesfaye 2003).
2.3 Acid Soils in Australia
Like many regions of the world, Australia faces a serious problem with soil
acidification. Acid soil has caused major land degradation and has decreased plant
production over several million hectares of agricultural land in Australia (Evans,
1991). Approximately 35 million hectares of agriculturally productive land presently
have strongly acid soils (pHCa < 4.8) and 55 million hectares are fairly or slightly acid
(pHCa 4.8-6.0) (AACM 1995). Coventry (1985) estimated that Western Australia has
1.0 million hectares of severely acid soil in the eastern wheat belt, with a further 0.5-
0.75 million hectares in the high rainfall southern region.
Maps derived from commercial farm top soil testing data over the past decade (Figure
2.2) show considerable spatial variation in surface soil pH within Australia's
agricultural land and there are major areas of acidic soils (pH CaCl2 less than or equal
to 5.5) in all States (Table 2.1) (The Australian Agriculture Assessment Report 2001).
According to The Australian Agriculture Assessment Report (2001), the largest areas
of strongly acidic soils (pH 4.3 - 4.8) exist in New South Wales (5 to 7 million
hectares), Victoria (4 to 5 million hectares) and Western Australia (1 to 7 million
hectares). The largest areas of moderately acidic soils (pH 4.8 - 5.5) are in Western
Australia (7 to 19 million hectares) and New South Wales (11 to 13 million hectares)
and to a lesser extent Victoria (2 to 3 million hectares). These estimations do not
include all of the area where severe subsoil acidity occurs beneath a less acid topsoil.
5
Table 2.1 National and State areas of surface soil (0 - 10 cm) in several pH (measured
in calcium chloride solution) bands based on information from the
Australian Soil Resources Information System (first number) and
commercial laboratories (second number) (The Australian Agriculture
Australiac 1.1 - 3.3 11.3 - 21.2 36.8 - 25.2 36.3 - 22.9 11.8 - 23.5 0.0b - 0.1 97.3 - 96.2 aInclusive b Numbers rounded to 0.0 range from 0.01 - 0.03. c Total values may be slightly different to those obtained by adding up the values in the table because of rounding errors.
Figure 2.2. Interpolated topsoil pH (1990-1999) (The Australian Agriculture Assessment Report 2001).
6
Many Western Australian agricultural soils require lime applications to overcome soil
acidity, which is widespread and which can affect both topsoils and subsoils (Penny
2002). Two thirds of 10 million hectares of the Western Australian wheatbelt are
affected by soil acidity (Leonard and Boland 1995). It is estimated that potential
agricultural production worth $70 million is lost annually in Western Australia
because of acid soil (Leonard and Boland 1995). Miller (2002) reported that 575,980
tonnes of lime were used on agricultural land of Western Australia in 1999/2000 and
in more recent years the amount is about 1M tonnes/year.
2.4 Liming Resources and Lime Requirement
Liming is one of the most common ways to ameliorate acid soils. Barber (1984)
defined liming material as a material, which contains calcium and/or magnesium,
which reduce the effects of soil acidity. Liming reduces the toxicity of aluminium
(Ritchie 1989), the concentration of hydrogen ions and also adds base-forming cations
to the soil (Thompson 2004). The solubility and plant availability of most of the
nutrient ions in soil is affected by liming (Seatz and Peterson 1969). Furthermore,
liming can improve soil structure, increase soil biological activity, and enhance the
distribution of roots in soil.
The mechanisms of CaCO3 reaction with acid soils are complex (Bear 1969). CaCO3
dissolves and hydrolyses to form OH- ions, the reaction is as follows:
CaCO3 + H2O Ca2+ + HCO3- +OH- (Seatz and Peterson 1969; Thomas and
Hargrove 1984).
In general, the reaction of lime and acid soils (Seatz and Peterson 1969) may be
written as:
2Al-soil + 3 CaCO3 + 3H2O 3Ca-soil + 2Al (OH)3 + 3 CO2 and
2H-soil + CaCO3 Ca-soil + H2O + CO2
Liming resources are valued for their capacity to ameliorate soil acidity and to
maintain the availability of calcium and magnesium for crops. There are a number of
liming materials and each liming material has a specific composition and capacity to
neutralize acidity. The quality of the materials depends on their mineralogy, purity,
and on the size of the particles (Heckman 2000).
7
The standard for measuring purity is calcium carbonate equivalence (CCE) (Spies and
Harms, 2004) so that the CCE value for pure calcium carbonate is 100 % (Whitney
and Lamond 1993). The CCE values of some liming materials are shown in Table 2.2.
Table 2.2. Calcium carbonate equivalence values of some liming materials (aHeckman
2000; bThompson 2004).
Liming Material a, b Source b Chemical Formula a, b
Table 2. 8. The chemical composition of ash derived from diverse plant species (n.a. not analysed) (*Lerner and Utzinger 1986; #Onderwater et
al. 2001).
15
2.5.2.2 Application of wood ash in agriculture
The application of wood ash to agricultural land increases soil pH and may increase
productivity (Etiegni et al. 1991). According to Rumf et al. (2001) the addition of
wood ash increased pH and base saturation, improved biotic conditions of soils, and
did not have any detrimental effects in the short term.
Clapham and Zibilske (1992) have conducted glasshouse and laboratory experiments
in order to determine the effectiveness of wood ash as a liming agent and found that
soil EC, K, Ca, extractable soil P, Fe, Zn, Cu, and Mn increased linearly with
increasing application rate of wood ash (0 to 20.17 g/kg soil). Mbahrekire et al.
(2003) measured the nutrient element composition of bean (Phaseolus vulgaris) and
soybean (Glycine max L.) grown on soils with wood ash amendment. They
demonstrated that the application of wood ash to the soil at rates of up to 40 ton/ha
increased the plant height by a factor of 1.5 for beans and 1.2 for soybeans with
associated increases in biomass of 1.7 and 1.9 respectively. The increases in plant
height and biomass are attributed mainly to the presence of P, K, Ca and Mg in wood
ash.
2.5.3 Chicken Litter Ash
2.5.3.1 The Nature of Industrial Chicken Litter ash
Chicken litter is a mixture of chicken manure, plant materials including wood
shavings and sometimes mineral particles. For a number of physical and chemical
properties (e. g. heating value, moisture content) it is comparable to wood chips
(Power Plant Research Program 1998). Chicken litter provides a rich source of plant
nutrients and is commonly used in agriculture (Pote et al. 2003). Chicken litter is
commonly applied directly to agricultural land as a fertilizer, however, this has
resulted in excessive levels of phosphorous and nitrogen leachate in some places and
it may contribute to the appearance of flies and toxic micro- organisms (Power Plant
Research Program 1998).
16
One method to overcome these problems is by burning the chicken litter as a fuel
source for power production (Power Plant Research Program 1998). Although all N
and most S are lost during combustion, the ash resulting from the burning process has
value as a multi-element fertilizer and is now recognised as a valuable source of plant
nutrients. Codling et al. (2002) summarised the characteristics of chicken litter ash as
a potential source of plant nutrients (Table 2.9).
Table 2.9. Chemical properties of chicken litter ash (Codling et al. 2002)
Analyte Chicken litter ashpH (1:2 H20) 12.2 EC (1:2 H20), mS/cm 27.5 Water soluble phosphorus, mg/kg <0.1 Mehlich-3-extractable phosphorus g/kg 43 Total P, g/kg 53 Total Ca, g/kg 9 Total Mg, g/kg 1.8 Total K, g/kg 3.9 Total Cd, mg/kg 0.4 Total Ni, mg/kg 14.8 Total As, mg/kg 15 Total Pb, mg/kg 6 Total Cu, mg/kg 43.1 Total Fe, g/kg 4.3 Total Mn, g/kg 1.6 Total Zn, g/kg 0.6
John Hatcher, a company in the UK has developed a fertilizer named Fibrophos
(Fibrophos 2006). It is derived from the incineration of deep chicken litter at a
temperature in excess of 800oC, as a fuel for state of the art power stations. John
Hatcher provides the ash as a compound fertilizer containing most of the elements
required for plant growth (Table 2.10).
17
Table 2.10. Nutrients present in Fibrophos (a chicken litter ash) based on the grades in
Southern and Central England/Wales (Fibrophos 2006).
Analyte Concentration P (P2O5), % 22 K (K2O), % 12 Ca (CaO), % 25 S (SO3), % 7 Mg (MgO), % 5 Na (Na2O) 3 Fe, mg/kg 4000 Mn, mg/kg 2500 Zn, mg/kg 2000 Cu, mg/kg 500 B, mg/kg 150 Mo, mg/kg 30 Co, mg/kg 10 I, mg/kg 5 Se, mg/kg 5 Neutralising value, % 15
2.5.3.2 The use of Chicken Litter Ash in Agriculture
The application of chicken litter ash to agricultural land has not been widely adopted
and no research has been carried out in Australia. Codling et al. (2002) in USA have
conducted research into the effectiveness of poultry litter ash as a source of
phosphorus to agricultural crops. They grew wheat in an acidic soil and compared the
effectiveness of the ash as a P fertilizer with potassium phosphate. They found that
the two source of phosphorus were not significantly different. The metal
concentrations in wheat fertilised with poultry litter ash were lower, possibly due to
the liming effect of the ash reducing the availability of metals. They concluded that
poultry litter ash is an effective source of phosphorus.
The John Hatcher Company in the UK has carried out plant growth experiments over
the past 8 years to evaluate Fibrophos in relation to the yield and quality of various
crops. They have included Triple Superphosphate (TSP) and Muriate of Potash
(MOP) as standards (Fibrophos 2006). The results presented in sales literature show
that the phosphate and potash in Fibrophos are as effective as Triple Superphosphate
18
and Muriate of Potash and that Fibrophos also provides other major and minor
nutrients. These data have not been published in peer-reviewed journals so await
critical scrutiny. However the results are consistent with those published by Codling
et al. (2002).
19
Chapter 3
3.0 A Laboratory Evaluation of the Industrial Byproducts: Chicken Litter Ash,
Wood Ash and Iron Smelting Slag for use as a Combined Liming Agent and
Phosphorus Fertilizer
3.1 Introduction
Soil acidity is a major problem worldwide as it decreases plant growth by affecting
the availability of nutrients and causes various toxicities. Acid soils are commonly
deficient in phosphate (P) so that both conditions require correction, which can be
carried out by the application of a single mineral ameliorant with appropriate
properties. Some alkaline industrial byproducts may be suitable as they contain P,
which may be available to plants. These materials include iron smelting slag, wood
ash and chicken litter ash but their fertilizer effectiveness is poorly defined.
Byproducts are commonly dumped in landfill so that the use of byproducts to
ameliorate land will contribute to the preservation of alternate resources and provide
an effective solution for the disposal of byproducts (Francis and Youssef 2004).
A laboratory assessment of the potential agronomic effectiveness of a material to be
used as a P fertilizer has to be made to determine appropriate rates of application in
the field. In order for a material to be an effective P fertilizer, substantial amounts of P
should dissolve shortly after application to soils and all P should eventually dissolve
(Hughes and Gilkes 1984). Conventional chemical P fertilizers (SP, DAP, MAP) are
mostly soluble in water and are highly effective. Rock phosphate is almost insoluble
in water as it relies on soil acidity and rhizosphere acidity to promote dissolution and
is consequently much less effective than chemical fertilizers (Khasawneh and Doll
1978). The solubility of the above-mentioned byproducts in soil is not known.
The effectiveness of poorly soluble phosphate fertilizers such as rock phosphate and
phosphatic byproducts may be assessed by standard analytical procedures (AOAC
1975) that determine the solubility of phosphate in water, citric acid, neutral
ammonium citrate and alkaline ammonium citrate. Depending on the composition of
the fertilizer and its reactions in soil, a particular extractant may provide the best
prediction of fertilizer performance as determined by field or glasshouse experiments
20
and appropriate calibration is required (Colwell 1963). This chapter investigates the
nature of byproducts (chicken litter ash, wood ash, iron-smelting slag) that may act as
a combined liming agent and phosphate fertilizer and evaluates them using standard
AOAC fertilizer analyses.
Table 3.1. The nomenclature for calcined chicken litter samples produced by
calcination at various temperatures and their pH measured in water
Key Explanation pH H2O
(1:5)
C500 Chicken litter burnt at 500oC 10.18
C550 Chicken litter burnt at 550oC 10.27
C600 Chicken litter burnt at 600oC 10.29
C650 Chicken litter burnt at 650oC 10.33
C700 Chicken litter burnt at 700oC 10.37
C750 Chicken litter burnt at 750oC 10.38
C800 Chicken litter burnt at 800oC 10.52
C850 Chicken litter burnt at 850oC 10.55
C900 Chicken litter burnt at 900oC 10.56
C950 Chicken litter burnt at 950oC 10.59
C1000 Chicken litter burnt at 1000oC 10.62
CLA Chicken litter partly burnt in incinerator at 700oC to 800oC 9.93
CLAT CLA heated in furnace at 700oC 11.31
RP Sechura rock phosphate 7.96
WA Wood ash 12.77
Slag Iron smelting slag 10.59
3.2 Materials and Methods
3.2.1. Calcination of chicken litter
A bulk sample of chicken litter was supplied by Blair Fox Generation, which is
developing a power station to be fired by this material. Combustion temperatures and
conditions may vary substantially during this process, so that diverse combustion
products may be produced. Subsamples of 1 kg of the chicken litter were burnt in a
21
ventilated electric muffle furnace for 1 hour at 500o, 550o, 600o, 650o, 700o, 750o,
800o, 850o, 900o, 950o, and 1000oC respectively. Large amounts (>100kg) of chicken
litter were partially and totally burnt in a commercial incinerator. Chicken litter was
partially burnt (CLA) for 36 hours at temperatures that varied between 700oC to
800oC. Combustion was only partial as much carbonised litter (charcoal) remained.
Totally burnt chicken litter (CLAT) was derived from CLA, by heating overnight in a
fully oxidising environment at 700oC to remove residual charcoal from CLA. A key to
the materials investigated, abbreviations used to identify these materials and the pH of
these materials including Sechura rock phosphate are given in Table 3.1.
3.2.2 Industrial Byproducts
Iron smelting slag came from the HIsmelt Kwinana Demonstration Plant, Western
Australia, which utilises iron ore, lime and coal. Wood ash was from eucalyptus
(Mallee sp.) timber and litter, which is burnt in an experimental bioenergy Power
Station at Narrogin Western Australia. The chemical compositions of the byproducts
and Sechura rock phosphate, which as it acts as a combined P fertilizer and liming
agent (Khasawneh et al. 1980) was included for comparative purposes, are given in
Table 3.3.
3.2.3 Characterisation of the materials
The pH of the materials was determined in a 1:5 deionized water extract. Calcium
carbonate equivalent (CCE) was determined as in the AOAC 1.005 procedure,
(AOAC 1975). Major elements were determined by atomic absorption
spectrophotometry (AAS) (Perkin-Elmer, Analyst 300, Norwalk, CT, USA) and trace
elements with a model PE ELAN 600 inductively coupled plasma – mass
spectrometry (ICPMS) instrument (Perkin-Elmer, Norwalk, CT, USA) after
perchloric acid digestion. Total phosphorous in these digest was determined
colorimetrically using the molybdovanadophosphate (yellow) method (Rayment and
Higginson 1992). The compounds in byproducts were identified by X-ray powder
diffraction (XRD) using a Philips PW3020 diffractometer. Samples for scanning
electron microscopy and energy dispersive X-ray spectrometry (EDS) using a JEOL
3600 instrument were placed on metal stubs and carbon coated.
22
3.2.4 Chemical extraction of the materials (AOAC Method)
Unlike many commercial P fertilizers little of the P in byproducts is soluble in water
(Table 3.2). The byproducts were analysed for available P using Association of
Official Analytical Chemistry (AOAC) standard methods (AOAC 1975) utilising
The internal efficiency of P utilization by ryegrass is indicated by plots of plant dry
matter versus the P content of plants (Palmer and Gilkes, 1982). For each harvest the
48
existence of a single internal efficiency curve for all P sources (Figure 4.3) indicates
that differences in yield were due predominantly to differences in plant P content as
was also observed by Snars et al. (2004) in an experiment with the same ryegrass
cultivar.
Harvest I
y = 1.25x + 0.090R2 = 0.9977
0
0.5
1
1.5
2
2.5
0 0.5 1 1.5 2
P Content (mg P/pot)
Yiel
d(g
/pot
)
Harvest II
y = 1.69x - 0.14R2 = 0.9964
0
0.5
1
1.5
2
2.5
0 0.5 1 1.5 2
P Content (mg P/pot)
Yiel
d(g
/pot
)
Harvest III
y = 1.39x + 0.03R2 = 0.9928
0
0.5
1
1.5
2
2.5
0 0.5 1 1.5 2
P Content (mg P/pot)
Yie
ld(g
/pot
)
Harvest IV
y = 1.61x + 0.02R2 = 0.9954
0
0.5
1
1.5
2
2.5
3
0 0.5 1 1.5 2
P Content (mg P/pot)
Yiel
d(g
/pot
)
Figure 4.3. Internal efficiency of P utilization curves for each harvest: ◆ MCP, ■
DCP, ▲ RP, x Slag, WA, ● CLA, + CLAT
49
Harvest I
0
0.5
1
1.5
2
1 10 100 1000
Log P applied (mg/kg)
PC
onte
nt(m
g/po
t)
Harvest II
0
0.5
1
1.5
2
1 10 100 1000
Log P applied (mg/kg)
P C
onte
nt (m
g/po
t)
Harvest III
0
0.5
1
1.5
2
1 10 100 1000
Log P applied (mg/kg)
P Co
nten
t (m
g/po
t)
Harvest IV
0
0.5
1
1.5
2
1 10 100 1000
Log P applied (mg/kg)
P Co
nten
t (m
g/po
t)
Figure 4.4. P content versus log P applied for all harvests: ◆ MCP, ■ DCP, ▲ RP, x
Slag, WA, ● CLA, + CLAT
Figures 4.4. show the response curves for P content versus P applied for all the
harvests. There was a large response in P content to MCP, DCP and RP application
for all harvests. For the byproducts there was a much smaller response for harvest I
and II; for harvest III and IV there was no systematic trend in response for the
byproducts. Some plants died before the third harvest for slag, WA and CLAT. The
growth and P content of ryegrass for soil amended with these byproducts may not
simply reflect a response to applied P. For instance the liming effect of these materials
increased soil pH (Turner 1993) and this may have affected the availability of
nutrients, although this is not evident in the plant analyses. Similarly the presence of
50
abundant Ca and other ions in soil solutions due to dissolution of the byproducts in
the soil may have reduced the availability of P (Sample et al. 1980). Plants may have
ceased to grow or died from a combination of P deficiency and the high level of pH in
the soil (Barber, 1980).
4.3.4 Relative Effectiveness (RE)
The agronomic relative effectiveness (RE) of the phosphate fertilizers based on plant
data was derived by comparing the initial slope of response curves for plant yield and
P content for the various materials with the slope for MCP as the reference (Figure
4.5). This is a reliable procedure providing that the yield values are well below the
non P limiting yield plateau (Bolland and Gilkes 1990)
Due to the death after the second harvest of some plants fertilised with WA and
CLAT, no RE values could be calculated for these P sources for the later harvests. For
the last two harvests, application of WA and CLAT as phosphorus fertilizers
produced no systematic responses in yield and P content, so that response curves were
poorly defined (low R2 values) (Appendix 4.4).
The effectiveness of CLA, DCP, and RP relative to MCP showed an increasing trend
with the harvest number. There was a systematic increase in RE values for the first
three harvests of CLA, DCP and RP. It must be stressed that values of RE have been
calculated relative to MCP for which the absolute effectiveness decreases with time
since application (Bolland and Gilkes 1990). Thus despite the increase in RE values,
the absolute effectiveness of the other P fertilizers may not have increased. However
it is evident that chicken litter ash has appreciable rapid effect and a good residual
value as a phosphate fertilizer (Codling et al. 2002) whereas wood ash and slag were
relatively ineffective.
51
Plant Yield
0
20
40
60
80
100
120
1 2 3 4
Harvest
RE (%
)
P Content
0
20
40
60
80
100
120
1 2 3 4
Harvest
RE
(%)
MCP DCP RP Slag WA CLA CLAT
Figure 4.5. RE values for the byproducts based on yield and P content for the four
harvests
4.4 Conclusion
The results of this study provide strong evidence that chicken litter ash is a
moderately effective P fertilizer but that it is inferior to MCP, DCP and RP. Slag and
WA were relatively poor sources of P probably due to the alkaline pH of the
materials, which would have reduced the solubility of P in soil solution. However as
52
CLA, CLAT, slag and WA have excellent liming value and as they would be applied
at much higher rates as lime than are used for fertilizers it is likely that all four
materials will provide substantial additional P to plants. They may be more suited for
use on permanent pastures or for tree crops where a rapid response to P fertilizer
application is less important than is the case for fast growing cereals or horticultural
crops.
53
Chapter 5
5.0 General Summary, Limitations and Future Work
5.1 General Summary The main purposes of the research as discussed in the general introduction were to
characterize iron-smelting slag, wood ash and chicken litter ash and evaluate the use
of these materials as liming agents and sources of P for agricultural land in Western
Australia. The main findings of the study were that the byproducts differ in
mineralogy, morphology and chemistry. They provide P to plants and effectively
ameliorate acid soils.
The byproducts used in the study were chicken litter ash burnt at several temperatures,
partly burnt chicken litter ash, totally burnt chicken litter ash, wood ash, and iron
smelting slag. The pH of all the materials were above 9 and calcium carbonate
equivalence values were above 90%, indicating that these materials will be effective
liming agents. Chicken litter ash contains more than 3% total P while the values for
slag and WA were above 0.25%. Other plant nutrients present in byproducts include
calcium, magnesium, sodium, potassium and trace elements.
For calcined chicken litter, the amount of P dissolved by citrate extractants varied
with the extractant and calcination temperature. The P dissolved for short and long
periods of extraction of the various calcines increased followed the sequence
CA>NAC>AAC. The amounts of soluble P in CLA and CLAT also followed the
sequence CA>NAC>AAC with little additional dissolution after 6 hours of extraction.
Dissolution of P in WA was quite rapid for all the three extractants while P in slag
dissolved slowly and at slower rate for NAC and AAC compared to CA.
CLA, and CLAT were consisted of mixtures of apatite, calcite, and quartz together
with much charcoal in CLA. The intensity and the sharpness of apatite XRD
reflection for chicken litter ash increased with increased calcination temperature.
Apatite persisted in the three extractant residues and followed the sequence
CA<NAC<AAC. SEM micrographs before and after the extractions provided
54
explanations for the chemical and XRD analysis. Some grains micrographs consist
mostly of carbon but also contain P and cations.
The minerals presents in RP were apatite and quartz and much apatite persisted in the
residues for all three extractants. WA consisted mostly of calcite and quartz, with no
apatite being observed. Calcite in WA dissolved in CA but remained in NAC and
AAC residues. Calcium magnesium silicate (akermanite) and calcium aluminium
silicate (gehlenite) were the main constituents of slag. CA dissolved much akermanite
and lesser gehlenite in slag, while NAC and AAC dissolved less of both compounds.
In the glasshouse experiment all P sources produced initial yield responses but for
iron smelting slag and wood ash, many plants died of P deficiency before the third
harvest. Based on plant yield data, the relative effectiveness (RE) of DCP compared
to MCP was 57%, 72%, 73%, and 94 % respectively for four harvests, for RP was
24%, 34%, 70% and 56%, for chicken litter ash was 13%, 16%, 33% and 39%, for
slag was 8%, 9%, 16% and 10%, for WA was 6%, 9% and effectively zero for the
final two harvests. Thus chicken litter ash could be used as a P fertilizer but it is less
effective than MCP. Iron smelting slag and wood ash were much less effective
fertilizers but may still provide significant amount of P to plant where large
application of these materials are used as liming agents. Application of the byproducts
increased the pH of the soil.
Chicken litter ash is a moderately effective P fertilizer but inferior to DCP and RP.
Slag and WA were relatively poor sources of P. However as CLA, CLAT, slag and
WA have a liming action and would be applied at much higher rate than are used for
fertilizers it is likely that all four materials will provide additional P to plants.
5.2 Limitation and Future Works
This research has several limitations and further research is needed. For example, the
study was based on laboratory and glasshouse research and it is important that the
assessment of industrial byproducts be carried out under field conditions. Importantly,
an economic analysis including cost-benefit evaluation of the use of the byproducts
needs to be carried out.
55
Application of the industrial byproducts in large amounts to large areas of agricultural
land has the potential to create unanticipated environmental problems. For example if
the materials, especially in finely ground and ash form are used at a large scale there
may be a dust problem that could be dangerous for human and animal respiratory
systems. It may be possible to combine the byproducts with compost or other
materials to reduce dust and possibly to increase the effectiveness of the byproducts.
The glasshouse experiment to evaluate the agronomic effectiveness of the byproducts,
was based on ryegrass which has a low P demand. A next step would be to study the
effectiveness of the byproducts for cereals and other species with diverse P
requirements (e.g. plantation forestry).
This research has clearly demonstrated the value of byproducts as combined P
fertilizers and liming agents. In view of the large amounts of these materials that will
be produced in future years, there is a clear opportunity for integrating the materials
into appropriate land management practices.
56
Chapter 6 6.0 Publications from this thesis
Conferences Publications
Yusiharni, B. E., and Gilkes, B. 2006. The Use of Industrial Byproducts as Liming
Agents And Phosphate Fertilizers. Proceedings The 18th World Congress of Soil
Science, Philadelphia USA, 8-15 July 2006.
Yusiharni, B. E., and Gilkes, B. 2006. Mineralogy of Chicken Poo. Proceedings
AXAA/WASM 2006 Conference, Margaret River, Western Australia, 22-24
September 2006.
Yusiharni, B. E., and Gilkes, B. 2006. Chicken Litter Ash: An Evaluation of an
Agronomic Resource. Reviewed Conference. Proceedings ASSSI - ASPAC National
Soils Conference, Soil Science Solving Problems. The University of Adelaide
North Terrace 3-7 December 2006.
Journals Publications
Chapter 3
Yusiharni, B. E., Gilkes, R. J., and H. Ziadi., 2006. A laboratory evaluation of chicken
litter ash, iron smelting slag and wood ash. In press. Aust. J. of Soil. Res.
Chapter 4
Yusiharni, B. E., Gilkes, R. J., 2006. An evaluation as phosphorus fertilizers of the
byproducts: chicken litter ash, iron smelting slag and wood ash. Submitted to Aust. J.
Agric. Res.
57
References Adams, F., 1984, Soil acidity and liming, 2nd edn., Wisconsin: American Society of
Agronomy, 57-59 Alloway, B. J., Ayres, D.C., 1993, Chemical principles of environmental pollution.
Blackie Academic Professional, an imprint of Chapman & Hall. Alvarez, J., Snyder, G. H., Anderson, D. L., Jones, D. B., 1988, Economics of calcium
silicate slag application in a rice-sugarcane rotation in the everglades, Agricultural Systems, 28:179-188.
Anderson, D.L., Kussow, W.R., Corey, R.B., 1985. Phosphate rock dissolution in
soil: Indications from plant growth studies. Soil Science Society of America Journal, 49, 918-925.
Anderson, D. L., Snyder, G. H., and Martin, F. G., 1991, Multi-year response of
sugarcane to calcium silicate slag on everglades Histosols, Agron. J., 83:870-874. ANZECC/NHMRC, 1992, Australian and New Zealand guidelines for the assessment
and management of contaminated sites. Australia and New Zealand Environment and Conservation Council/National Health and Medical Research Council: Canberra.
Association of Official Agricultural Chemists, 1975, Association of Official
Agricultural Chemists, Official Methods of Analysis.’12th Edn. AOAC: Washington.
Barber, S. A., 1984, Liming materials and practices, In Ed. F. Adams, Soil Acidity and
Liming 2nd Edition, Wisconsin; American Society of Agronomy, 171-210 Barber, S.A., 1980, Soil-plant interactions in the phosphorus nutrition of plants. In
The Role of Phosphorus in Agriculture. 1st Ed. Soil Science Society of America, Madison, Wisconsin, USA.
Barker, A.V., O’Brien, T. A., and Stratton, M. L., 2000, Description of food
processing by-products, pp. 63-106, In ‘Land Application of Agricultural, Industrial, and Municipal By-Products’, (Eds. J. F. Power and W. A. Dick)., Soil Science Society of America. Book series No 6
Bear, F. E., 1969, Chemistry of The Soil, Second edition, American Chemical society
Monograph Series, 292-319 Bolan, N., 2004, Basics on basic slag, available on
http://soilsearth.massey.ac.nz/cybsoil/article/slag.htm [accessed on 27 August 2004]
Bolland, M.D. A. , Gilkes, R.J., 1990, The poor performance of rock phosphate
fertilizers in Western Australia: Part 1. The crop and pasture response. Agricultural Science, 3: 8-43
Boxma, R., 1977, Evaluation of phosphate in fertilizers by means of the alkaline ammonium citrate extraction according to Petermann. Neth. J. Agric. Sci. 25: 42-50.
Clapham, W. M., and Zibilske, L. M., 1992, Wood ash as a liming amendment,
Commun., Soil Sci., Plant Anal., 23, 1209-1227 Clark, R. B., 1982, Plant response to mineral element toxicity and deficiency. In ‘Eds.
M. N. Christiansen and C. F. Lewis, Breeding plants for less favourable environments, John Wiley and Sons, Inc, New York, p. 71-142
Codling, E.E., Rufus, L.C., Sherwell, J., 2002, Poultry litter ash as a potential
phosphorus source for agricultural crops. Journal of Environmental Quality, 31: 954-961
Colwell, J.D., 1963, The estimation of the phosphorus fertilizer requirements of wheat
in southern New South Wales by soil analysis. Australian Journal of Experimental Agriculture and Animal Husbandry, 3:190–197
Coventry, D. R., 1985, Changes in agricultural systems on acid soils in southern
Australia, Australian Agronomy conference, Proceedings, 45-126. Cregan, P. D., Hirth, J. R., and Conyers, M. K., 1989, Amelioration of soil acidity by
liming and other amendments. In ‘Ed. A. D. Robson, Soil Acidity and Plant Growth, Sydney, Academic Press, 205-264
Demeyer, A., Nkana, J. C. V., and Verloo, M. G., 2001, Characteristics of wood ash
and influence on soil properties and nutrient uptake: an overview, Bioresource Technology, 77: 287-285.
Doak, B. W, Gallaher, P. J., Evans, L., Muller, F. B., 1965, Low temperature
calcination of C-grade phosphate from Christmas Island. N. Z. J. Agric. Res. 8: 15-29
Etiegni, L., Campbell, A. G., and Mahler, R. L., 1991, Evaluation of wood ash
disposal on agricultural land. I. Potential as a soil additive and liming agent, Commun. Soil Sci. Plant Anal, 22, 243-256.
Evans, G., 1991, Acid soils in Australia, Bureau of Rural Resources, Department of
Primary Industries and Energy: Canberra, p: 4 Fibrophos, 2006, available on www.fibrophos.co.uk [accessed on 2 May 2006] Foy, C. D., 1984, Physiological effects of hydrogen, aluminium and manganese
toxicities in acid soil, In Pearson, R. W., Adams, F., eds., Soil acidity and liming, 2nd edn., Wisconsin: American Society of Agronomy, 57-59
Francis, A. A., and Youssef, N. F., 2004, Glass ceramic from industrial waste
materials. Scandinavian Journal of Metallurgy, 33: 236-241.
Gilkes, R. J., Palmer, B. 1979. Calcined Christmas island C-grade rock phosphate
fertilizers: Mineralogical properties, reversion and assessment by chemical extraction. Australian Journal of Soil Research. 17: 467– 481.
Gilkes, R. J., Rate, A. W., Hinz, C. and Aylmore, L. A. G., 2003, Soil science 230-
laboratory manual. Soil Science Group, School of Earth and Geographical Sciences, The University of Western Australia, pp:71-72
Harper, R.J., Gilkes, R.J., Robson, A.D., 1982. Biocrystallization of quartz and
calcium phosphates in plants- a re-examination of the evidence. Aust. J. Agric. Res 33, 565-571.
Heckman, J. R., 2000, Agricultural liming materials, available on
www.rce.rutgers.edu. [accessed on 29 July 2004] Helyar, K. R., and Porter, W. M., 1989, Soil acidification its measurement and the
processes involved. In Ed. A. D. Robson, Soil Acidity and Plant Growth, Sydney, Academic Press, 61-102
Hughes, J. C., Gilkes, R. J. 1984. The effect of chemical extractant on the estimation
of rock phosphate fertilizer dissolution. Aust J. Soil Research. 22: 475-481. Humphreys, G.S., Hunt, P.A., Buchanan, R., 1987. Wood ash stone near Sydney, N.
S. W.: A carbonate pedological feature in an acidic soil. Aust J. Soil Research 25, 115-124.
Kalyoncu, R. S., 1998, Slag-iron and steel, available on http://www.scirus.com.
[accessed on 5 July 2004] Kato, N. and Owa, N., 1997a, Dissolution of slag fertilizers in paddy soil and Si
uptake by rice plant, Soil Science & Plant Nutrition, 43(2): 329-341 Kato, N., Yanagisawa, K. and Owa, N., 1997, Measurement of Si adsorption and
“active Si” in a soil amended with slag fertilizers by using stable isotope Si. Soil science & Plant Nutrition, 43: 623-631
Kauffman, M. D., 1977, The effect of soil acidity and lime placement on root growth
and yield of winter wheat and alfalfa, Ph.D. Diss. Oregon State Univ., Corvallis. Diss. Abstr. 37B:7.3192-3193
Khan, H. Rahman, S., Hussain, M. S., and Adachi, T., 1994, Growth and yield
response of rice to selected amendments in an acid sulphate soil, Soil Science and Plant Nutrition, 40:231-242
Khasawneh, F. E., Doll, E. C., 1978. Increasing the productivity of Brazilian cerrado
soils. Proc. Int. Seminar on Soil Environ. Fertil. Manage. In Intensive Agric, Tokyo, Japan. pp. 462-471.
Khasawneh, F.E., Sample, E.C., Kamprath, E.J., 1980. Role of Phosphorus in Agriculture. 1st Ed. Soil Science Society of America, Madison, Wisconsin, USA.
Kinraide, T. B., 1991, Identity of the rhizotoxic aluminium species, Plant Soil,
amorphous materials. 2nd ed. John Wiley & Sons Inc, New York. Lee, A. R., 1974, Blastfurnace and steel slag, Edward Arnold., London, 119 pp. Lehr, J.L., 1980. Phosphate raw materials and fertilizers: Part I-a look ahead. In The
Role of Phosphorus in Agriculture. 1st Ed. Soil Science Society of America, Madison, Wisconsin, USA.
Lim, H.H., Gilkes, R.J., 2001. Beneficiation of apatite rock phosphate by calcination:
effects on chemical properties and fertiliser effectiveness. Aust. J. Soil. Res 39, 397-402.
Lindsay, W.L., Paul, L.G.V., Chien, S.H., 1989. Phosphate minerals. In Minerals in
soil environments. 2nd ed. (Eds). Soil Science Society of America, Madison, Wisconsin, USA.
Leonard, L., and Boland, M., 1995, Soil acidity- a reference manual, Agriculture
Western Australia, Perth Lerner, B. R., and Utzhinger, J. D., 1986, Wood ash as soil liming material.
HortScience, 21 (1): 76-78 Li, J., and Gilkes, R. J., 2002, Summary of the first stage experimental results for
environmental uses of HIsmelt slag, Report to HIsmelt, Unpublished, The University of Western Australia
Lindsay, W.L., 1979, Phosphorus. In Chemical equilibria in soils. pp. 169-209. Wiley
Interscience: New York Male, D. W., Leduc, L. G., and Ferroni, G. D., 1997, The potential of mining slag as a
substrate for microbial growth and the microbiological analysis of slag and slag seepage, Kluwer Academic publisher, Antonie van Leeuwenhock
71:379-386 Mbaherekire, B. J., Oryem-origa, H., Kashambuzi, J., Mutumba, G. M., and
Nyangababo, J. T., 2003, Elemental composition of bean (Phaseolus vulgaris) and soy bean (Glycine max L.) grown on wood ash amended soil, Bull. Environ. Contam. Toxicol, 70: 817-823.
McArthur, W.M., 1991, Reference soils of south-Western Australia. ASSS (W.A.
Branch). Perth
61
McClellan, G.H., Gremillion, G.H., 1980. Evaluation of phosphatic raw materials. In The Role of Phosphorus in Agriculture. 1st Ed. Soil Science Society of America, Madison, Wisconsin, USA.
Miller, A., Lime use in Western Australia, 2002, Western Australia Soil Acidity
Research and Development update 2001, Department of Agriculture, Western Australia
Miller, D. M., Miller, W. P., O’Brien, T. A., and Sumner, M. E., 2000,
Characterization of Industrial by-products. pp. 107-126, In ‘Land Application of Agricultural, Industrial, and Municipal By-Products’, (Eds. J. F. Power and W. A. Dick)., Soil Science Society of America. Book series No 6
Moore, G., 1998, Soil Guide. A handbook for understanding and managing
agricultural soils’. Department of Agriculture, Western Australia. Bulletin No. 4343. pp. 318
Nkana, J. C. V., Demeyer, A., and Verloo, M. G., 2002, Effect of wood ash
application on soil solution chemistry of tropical acid soils: incubation study. Bioresource Technology, 85: 323-325
Onderwater, M,Z., Backman, R., Skrifvars, B.J., and Hupa, M., 2001, The ash
chemistry in fluidised bed gasification of biomass fuels. Part I: predicting the chemistry of melting ashes and ash-bed material interaction. Fuel, 80:1489-1502
Palmer, B., and Gilkes, R.J., 1982, Reversion of calcined calcium aluminium
phosphate fertilizers due to rehydroxylation of crandallite. Aust. J. Soil Res, 20:243-250
Penny, S. A., 2002, Methods of lime storage and stabilisation, Farmnote, Soil acidity
Series, Department of Agriculture, Western Australia Perkiomaki, J., 2004, Wood ash use in coniferous forests, a soil microbiological study
into the potential risk of cadmium release, Metsantutkimuslaitoksen Tiedonantoja 917, Finish Forest Research Institute, Research Papers 917
Porter, W. M., 1981, Soil acidification - the cause, available on
http://www.regional.org.au/au/roc/1981/roc198131.htm, [accessed on 3 August 2004]
Pote, D.H., Kingery, W.L., Aiken, G.E., Han, F.X., Moore, P.A., and Buddington, K.,
2003, Water-quality effects of incorporating poultry litter into perennial grassland soils. J. Environ. Qual, 32:2392-2398
Power Plant Research Program, 1998, Engineering and economic feasibility of using
poultry litter as a fuel to generate electric power at Maryland’s Eastern Correctional Institute.PPES–96-1. Department of Natural Resources Annapolis, MD, America.
CSIRO Publishing: Melbourne Ritchie, G. S. P., 1989, The chemical behaviour of aluminium, hydrogen and
manganese in acid soils. In Ed. A. D. Robson, Soil Acidity and Plant Growth, Sydney, Academic Press, 1-60
Robson, A. D., and Abbott L. K., 1989, The effect of soil acidity on microbial activity
in soils. In Ed. A. D. Robson, Soil Acidity and Plant Growth, Sydney, Academic Press, 139-166
Rodriguez, M., Lopez, F. A., Pinto, M., Balcazar, N., and Besga, G., 1994, Basic
Linz-Donawitz slag as a liming agent for pastureland. Agron. J. 86,904-909 Rumpf, S., Ludwig, B., and Mindrup, M., 2001, Effect of wood ash on soil chemistry
of a pine stand in Northern Germany. J. Plant. Nutr. Soil Sci. 164, 569-575 Russell, E. W., 1988, Soil conditions and plant growth, Ed. A. Wild, New York, John
Wiley and Sons, 844-898 Samac, D. A., and Tesfaye, M., 2003, Plant improvement for tolerance to aluminium
in acid soils- a review. Plant Cell, Tissue and Organ Culture, 75:189-207 Sample, E.C., Soper, R.J., and Racz, G.J., 1980, Reactions of phosphate fertilizers in
soils. In The Role of Phosphorus in Agriculture. 1st Ed. Soil Science Society of America, Madison, Wisconsin, USA.
Sander, M.S., Andren, O., 1997. Ash from cereal and rape straw used for heat
production: Liming effect and contents of plant nutrients and heavy metals. Water, Air, and Soil Pollution, 93, 93-108.
Seatz, L. F., Peterson, H. B., 1969, Acid, alkaline, saline, and sodic soils. In Ed. F. E.
Bear, Chemistry of The Soil, Second edition, American Chemical Society Monograph Series, 292-319
Sims, J. T., Pierzynski, G. M., 2000, Assessing the impacts of agricultural, municipal,
and industrial by-products on soil quality, pp. 237-288, In ‘Land Application of Agricultural, Industrial, and Municipal By-Products’, (Eds. J. F. Power and W. A. Dick)., Soil Science Society of America. Book series No 6
Slattery, W. J., Conyers, M. K., and Aitken, R. L., 1999, Soil pH, aluminium,
manganese and lime requirement, In Eds. K. I. Peverill, L. A. Sparrow, D. J. Reuter, Soil Analysis an Interpretation Manual, CSIRO Publishing; Victoria, 103-128
63
Snars, K., Hughes, J.C., and Gilkes, R.J., 2004, The effects of addition of bauxite red mud to soil on P uptake by plants. Australian Journal of Agricultural Research, 55: 25-31
Snyder, G. H., Jones, D. B., and Gascho, G. J., 1986, Silicon fertilization of rice on
everglades Histosols, J. Soil Sci, Soc. Am, 50, 1259-1263 Spies, C. D., and Harms, C. L., 2004, Soil acidity and liming of Indiana soils,
available on http://www.agry.purdue.edu/ext/forages/publications/ay267.htm, [accessed on 5 August 2004]
Tan, K. H., 1994, Environmental soil science, p: 218-251, Marcel Dekker, Inc, New
York Tan, K. H., 1998, Principles of soil chemistry, p: 363, 3rd ed. Marcel Dekker, Inc,
New York The Australian Agriculture Assessment 2001 Report, 2001, available on
www.nlwra.gov.au [accessed on 15 Oct 2004]. Thomas, G. W., and Hargrove, W. L., 1984, The chemistry of soil acidity. In Ed. F.
Adams, Soil Acidity and Liming, Second Edition, American Society of Agronomy, Inc, 3-56
Thompson, J., 2004, Managing soil acidity, available on
http://www.soil.ncsu.edu/lockers/Thompson_J/ssc012/Lecture/Oy_Liming.htm [accessed on 28 July 2004)
Turner TR (1993) Turfgrass. In ‘Nutrient deficiencies & toxicities in crop plants’.
(Ed: Bennett WF). pp. 187 – 196. APS Press, The Am. Phytopath. Soc.: St Paul Minnesota
Vance, E. D., and Mitchell, C. C., 2000, Beneficial use of wood ash as an agricultural
soil amendment: Case studies from the United States forests products industry. In Land Application of Agricultural, Industrial, and Municipal By-Products, (Eds. J. F. Power and W. A. Dick), Soil Science Society of America, Book series no 6, 567-582
White, M.S., 1971. Calcination of Christmas Island phosphate. N. Z. J. Sci 14, 971-
992. Whitney, D. A., and Lamond, R. E., 1993, Liming acid soils, Kansas State University,
Agricultural Experiment Station and Cooperative Extension Service, available on http://www.oznet.ksu.edu/library/CRPSL2/MF1065.Pdf, [accessed on 12 August 2004)
Yusiharni, B. E., Gilkes, R. J., 2006. An evaluation as phosphorus fertilizers of the
byproducts: Chicken litter ash, iron smelting slag and wood ash. Submitted to Aust. J. Agric. Res.
Appendix 4.2.1 The growth of ryegrass before the first harvest for the highest (a) and lowest (b) rates of all the fertilizers, including zero rate of application (control).
69
A. The Highest Rates of P Application
B. The Lowest Rates of P Application
Appendix 4.2.2 The growth of ryegrass before the second harvest for the highest (a) and lowest (b) rates of all the fertilizers, including zero rate of application (control).
70
A. The Highest Rates of P Application
B. The Lowest Rates of P Application
Appendix 4.2.3 The growth of ryegrass before the third harvest for the highest (a) and lowest (b) rates of all the fertilizers, including zero rate of application (control).
71
Appendix 4.3 Concentration of Phosphorus in Plants Tissue
P Concentration (%) Rate of P Applied mg/kg I Harvest II Harvest III Harvest IV Harvest
Appendix 4.4.1 RE Values Based on P Applied and Yield for Each Harvest Harvest Fertilizer Equation RE (%) I MCP Y=0.033X+0.02 (R2= 0.96) 100 DCP Y=0.017X+0.10 (R2= 0.97) 57 RP Y=0.0057X+0.12 (R2= 0.97) 24 Slag Y=0.00033X+0.13 (R2= 0.71) 8 WA Y=0.00021X+0.09(R2= 0.12) 6 CMA Y=0.0014X+0.16 (R2= 0.98) 13 CMAT Y=0.0012X+0.06 (R2= 0.89) 7 II MCP Y=0.029X+0.22 (R2= 0.99) 100 DCP Y=0.018X+0.33 (R2= 0.83) 72 RP Y=0.0067X+0.23 (R2= 0.98) 34 Slag Y=0.00043X+0.12 (R2= 0.66) 9 WA Y=0.00081X+0.11 (R2= 0.66) 9 CMA Y=0.0018X+0.17 (R2= 0.99) 16 CMAT Y=0.0016X+0.12 (R2= 0.97) 12 III MCP Y=0.017X+0.57 (R2= 0.71) 100 DCP Y=0.011X+0.52 (R2= 0.82) 74 RP Y=0.0056X+0.72 (R2= 0.75) 70 Slag Y=0.0011X+0.18 (R2= 0.43) 16 WA Y=-0.00024X+0.27 (R2= 0.01) 18 CMA Y=0.0018X+0.38 (R2= 0.83) 33 CMAT Y=0.00062X+0.22 (R2= 0.33) 17 IV MCP Y=0.019X+0.55 (R2= 0.76) 100 DCP Y=0.019X+0.45 (R2= 0.94) 94 RP Y=0.0063X+0.53 (R2= 0.88) 56 Slag Y=0.0013X+0.08 (R2= 0.36) 10 WA Y=-0.00041X+0.35 (R2= 0.01) 22 CMA Y=0.0014X+0.52 (R2= 0.47) 39 CMAT Y=-0.00006X+0.27 (R2= 0.001) 18
73
Appendix 4.4.2 RE Values Based on P Content and P Applied for Each Harvest Harvest Fertilizer Equation RE (%) I MCP Y=0.027X-0.053 (R2= 0.95) 100 DCP Y=0.012X+0.046 (R2= 0.97) 52 RP Y=0.0045X+0.030 (R2= 0.99) 20 Slag Y=0.00021X+0.069 (R2= 0.74) 6 WA Y=0.00022X+0.054 (R2= 0.27) 5 CMA Y=0.00083X+0.069 (R2= 0.99) 9 CMAT Y=0.00082X+0.035 (R2= 0.91) 6 II MCP Y=0.016X+0.22 (R2= 0.96) 100 DCP Y=0.0097X+0.29 (R2= 0.84) 77 RP Y=0.0043X+0.22 (R2= 0.97) 42 Slag Y=0.00032X+0.11 (R2= 0.53) 12 WA Y=0.00064X+0.096 (R2= 0.61) 12 CMA Y=0.0013X+0.13 (R2= 0.99) 20 CMAT Y=0.0015X+0.10 (R2= 0.97) 18 III MCP Y=0.012X+0.32 (R2= 0.79) 100 DCP Y=0.0083X+0.31 (R2= 0.91) 80 RP Y=0.0041X+0.49 (R2= 0.74) 78 Slag Y=0.00092X+0.16 (R2= 0.43) 23 WA Y=-0.00033X+0.19 (R2= 0.01) 24 CMA Y=0.00091X+0.38 (R2= 0.47) 48 CMAT Y=0.00043X+0.19 (R2= 0.18) 24 IV MCP Y=0.0081X+0.39 (R2= 0.51) 100 DCP Y=0.012X+0.26 (R2= 0.95) 107 RP Y=0.0039X+0.38 (R2= 0.84) 72 Slag Y=0.0012X+0.036 (R2= 0.39) 12 WA Y=-0.00043X+0.24 (R2= 0.03) 33 CMA Y=0.00072X+0.32 (R2= 0.37) 45 CMAT Y=-0.00006X+0.21 (R2= 0.003) 26
74
Appendix 4.4.3 RE Values Based on Soil Bic P and P Applied for Each Harvest Fertilizer Equation RE (%) MCP Y=0.10X+2.81 (R2= 0.84) 100 DCP Y=0.028X+3.27 (R2= 0.64) 59 RP Y=0.029X+1.72 (R2= 0.98) 40 Slag Y=0.0093X+1.02 (R2= 0.72) 19 WA Y=0.010X+1.78 (R2= 0.84) 29 CMA Y=0.0091X+2.59 (R2= 0.88) 39 CMAT Y=0.015X+2.75 (R2= 0.82) 45