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  • 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

    evaluate the industrial byproducts; partly burnt chicken litter ash (CLA), totally burnt

    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 = 3.43), A = apatite (d = 2.84 ) Cu K 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...

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