CHEMICAL AMENDMENT OF DAIRY CATTLE SLURRY FOR THE CONTROL OF PHOSPHORUS

CHEMICAL AMENDMENT OF DAIRY CATTLE SLURRY FOR THE CONTROL OF PHOSPHORUS
NATIONAL UNIVERSITY OF IRELAND GALWAY
CHEMICAL AMENDMENT OF DAIRY CATTLE
SLURRY FOR THE CONTROL OF PHOSPHORUS
IN RUNOFF FROM GRASSLAND
Raymond B. Brennan, B.E.
Research Supervisors:
Dr. Mark G. Healy, Civil Engineering NUI Galway
Dr. Owen Fenton, Teagasc, Johnstown Castle, Wexford
Professor of Civil Engineering: Padraic E. O‘Donoghue
Thesis submitted in fulfilment of the requirements for the degree of Doctor of
Philosophy.
September 2011
The National University of Ireland requires the signatures of all persons using or
photocopying this thesis. Please sign below, and give the address and date.
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I would like to dedicate this work to my wonderful family, and to the memory of Eileen
Armstrong, Helena Brennan and baby Helena Brennan.
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‗Don't let your success determine your attitude, let your attitude determine your success.‘
(Adapted from Ken Brown)
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ABSTRACT
Phosphorus (P) loss from grassland to a waterbody can adversely affect water quality.
Land application of dairy cattle slurry can result in incidental P losses to runoff in
addition to increased chronic P losses from soil as a result of a build-up in Soil Test P
(STP). A literature review identified chemical amendment of dairy cattle slurry as a
possible mitigation measure to prevent such losses. This study comprised laboratory and
field-scale experiments, which investigated the effectiveness and feasibility of chemical
amendments in reducing P solubility, taking into account for the first time their pollution
swapping potential.
First, a controlled agitator experiment was designed to identify the most effective
chemical amendment to reduce Dissolved Reactive Phosphorus (DRP) release to water
overlying grassed soil cores, which received un-amended and amended dairy cattle slurry.
In addition to effectiveness, the feasibility of these amendments was determined based on
several criteria: estimated cost of amendment, amendment delivery to farm, addition of
amendment to slurry, and slurry spreading costs due to any volume increases. The four
best amendments based on effectiveness and feasibility, at optimum application rates
were: ferric chloride (FeCl2), which reduced the DRP in overlying water by 88%,
aluminium chloride (AlCl3) (87%), alum (83%) and lime (81%). These amendments were
then added to slurry immediately before it was surface applied to grassed soil in runoff
boxes, which were subjected to simulated rainfall events. Analysis of overland flow
showed that PAC (Poly-Aluminium Chloride, a commercially available form of AlCl3)
was the most effective amendment for decreasing DRP losses in runoff following slurry
application, while alum proved to be the most effective for total P (TP) and particulate P
(PP) reduction. The incidental loss of metals (aluminium (Al), calcium (Ca) and iron
(Fe)) in runoff during all experiments was below the maximum allowable concentrations
(MAC) for receiving waters.
Once the effectiveness of the amendments under laboratory conditions were quantified,
their ‗pollution swapping‘ potential was examined. A laboratory-scale gas chamber
experiment was conducted to examine emissions of ammonia (NH3), nitrous oxide (N2O),
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methane (CH4) and carbon dioxide (CO2). After considering pollution swapping in
conjunction with amendment effectiveness, the amendments recommended for a micro
plot study were, from best to worst: PAC, alum and lime. This component of the study
investigated how soil and chemically amended slurry interactions affect amendment
effectiveness under field conditions. The results of this micro-plot study validated the
results from the laboratory-scale studies. Alum and PAC reduced average flow-weighted
mean concentration (FWMC) and total loads of DRP, dissolved un-reactive phosphorus
(DUP), PP and TP in runoff, while amendment of slurry with lime at the rate examined in
this study was not effective at reducing P losses. Alum amendment significantly
increased average FWMC of ammonium-N (NH4-N) in runoff water during the first
rainfall event after the slurry was applied (an 84% increase). This indicates that chemical
amendment of dairy cattle slurry conducted on a large scale could increase soluble N
losses. Finally, a 9-month incubation experiment was conducted using five Irish grassland
soils to examine the effect of amendments on the long-term plant availability of P in soil
and the effect of soil type on the stability of reductions in P solubility. The study showed
that, with the exception of FeCl2, the chemical amendments reduced water extractable
phosphorus (WEP) without affecting STP.
This study showed that amendments are effective and that there is no major risk of
pollution swapping associated with alum and PAC. This is a significant finding as there is
now potential to use amendments strategically, in combination with existing POM
(programme of measures), to mitigate P losses. The next step will be to examine the use
of chemical amendments at catchment-scale. It is hoped that there will be economic
incentives given to farmers to reduce nutrient losses. It is possible that P mitigating
methods, such as chemical amendment of dairy cattle slurry, may be used strategically
within a catchment to bind P in cow and pig slurries.
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DECLARATION
This dissertation is the result of my own work, except where explicit reference is made to
the work of others, and has not been submitted for another qualification to this or any
other university.
Raymond Brennan
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ACKNOWLEDGEMENTS
I wish to thank An tOllamh Padraic O‘Donoghue for his encouragement and help during
the research study and during the preparation of this thesis.
I am grateful to Teagasc for providing a Walsh fellowship and funding for this project,
and to the authorities in the National University of Ireland, Galway for providing the
facilities to carry out the research work. I would like to express my gratitude to my NUI,
Galway supervisor, Dr. Mark Healy and my Teagasc supervisor, Dr. Owen Fenton, who
were always encouraging, patient and generous with their time. It has been a wonderful
experience working with them and I owe them my deepest gratitude.
I have been very fortunate and received help from many people along the way. I would
however like to express a special thanks to Drs. Gary Lanigan and Jim Grant for their
time and patience. This work would not have been possible without tremendous
cooperation and help from many people, in particular technical staff in Johnstown Castle,
Teagasc in Athenry and NUI Galway. A special thanks to Ana Serrenho, Kathy Carney,
Maja Drapiewska, Mary O‘Brien, Peter Fahy, Gerry Hynes, Aoife Keady, Liwen Xiao,
Eoghan Clifford, Denis Brennan, Stan Lalor, Theresa Cowman, Linda Finn, Paddy Sills,
Pat Donnelly, Paddy Hayes and Maria Radford. I would also like to extend a special
thanks to John Regan for setting up the rainfall simulator and for training me in the lab. I
wish to thank my fellow post-grads for their support and time. I also wish to thank the tag
rugby team, past and present, for giving me something to look forward to all summer. I
have enjoyed my time in NUI Galway immensely and I will always hold my memories of
my time in university close to my heart. I wish to thank my friends for their support and
patience, especially Joe McGovern for managing to live with me through most of the
PhD. I would also to thank my girlfriend, Joanne, for being so kind, encouraging and
understanding. Finally, I would like to thank my wonderful father, Michael, and my
brothers, Michael, Kieran, Bernard, Dermot and Shane, for their support and endless
encouragement throughout this process.
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ABBREVIATIONS
a
A constant related to the binding strength of molecules onto the
amendments
AD
Anaerobic digestion
Al
Aluminium
AlCl3
Aluminium chloride
Al2O3
Aluminium oxide
Alum
aluminium sulphate (analytical grade (Al2(SO4)3nH2O) and commercial
grade)
Al-WTR-1
Al-WTR-alum-based water treatment residual which was dried and
crushed to pass 2 mm sieve
Al-WTR-2
Al-WTR-alum-based water treatment residual in sludge form
AOD
Above ordnance datum
APHA
American Public Health Association
AVC
Ammonia volatilisation chamber
b
The theoretical amount of P adsorbed to form a complete monolayer on
the surface
bgl
Below ground level
BOD5
Five day biological oxygen demand
BS
British Standards
C
The final P concentration of the solution in isotherm test
Ca
Calcium
CaCO3
Calcium carbonate
CaCl2
Calcium chloride
Ca(OH)2
Lime
CC
Container capacity approximate field capacity in incubation experiment
Ce
The concentration of P in solution at equilibrium (mg L-1)
CH4
Methane
CO2
Carbon dioxide
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CSA
Critical source areas
CSO
Central Statistics Office
CWs
Constructed wetlands
DAFF
Department of Agriculture, Fisheries and Food
d
Day
DM
Dry matter
DRP
Dissolved reactive phosphorus
DUP
Dissolved un-reactive phosphorus
EC
Electrical conductivity
EEC
European Economic Community
EPA
Environment Protection Agency
EPC0
Equilibrium P concentration (i.e. the point where no net desorption or
sorption occurs) in Langmuir Isotherm
EU
European Union
Fe
Iron
FeCl2
Ferrous chloride
FeCL3
Ferric chloride
FeSO4
Ferric chloride
FGD
Flue gas desulphurization
FWMC
Flow-weighted mean concentration
FWS
Free water surface
GHG
Green house gas
GWP
Global warming potential
H
Hour
ha
Hectare
H2
Hydrogen gas
H2S
Hydrogen sulphide
H2SO4
Sulphuric acid
HCl
Hydrochloric acid
ICP
Inductive coupled plasma
IPCC
Intergovernmental Panel on Climate Change
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K
Potassium
kd
The slope of the relationship between S‘ and C
LOI
Loss on ignition
M3
Mehlich-III P
MAC
Max allowable concentration
Mg
Magnesium
MgCl2
Magnesium chloride
N
Nitrogen
mo
Month
N2
Nitrogen gas
N2O
Nitrous oxide
NH3
Ammonia
NH4
Ammonium
NH4
Ammonium ion
NH4-N
Ammonium nitrogen
NO2
Nitrite
NO2-N
Nitrite nitrogen
NO3
Nitrate
NO3-N
Nitrate nitrogen
OJEC
Official Journal of the European Community
OM
Organic matter
P
Phosphorus
PAA
Photo-acoustic-analyser
PAC
Poly-aluminium chloride
PAM
Polyacrylamide
PDS
Particle size distribution
POM
Programme of measurements
PP
Particulate phosphorus
PSM
Phosphorus sorbing material
R2
Regression coefficient
RS1
Rainfall simulation event 1
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RS2
Rainfall simulation event 2
RS3
Rainfall simulation event 3
rpm
Revolutions per minute
S'
The mass of P adsorbed from slurry (mg kg-1),
S0
The amount of P originally sorbed to the amendment (mg L-1)
SAS
Statistical Analysis Software
SI
Statutory Instrument
SS
Suspended sediment
STP
Soil test phosphorus
T0.5
The time for half of ammonia losses to occur
TAN
Total ammonical nitrogen
TDP
Total dissolved phosphorus in water
TDS
Total dissolved solids
TK
Total potassium
TN
Total nitrogen
TON
Total oxidized nitrogen
TP
Total phosphorus
TR
Time from commencement of simulated rainfall event and start of runoff
UK
United Nations
UN
United Nations
U.S.A.
United States of America
USDA
United States Department of Agriculture
USEPA
United States Environment Protection Agency
WEP
Water extractable phosphorus
WFD
Water Framework Directive
WTR
Water treatment residuals
x/m
The mass of P adsorbed per unit mass of amendments (g kg-1) at Ce
Ω
Stream power of overland flow
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TABLE OF CONTENTS
ABBREVIATIONS ..................................................................................... IX
LIST OF FIGURES ................................................................................XVIII
LIST OF TABLES ..................................................................................XXIII
CHAPTER 1
INTRODUCTION ................................................................................ 1
1.1.
OVERVIEW.............................................................................................. 1
1.2.
PROCEDURE............................................................................................ 3
1.3.
STRUCTURE OF DISSERTATION .............................................................. 4
CHAPTER 2
LITERATURE REVIEW .................................................................... 6
2.1.
OVERVIEW.............................................................................................. 6
2.2.
AGRICULTURE IN IRELAND .................................................................... 6
2.3.
LEGISLATION AND COMPLIANCE ........................................................... 8
2.4.
CURRENT WATER QUALITY STATUS IN IRELAND .................................. 8
2.5.
IMPACT OF AGRICULTURE ON WATER QUALITY ................................. 10
2.6.
NUTRIENTS LOSS AND PATHWAYS DURING LAND APPLICATION OF
DAIRY SLURRY ......................................................................................................... 11
2.7.
PHOSPHORUS ........................................................................................ 11
2.7.1.
2.7.2.
2.8.
Phosphorus in soil ............................................................................. 12
Methods used to determine risk of P loss to water ........................... 12
NITROGEN ............................................................................................ 16
2.9.
LOSS OF SOLUBLE AND PARTICULATE NUTRIENTS IN RUNOFF............ 19
2.9.1.
2.9.2.
2.10.
Soluble nutrient loss .......................................................................... 19
Particulate nutrient loss ..................................................................... 20
GASEOUS EMISSIONS AND THE IMPORTANCE OF CONSIDERING
POLLUTION SWAPPING WHEN SELECTING A P MITIGATION MEASURE .................. 24
2.11.
PRESENT AND EMERGING P MITIGATION MEASURES .......................... 24
2.11.1.
2.11.2.
2.11.3.
2.11.4.
2.11.5.
2.11.6.
2.11.7.
Constructed wetlands ...................................................................... 25
Anaerobic digestion ......................................................................... 27
Biochar ............................................................................................ 29
Buffer strips and enhanced buffer strips.......................................... 30
Composting ..................................................................................... 31
In-stream and edge of field filters ................................................... 32
Sand and woodchip filter systems ................................................... 35
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2.11.8. Slurry separation.............................................................................. 35
2.11.9. Use of P sorbing amendments ......................................................... 37
2.11.9.1.
2.11.9.2.
2.12.
Amendments applied directly to soil ..............................................37
Amendments to slurry ....................................................................38
RECOMMENDATIONS AND KNOWLEDGE GAPS .................................... 40
CHAPTER 3 EVALUATION OF CHEMICAL AMENDMENTS TO CONTROL
PHOSPHORUS LOSSES FROM DAIRY SLURRY .................................................. 42
3.1.
OVERVIEW............................................................................................ 42
3.2.
INTRODUCTION..................................................................................... 42
3.3.
MATERIALS AND METHODS .................................................................. 43
3.3.1.
3.3.2.
3.3.3.
3.3.4.
3.3.5.
3.3.6.
3.3.7.
Soil preparation and analysis ............................................................ 43
Slurry sampling and analysis ............................................................ 45
PSM sourcing and analysis ............................................................... 45
Agitator test ....................................................................................... 46
Water sampling and analysis ............................................................ 50
Statistical Analysis ............................................................................ 50
Cost analysis ..................................................................................... 50
RESULTS ............................................................................................... 51
3.4.1.
3.4.2.
3.5.
Results of agitator test ....................................................................... 51
Cost and feasibility analysis.............................................................. 53
DISCUSSION .......................................................................................... 56
3.6.
CONCLUSIONS ...................................................................................... 58
3.7.
SUMMARY ............................................................................................. 58
3.4.
CHAPTER 4 LABORATORY-SCALE RAINFALL SIMULATION
EXPERIMENT 59
4.1.
OVERVIEW............................................................................................ 59
4.2.
INTRODUCTION..................................................................................... 59
4.3.
MATERIALS AND METHODS ................................................................. 60
4.3.1.
4.3.2.
4.3.3.
4.3.4.
4.3.5.
Soil sample collection and analysis .................................................. 60
Slurry collection and analysis ........................................................... 60
Slurry amendment and runoff set-up ................................................ 61
Sample handling and analysis ........................................................... 67
Statistical analysis ............................................................................. 67
RESULTS ............................................................................................... 68
4.4.1.
4.4.2.
4.4.3.
Slurry and amended slurry analysis .................................................. 68
Water quality analysis ....................................................................... 69
Metals in runoff water ....................................................................... 73
DISCUSSION .......................................................................................... 76
4.4.
4.5.
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4.5.1.
4.5.2.
4.5.3.
4.6.
Slurry and amended slurry analysis .................................................. 76
Water quality ..................................................................................... 77
Metals in runoff water ....................................................................... 79
CONCLUSIONS ...................................................................................... 80
4.7.
SUMMARY ............................................................................................. 81
CHAPTER 5 EFFECT OF CHEMICAL AMENDMENT OF DAIRY CATTLE
SLURRY ON GREENHOUSE GAS AND AMMONIA EMISSIONS ...................... 82
5.1.
OVERVIEW............................................................................................ 82
5.2.
INTRODUCTION..................................................................................... 82
5.3.
MATERIALS AND METHODS ................................................................. 83
5.3.1.
5.3.2.
5.3.3.
5.3.4.
5.3.5.
5.3.6.
Soil sample collection and analysis .................................................. 83
Dairy slurry collection and analysis .................................................. 84
Chemical amendment of slurry ......................................................... 84
Measurement of ammonia................................................................. 85
Measurement of CH4, N2O and CO2 ................................................. 87
Statistical analysis ............................................................................. 87
RESULTS ............................................................................................... 88
5.4.1.
5.4.2.
5.4.3.
5.4.4.
5.4.5.
5.4.6.
Slurry and amended slurry results..................................................... 88
Ammonia........................................................................................... 89
Nitrous oxide ..................................................................................... 91
Carbon dioxide .................................................................................. 91
Methane emissions ............................................................................ 94
Impact of amendments on global warming potential ........................ 95
DISCUSSION .......................................................................................... 97
5.5.1.
5.5.2.
5.5.3.
5.5.4.
5.6.
Ammonia emissions .......................................................................... 97
Nitrous oxide ..................................................................................... 99
Carbon emissions ............................................................................ 100
Impacts of pollution swapping ........................................................ 101
CONCLUSIONS .................................................................................... 102
5.7.
SUMMARY ........................................................................................... 103
CHAPTER 6
PLOT-SCALE RAINFALL SIMULATION STUDY ................... 104
6.1.
OVERVIEW.......................................................................................... 104
6.2.
INTRODUCTION................................................................................... 104
6.3.
MATERIALS AND METHODS ............................................................... 105
5.4.
5.5.
6.3.1.
6.3.2.
6.3.3.
6.3.4.
6.3.5.
Study site ......................................................................................... 105
Slurry analysis ................................................................................. 107
Treatments....................................................................................... 109
Rainfall simulation .......................................................................... 110
Statistical analysis ........................................................................... 113
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6.4.
RESULTS ............................................................................................. 114
6.4.1.
6.4.2.
6.4.3.
6.5.
Phosphorus (FWMC of DRP, DUP, PP and TP) ............................ 114
Nitrogen .......................................................................................... 116
Time to runoff, soil volumetric water content and runoff volume . 117
DISCUSSION ........................................................................................ 119
6.5.1. Phosphorus (FWMC of DRP, DUP, PP and TP) ............................ 119
6.5.2. Nitrogen .......................................................................................... 120
6.5.3. Rainfall intensity, soil volumetric water content, time to runoff and
runoff volume ............................................................................................... 121
6.5.4. Outlook for future implementation of chemical amendment of dairy
cattle slurry as a management practice for high P soils ............................... 122
6.6.
CONCLUSIONS .................................................................................... 124
6.7.
SUMMARY ........................................................................................... 124
CHAPTER 7 THE LONG-TERM IMPACT OF THE ADDITION OF
CHEMICALLY AMENDED DAIRY SLURRY ON PHOSPHORUS CONTENT
AND PH OF FIVE SOIL TYPES ................................................................................ 125
7.1.
OVERVIEW.......................................................................................... 125
7.2.
INTRODUCTION................................................................................... 125
7.3.
MATERIALS AND METHODS ................................................................ 126
7.3.1.
7.3.2.
7.3.3.
7.3.4.
Soil collection and analysis ............................................................. 126
Slurry collection and analysis ......................................................... 126
Incubation experiment .................................................................... 128
Statistical analysis ........................................................................... 131
RESULTS ............................................................................................. 132
7.4.1.
7.4.2.
7.4.3.
Water extractable phosphorus ......................................................... 132
Soil test phosphorus ........................................................................ 133
Soil pH ............................................................................................ 134
DISCUSSION ........................................................................................ 134
7.5.1.
7.5.2.
7.5.3.
7.6.
WEP ................................................................................................ 134
Soil test phosphorus ........................................................................ 139
Soil pH ............................................................................................ 139
CONCLUSIONS .................................................................................... 140
7.7.
SUMMARY ........................................................................................... 140
CHAPTER 8
CONCLUSIONS AND RECOMMENDATIONS ......................... 141
8.1.
OVERVIEW.......................................................................................... 141
8.2.
CONCLUSIONS .................................................................................... 141
8.3.
RECOMMENDATIONS FOR FUTURE WORK ......................................... 143
8.4.
CONTEXT ............................................................................................ 144
7.4.
7.5.
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REFERENCES .............................................................................................................. 146
APPENDIX ................................................................................................... 171
APPENDIX A LIST OF PUBLICATIONS ................................................................................... 172
APPENDIX B RESULTS OF AGITATOR TEST ........................................................................... 174
APPENDIX C RUNOFF BOX STUDY RESULTS ......................................................................... 194
APPENDIX D RESULTS FROM CHAPTER 5 ........................................................................... 212
APPENDIX E PHOTOGRAPHS OF SLURRY AND AMENDED SLURRY APPLIED TO PLOTS (CHAPTER
6) ............................................................................................................................. 238
APPENDIX F RESULTS OF PLOT STUDY................................................................................ 240
APPENDIX G INCUBATION STUDY RESULTS ......................................................................... 259
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LIST OF FIGURES
FIGURE 2.1 NUMBER OF GROUND WATER MONITORING SITES WITH
PHOSPHATE CONCENTRATIONS FROM 1995 TO 2009 (MCGARRIGLE ET
AL., 2011) ................................................................................................................... 9
FIGURE 2.2 NUMBER OF REPORTED FISH KILLS ATTRIBUTED TO
AGRICULTURE, INDUSTRY, LOCAL AUTHORITY, OTHER AND
UNKNOWN SOURCES (MCGARRIGLE ET AL., 2011) ..................................... 10
FIGURE 2.3 THE SOIL P CYCLE: ITS COMPONENTS AND MEASURABLE
FRACTIONS (STEWARD AND SHARPLEY, 1987) ............................................ 13
FIGURE 2.4 SCHEMATIC OF THE SOIL N CYCLE (KETTERINGS ET AL., 2011) 17
FIGURE 2.5 RELATIONSHIP BETWEEN THE AMMONIA/AMMONIUM
(NH3/NH4+) RATIO AND PH (GAY AND KNOWLTON, 2005) .......................... 18
FIGURE 2.6 DETACHMENT OF SOIL PARTICLES IN A RAINFALL EVENT
(ROSE, 2004) ............................................................................................................ 21
FIGURE 2.7 RATE OF SEDIMENT DEPOSITION IN SURFACE RUNOFF (ROSE,
2004) ......................................................................................................................... 22
FIGURE 2.8 ENTRAINMENT AND RE-ENTRAINMENT OF SEDIMENT (ROSE,
2004). ........................................................................................................................ 23
FIGURE 2.9 COMPOST FILLED SOCKS IN INSTRUMENTED DRAINAGE
CHANNEL (SHIPITALO ET AL., 2010A) ............................................................. 33
FIGURE 2.10 PERMEABLE EDGE OF FIELD BARRIERS (O‘CONNOR ET AL.,
2010) ......................................................................................................................... 34
FIGURE 2.11 SCHEMATIC AND PHOTO OF FERRIC-SULPHATE DOSER IN
OPERATION IN JOKIOINEN, FINLAND (NARVANEN ET AL., 2008) ............ 35
FIGURE 2.12 PILOT SCALE WOOD CHIP FILTER USED TO TREAT THE LIQUID
PORTION OF PIG SLURRY FOLLOWING SEPARATION (CARNEY ET AL.,
2011) ......................................................................................................................... 36
FIGURE 3.1 BEAKERS PLACED IN FLOCCULATOR DURING AGITATOR TEST
................................................................................................................................... 43
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FIGURE 3.2 UNITED STATES DEPARTMENT OF AGRICULTURE (USDA) SOIL
TEXTURE CLASSIFICATION TRIANGLE USED TO DETERMINE SOIL
TEXTURE ................................................................................................................ 44
FIGURE 3.3 SCHEMATIC DIAGRAM OF SOIL SAMPLE IN AGITATOR .............. 48
FIGURE 3.4 PHOSPHORUS CLASSIFICATION SYSTEM USED IN THIS STUDY
(APHA, 1995) ........................................................................................................... 51
FIGURE 3.5 MASS OF DRP AND DRP CONCENTRATION IN OVERLYING
WATER .................................................................................................................... 52
FIGURE 3.6 TOTAL COST OF CHEMICAL AMENDMENT OF DAIRY CATTLE
SLURRY PLOTTED AGAINST THE REDUCTION IN DISSOLVED REACTIVE
PHOSPHORUS (DRP) LOST TO OVERLYING WATER AND THE
PERCENTAGE REDUCTION IN DRP RELEASE TO OVERLYING WATER .. 53
FIGURE 3.7 HISTOGRAM OF SLURRY PH AT TIME OF
AMENDMENT/APPLICATION (CLEAR BOX) AND PH OF SLURRY AFTER
24 H (HATCHED BOX) .......................................................................................... 55
FIGURE 4.1 LANGMUIR ISOTHERM FITTED TO PHOSPHORUS IN AMENDED
SLURRY DATA ....................................................................................................... 62
FIGURE 4.2 PHOSPHORUS SORPTION ISOTHERMS FOR AMENDED SLURRY
DATA ....................................................................................................................... 63
FIGURE 4.3 RUNOFF BOX IMMEDIATELY (A) BEFORE AND (B) AFTER
SLURRY APPLICATION........................................................................................ 65
FIGURE 4.4 PHOTOGRAPHS SHOWING SOIL SOD PREPARATION AND
PLACEMENT METHODOLOGY .......................................................................... 66
FIGURE 4.5 PHOTOGRAPHS OF SLURRY AND AMENDED SLURRY
IMMEDIATELY AFTER APPLICATION TO GRASSED SOIL IN BOXES ....... 69
FIGURE 4.6 THE AVERAGE FLOW-WEIGHTED MEAN CONCENTRATION OF
DISSOLVED REACTIVE PHOSPHORUS (DRP), DISSOLVED UNREACTIVE
PHOSPHORUS (DUP) AND PARTICULATE PHOSPHORUS (PP), WHICH
COMPRISE TOTAL PHOSPHORUS (TP) IN RUNOFF FROM THREE
RAINFALL SIMULATION EVENTS..................................................................... 71
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FIGURE 4.7 THE AVERAGE % OF DISSOLVED REACTIVE PHOSPHORUS (DRP)
DISSOLVED UNREACTIVE PHOSPHORUS (DUP) AND PARTICULATE
PHOSPHORUS (PP), WHICH COMPRISE TOTAL PHOSPHORUS (TP) IN
RUNOFF AFTER THREE RAINFALL SIMULATION EVENTS ........................ 73
FIGURE 4.8 AVERAGE FLOW-WEIGHTED MEAN CONCENTRATIONS OF
SUSPENDED SEDIMENT IN RUNOFF ................................................................ 74
FIGURE 4.9 AVERAGE FLOW-WEIGHTED MEAN CONCENTRATIONS OF AL IN
RUNOFF AND RAIN WATER ............................................................................... 75
FIGURE 4.10 AVERAGE FLOW-WEIGHTED MEAN CONCENTRATIONS OF CA
IN RUNOFF AND RAIN WATER .......................................................................... 75
FIGURE 4.11 AVERAGE FLOW-WEIGHTED MEAN CONCENTRATIONS OF FE
IN RUNOFF AND RAIN WATER .......................................................................... 76
FIGURE 5.1 PHOTOGRAPH OF DYNAMIC CHAMBER APPARATUS ................... 83
FIGURE 5.2 DIAGRAM OF APPARATUS USED TO MEASURE AMMONIA
EMISSIONS ............................................................................................................. 85
FIGURE 5.3 DYNAMIC CHAMBER ............................................................................. 86
FIGURE 5.4 PHOTOGRAPH OF PAA DURING CARBON DIOXIDE, METHANE
AND NITROUS OXIDE MEASURING PERIOD .................................................. 88
FIGURE 5.5 CUMULATIVE AMMONIA EMISSIONS FROM UNTREATED AND
CHEMICALLY AMENDED SLURRY EXPRESSED AS A PERCENTAGE OF
TOTAL NITROGEN IN SLURRY AND AMMONIACAL NITROGEN IN
SLURRY ................................................................................................................... 90
FIGURE 5.6 NITROUS OXIDE EMISSIONS FROM SLURRY AND AMENDED
SLURRY IN CHAMBERS (MEAN ± STANDARD ERROR) ............................... 92
FIGURE 5.7 CARBON DIOXIDE EMISSIONS FROM SLURRY AND AMENDED
SLURRY IN CHAMBERS. (MEAN ± STANDARD ERROR) .............................. 93
FIGURE 5.8 CUMULATIVE CARBON DIOXIDE EMISSIONS FROM CHAMBERS
FOR DURATION OF STUDY. (MEAN ± STANDARD ERROR) ........................ 93
FIGURE 5.9 METHANE EMISSIONS FROM SLURRY AND AMENDED SLURRY
IN CHAMBERS. (MEAN ± STANDARD ERROR)............................................... 94
xx
FIGURE 5.10 NITROGEN CUMULATIVE EMISSIONS (NITROUS OXIDE AND
INDIRECT EMISSIONS RESULTING FROM AMMONIA LOSSES)
EXPRESSED IN CO2 EQUIVALENTS. (MEAN ± STANDARD ERROR) ......... 95
FIGURE 5.11 CUMULATIVE CARBON DIOXIDE (CO2), INDIRECT NITROUS
OXIDE (N2O), DIRECT N2O AND METHANE (CH4) MEASURED DURING
THE STUDY EXPRESSED IN CO2 EQUIVALENTS. (MEAN ± STANDARD
ERROR) .................................................................................................................... 96
FIGURE 5.12 RELATIONSHIP BETWEEN SLURRY AND AMENDED SLURRY PH
AT TIME OF APPLICATION AND (A) CUMULATIVE NH3 EMISSIONS AND
(B) AND LOG OF TIME FOR HALF OF AMMONIA EMISSIONS TO OCCUR
(T0.5) .......................................................................................................................... 99
FIGURE 6.1 MAP OF STUDY SITE SHOWING GROUND ELEVATION,
TOPOGRAPHY, SLOPE, SOIL CONDUCTIVITY, GROUNDWATER FLOW
DIRECTION, LOCATION OF SUBPLOTS AND OF GROUNDWATER WELLS.
................................................................................................................................. 106
FIGURE 6.2 PLOT SET UP AND RUNOFF COLLECTION PHOTOGRAPH .......... 109
FIGURE 6.3 PHOTOGRAPHS OF RAINFALL SIMULATOR ................................... 111
FIGURE 6.4 NATURAL RAINFALL AND AVERAGE DEPTH OF SIMULATED
RAINFALL RECEIVED BY THE PLOTS FOR EACH EVENT ......................... 112
FIGURE 6.5 PHOTO OF THE MEASUREMENT OF VOLUMETRIC WATER
CONTENT OF SOIL USING TIME DOMAIN REFLECTROMETRY............... 113
FIGURE 6.6 AVERAGE FLOW-WEIGHTED MEAN CONCENTRATIONS OF
DISSOLVED REACTIVE PHOSPHORUS (DRP), DISSOLVED UN-REACTIVE
P (DUP) AND PARTICULATE P (PP) COMPRISING TOTAL P (TP) FOR
THREE RAINFALL SIMULATION EVENTS, AND MAXIMUM ALLOWABLE
CONCENTRATIONS (MAC) IN WATERWAYS. .............................................. 115
FIGURE 6.7 AVERAGE FLOW-WEIGHTED MEAN CONCENTRATIONS OF
AMMONIUM NITRATE (NH4-N), NITRITE (NO2-N) AND NITRATE (NO3-N)
FOR THREE RAINFALL SIMULATION EVENTS, AND MAXIMUM
ALLOWABLE CONCENTRATIONS (MAC) IN WATERWAYS. .................... 117
xxi
FIGURE 6.8 AVERAGE RAINFALL INTENSITY, RUNOFF VOLUME, TIME TO
RUNOFF AND SOIL VOLUMETRIC WATER CONTENT FOR THE FIRST
(RS1), SECOND (RS2) AND THIRD (RS3) RAINFALL EVENTS. ................... 118
FIGURE 7.1 SITE LOCATIONS SHOWN ON MAP OF IRELAND .......................... 127
FIGURE 7.2 SCHEMATIC OF PACKER USED TO ACHIEVE APPROXIMATE
BULK DENSITY.................................................................................................... 130
FIGURE 7.3 WATER EXTRACTABLE PHOSPHORUS (WEP) OF INCUBATED
SOIL SAMPLES AT EACH SAMPLING TIME (N=3) ....................................... 135
FIGURE 7.4 SOIL TEST P OF INCUBATED SOIL SAMPLES AT EACH SAMPLING
TIME (N=3) ............................................................................................................ 136
FIGURE 7.5 PH OF INCUBATED SOIL SAMPLES AT EACH SAMPLING TIME
(N=3) ....................................................................................................................... 137
xxii
LIST OF TABLES
TABLE 2.1 SUMMARY STATISTICS FROM 41 IRISH CATTLE SLURRY
SAMPLES (MARTÍNEZ-SULLER ET AL., 2010)................................................... 7
TABLE 2.2 RESULTS OF LABORATORY AND PLOT-SCALE RUNOFF STUDIES
EXAMINING THE EFFECT OF LAND APPLICATION OF DAIRY CATTLE
SLURRY ON P IN RUNOFF WATER FROM GRASSLANDS ............................ 12
TABLE 2.3 ALTERNATIVE SOIL TEST PHOSPHORUS ANALYSIS METHODS
USED AROUND THE WORLD.............................................................................. 14
TABLE 2.4 DILUTION RATES USED TO DETERMINE WEP OF SOIL................... 15
TABLE 2.5 PHOSPHORUS INDEX SYSTEM USED FOR IRISH GRASSLANDS
(SCHULTE ET AL, 2010B) ..................................................................................... 15
TABLE 2.6 AVERAGE P INDEX OF SOILS TESTED IN JOHNSTOWN CASTLE
FOR THE PERIOD BETWEEN 2004 AND 2006 (MARK PLUNKETT, PERS
COM, 2009) .............................................................................................................. 16
TABLE 2.7 PERFORMANCE OF BUFFER STRIPS IN REDUCING TOTAL AND
SOLUBLE PHOSPHORUS IN RUNOFF (ADAPTED FROM KAY ET AL., 2009)
................................................................................................................................... 31
TABLE 2.8 REVIEW OF LABORATORY-SCALE STUDIES EXAMINING
CHEMICAL AIDED SEPARATION TO REDUCE P IN LIQUID FRACTION OF
SEPARATED DAIRY CATTLE SLURRY ............................................................. 37
TABLE 2.9 RESULTS OF LABORATORY AND PLOT-SCALE CHEMICAL
AMENDMENTS STUDIES TO DATE ................................................................... 39
TABLE 3.1 CHARACTERISATION OF PSMS AND ALUM USED IN THE
AGITATOR TEST (MEAN ± STANDARD DEVIATION) TESTS CARRIED OUT
IN TRIPLICATE ...................................................................................................... 47
TABLE 3.2 TABLE SHOWING AMENDMENTS IN ORDER OF EFFECTIVENESS
SCORE, BREAKDOWN OF COSTSA, COST/M3 SLURRYB, COST FOR 100
COW FARM, PERCENTAGE REDUCTION IN DRP IN OVERLYING WATER
AND WEP OF SLURRY AT 24 H .......................................................................... 49
TABLE 3.3 FEASIBILITY OF AMENDMENTS ........................................................... 54
xxiii
TABLE 4.1 STOICHIOMETRIC RATIO AT WHICH THE AMENDMENTS WERE
APPLIED AND SLURRY DRY MATTER (DM), PH AND AVERAGE
CONCENTRATIONS OF NH4- N, WATER EXTRACTABLE PHOSPHORUS
(WEP), TOTAL NITROGEN (TN), TOTAL PHOSPHORUS (TP) AND TOTAL
POTASSIUM (TK) (N=3) ........................................................................................ 68
TABLE 4.2 RESULTS FROM CHAPTER 3 AND 4, SHOWING COST OF
TREATMENTS AND TOTAL PHOSPHORUS (TP) LOST FROM RUNOFF BOX
................................................................................................................................... 72
TABLE 5.1 DAIRY CATTLE SLURRY AND AMENDED DAIRY CATTLE SLURRY
PROPERTIES ........................................................................................................... 89
TABLE 5.2. SUMMARY OF AMENDMENTS USED TO REDUCE AMMONIA
EMISSIONS IN PREVIOUS STUDIES .................................................................. 98
TABLE 5.3 SUMMARY OF FEASIBILITY OF AMENDMENTS (ADAPTED FROM
CHAPTER 3). MARKS FOR FEASIBILITY AND POLLUTION SWAPPING
ARE FROM 1 TO 5. 1 = BEST 5 = WORST......................................................... 102
TABLE 6.1 SOIL PH, MORGAN‘S EXTRACTABLE P, K AND MG, SAND SILT,
CLAY FRACTIONS, AND TEXTURAL CLASS OF SOIL USED IN THIS
STUDY. THE LOCATION OF THE PIEZOMETERS IS ILLUSTRATED IN
FIGURE 6.1 ............................................................................................................ 107
TABLE 6.2 THE AVERAGE SLOPE FOR EACH BLOCK, SOIL PH, WATER
EXTRACTABLE PHOSPHORUS (WEP), MORGAN‘S EXTRACTABLE P,
POTASSIUM (K), AND MAGNESIUM (MG) BEFORE APPLICATION OF
TREATMENTS. ..................................................................................................... 108
TABLE 6.3 SLURRY DM, PH, WATER EXTRACTABLE PHOSPHORUS (WEP),
TOTAL NITROGEN (TN), TOTAL PHOSPHORUS (TP) AND TOTAL
POTASSIUM (TK) AND AVERAGE CONCENTRATIONS OF NH4- N (N=5) 108
TABLE 7.1
SOIL PHYSICAL AND CHEMICAL PROPERTIES. ...................... 129
TABLE 7.2
SLURRY PROPERTIES .................................................................... 130
TABLE 8.1 SUMMARY OF FEASIBILITY OF AMENDMENTS (ADAPTED FROM
CHAPTER 3). MARKS FOR FEASIBILITY, POLLUTION SWAPPING,
xxiv
INCUBATION STUDY AND PLOT STUDY ARE FROM 1 TO 5. 1 = BEST; 5 =
WORST................................................................................................................... 143
xxv
Chapter 1
1.1.
Introduction
Overview
In Ireland, agriculture is an important national industry that involves approximately
270,000 people, 6.191 million cattle, 4.257 million sheep, 1.678 million pigs and 10.7
million poultry (CSO, 2006). It utilizes 64% of Ireland‘s land area (Fingleton and
Cushion, 1999), of which 91% is devoted to grass, silage and hay, and rough grazing
(DAFF, 2008). Livestock production is associated with external inputs of nitrogen (N)
and phosphorus (P), which include inorganic and organic fertilizers. Land application of
fertilisers followed by a rainfall event can result in incidental losses of P to runoff. In
addition, chronic P losses from the soil as a result of a build up in soil test P (STP) can
also contribute to losses in other times of the agricultural calendar. Land application of
fertilisers also result in N leaching through the soil to surface and ground waters. In
practice P is of particular importance as it is the critical nutrient in fresh water systems. In
order for Ireland to comply with the requirements of the European Union Water
Framework Directive (EU WFD; 2000/60/EC, OJEC, 2000) to achieve at least ‗good
status‘ of all surface and groundwater by 2015, programmes of measures (POM) should
be in place to prevent such losses. Ireland‘s agricultural POM is the Nitrates Directive (SI
610 of 2010). These measures have addressed the problem by limiting fertiliser
application rates and improving manure management. Particular focus has been given to
time of application and increasing slurry storage capacity on farms. A possible
supplementary mitigation method is the chemical amendment of slurries. However,
before chemical amendment of dairy cattle slurry may be considered for implementation
in Ireland, there is a need for an extensive study of their use.
1
The aim of this study is to examine the: (1) effectiveness of different amendments to
prevent P losses in runoff (2) feasibility of the different amendments to be used on a farm
(3) risk of metal release to overland flow and (4) possibility of ‗pollution swapping‘
(defined by Stevens and Quinton (2009) as the increase in one pollutant as a result of a
measure introduced to reduce a different pollutant). The present study comprised
laboratory and field-scale experiments, which were designed to address knowledge gaps
in these areas. For the first time in Ireland, a series of experiments were conducted to
examine the possibility of bringing such a supplementary mitigation measure to Irish
farms.
The specific objectives of this study were:
1. To review existing and emerging P mitigation measures for the control of P losses
arising from the land application of dairy cattle slurry to grasslands in Ireland.
Following this, the study aimed to select a measure suitable for further study and
to identify knowledge gaps which need to be addressed in order for this measure
to be considered for implementation at farm scale.
2. To evaluate the effectiveness and feasibility of potential chemical amendments
and to use such criteria to select the most suitable amendment for trial at field
scale.
3. In parallel to the P mitigation experiments, to examine the effects of pollution
swapping, the loss of N chemical species in runoff and gaseous emissions of
ammonia (NH3) and greenhouse gases (GHG) to the atmosphere. In addition, this
study aims to examine the effect of chemical amendment of dairy cattle of slurry
on metal losses in runoff.
4. To examine the effect of chemical amendment of dairy cattle slurry prior to
application to soil on long-term soil water extractable phosphorus (WEP) and
plant available P.
2
5. To examine the effect of soil type on P solubility in amended slurry applied to
soil.
1.2.
Procedure
A literature review of P loss mitigation technologies with the potential to reduce P losses
arising from land application of dairy cattle slurry was undertaken. Chemical amendment
of dairy cattle slurry was chosen for further study as chemical amendments have the
ability to be quickly implemented, are cost effective and capable of being used in
strategic locations for maximum benefit i.e. no capital cost or need to transport slurry
long distances. Several knowledge gaps were identified and experiments were designed
accordingly.
Following this, a novel experiment (an ‗agitator test‘) was used to determine the most
suitable amendments for addition to dairy cattle slurry with the aim of reducing P loss in
runoff. In this experiment, potential amendments (alum, aluminium chloride, ferric
chloride (FeCl2), flyash, flue gas desulphurisation by-product (FGD), lime, polyaluminium chloride hydroxide (PAC) and water treatment residuals (WTR)) were added
to slurry before slurry was applied to intact soil cores, which were overlain by water in a
1-L beaker. The overlying water was then stirred to simulate overland flow. The agitator
test successfully identified amendments with the potential to reduce dissolved reactive
phosphorus (DRP) in overlying water.
The most feasible amendments (alum, PAC, FeCl2 and lime) were then examined in a
runoff study conducted using laboratory runoff boxes subjected to simulated rainfall
applied at an intensity of 11.5 mm h-1 to develop a greater understanding of how chemical
amendments affected different forms of P in runoff.
It is critical that the potential for ‗pollution swapping‘ is examined when evaluating a
potential P mitigating technology such as those examined in this study. In particular, the
3
effects of any proposed treatments on GHG emissions must be examined. To address this,
a laboratory chamber experiment was used to examine the effect of chemical amendment
of dairy cattle slurry on emissions of NH3, nitrous oxide (N2O), methane (CH4) and
carbon dioxide (CO2). This allowed for the pollution swapping potential of amendments
to be considered in the selection of amendments chosen for field scale study.
The most feasible amendments were then examined at micro field plot-scale in
Johnstown Castle, Co. Wexford. Twenty five plots, each measuring 0.4 m-wide by 0.9 mlong, were hydraulically isolated before being amended with untreated or chemically
amended dairy cattle slurry. Three rainfall simulations were conducted over a period of
one month and the surface runoff was collected for half an hour during each event.
Finally, a laboratory incubation experiment was conducted to examine (1) the effect of
amendments on the long-term plant availability of P in soil and (2) the effect of soil type
on stability of reductions in P solubility. Five soils were subjected to six treatments (soil
only, slurry only and four chemically amended slurries) and destructively sampled at 0, 3,
6 and 9 months from the start of the experiment.
1.3.
Structure of dissertation
Chapter 2 reviews the current water quality status in Ireland and the impact of agriculture,
particularly dairy cattle slurry, on water quality. Chapter 2 also focuses on Ireland‘s
performance in relation to WFD water guidelines, with particular focus on the potential
need to explore P mitigating measures for possible implementation if current measures
are not sufficient to meet targets. Chapter 3 details the results of the agitator test which
was used to evaluate the effectiveness and appropriate application rates for amendments.
Chapter 3 also examines the feasibility of amendments and a detailed cost analysis is
presented. Chapter 4 describes the results of a laboratory-scale runoff-box study. Chapter
5 details the results of the gas chamber experiments designed to examine the pollution
swapping potential of amendments. Chapter 6 details the results of a plot-scale runoff
experiment conducted in Johnstown Castle Research Centre. Chapter 7 details the results
4
of the nine-month incubation experiment. Finally, in Chapter 8, conclusions from the
study are presented and recommendations for future research work are made.
To date, two international peer review papers have been published from this work:
Brennan, R.B., Fenton, O., Rodgers, M., Healy, M.G. 2011. Evaluation of chemical
amendments to control phosphorus losses from dairy slurry. Soil Use and
Management 27: 238-246.
Brennan, R.B., Fenton, O., Grant, J., Healy, M.G. 2011. Impact of chemical amendment
of dairy cattle slurry on phosphorus, suspended sediment and metal loss to runoff
from a grassland soil. Science of the Total Environment 403(23): 5111-5118.
A number of international and national conference papers have also been published
describing this work. A list of outputs and manuscripts in preparation for submission to
international journals are listed in Appendix A.
5
Chapter 2
2.1.
Literature review
Overview
This chapter introduces Irish agriculture, details Ireland‘s current water status under the
WFD and comments on the impact which agriculture has on this status. In addition it
details where nutrient losses occur from an agriculture system and investigates several
mitigation options to prevent such losses.
2.2.
Agriculture in Ireland
Agriculture accounts for approximately 56% of land use in the Republic of Ireland (CSO,
2009). Each year approximately 29 million tonnes of slurry are produced in Ireland, of
which 28% is produced by dairy cattle (Hyde and Carton, 2005). Dairy produce and
ingredients amounted to 29% of the value of all agricultural goods, and were estimated at
€5.7 billion at producer prices in 2007 (Common Agricultural Policy, 2011). This is
expected to increase as worldwide demand for dairy products increases (More, 2009).
Dairy cattle slurry may be defined as either ‗the excreta produced by livestock while in a
building or yard, or a mixture of such excreta with rainwater, washings or other
extraneous material, or any combination of these‘ (Statutory Instrument (SI) 610 of
2010). In Ireland intensive dairy farms (intensively managed farms operate with the
objective of maximising output per unit area with high levels of artificial inputs i.e.
concentrated feeds and artificial fertiliser). Cattle are typically housed in slatted sheds for
between 16 and 18 weeks in the winter months, during which time they are fed silage and
concentrates. During this time, the cow manure and urine produced are collected and
stored in storage tanks for the winter period. Slurry is rich in nutrients (particularly N, P
6
and potassium (K)), and is generally land applied in the spring and summer months as a
fertiliser. An average Irish slurry sample contains 5 kg total nitrogen (TN) m-3 and 0.8 kg
total phosphorus (TP) m-3 (SI 610 of 2010). Martínez-Suller et al. (2010) conducted a
study of Irish cattle slurry, the results of which are shown in Table 2.1. Slurry is a
valuable fertiliser (Lalor and Schulte, 2008a) and it is important that any change in slurry
management takes account of the fertiliser value of slurry. Immediately prior to land
application, slurry is agitated to improve workability of slurry, to ensure consistency of
nutrient concentrations in the slurry and to allow uniform application. After agitation,
slurry is land applied using a slurry spreader. Although research has been carried out on
alternative spreading techniques such as trailing shoe application (Lalor and Schulte,
2008b) the majority of slurry is applied using a splash plate slurry spreader (Ryan, 2005).
Table 2.1 Summary statistics from 41 Irish cattle slurry samples (Martínez-Suller et al.,
2010)
Variable
pH
Mean
Median
Maximum
Minimum
sd
CV (%)
7.3
7.3
7.8
6.8
0.2
2.9
-1
EC (S m )
1.43
1.6
2.33
4.1
4.9
34
Dry Matter (g kg-1)
62.7
65.1
97.3
5.7
20.7
33
-3
3.43
3.27
7.03
0.36
1.4
41
-3
P (kg m )
0.56
0.61
1.13
0.04
0.25
44
K (kg m-3)
4.41
4.91
7.75
0.94
2.04
46
N (kg m )
sd = standard deviation; CV = coefficient of variation
In concentrated feeding systems such as intensive dairy farms, P inputs into a farm may
exceed P outputs (Tunney, 1990). This may give rise to a build-up of STP (Sharpley et
al., 2004) as a result of land application of dairy cattle slurry to grassland, which poses a
risk to water quality. In addition, losses during and after land spreading also pose risk to a
waterbody. Therefore, there is a need for the development of management practices,
which allow maximum production with minimum negative environmental impacts i.e.
livestock numbers will not reduce.
7
2.3.
Legislation and compliance
The EU WFD (OJEC, 2000) aims to achieve at least ―good ecological status‖ in all
waterbodies by 2015 through the implementation of POM by 2012. In Ireland the
agricultural POM is the Nitrates Directive (EEC, 1991). The Nitrates Directive has been
implemented since 2009. Huge investment in farm infrastructure has resulted in reduced
P losses from agricultural point sources. Guidelines for farm management provide best
management practice for slurry and inorganic fertiliser application to grassland to
minimize diffuse P losses and increased STP. An Agricultural Catchments Programme
has been established to evaluate catchment-scale evaluation of their effectiveness
(Schulte et al., 2010a).
The statutory instrument which governs agricultural practice in Ireland is The European
Communities (Good Agricultural Practice for Protection of Waters) Regulations 2010 (SI
610 of 2010). This places a responsibility on the individual farmer and the public
authority to adhere to the conditions set out within the Nitrates Directive (EEC, 1991) and
the WFD. Individual farmers are required to maintain records of activities with regard to
soil testing, storage capacity, nutrient management, minimum storage period, and periods
when application to land is prohibited. Land spreading of slurry is forbidden if (1) heavy
rainfall is forecast within the 48 h of application (2) land is frozen or snow-covered (3)
the land slopes steeply towards a river or stream, or (4) slurry is to be applied directly to
bedrock (SI 610 of 2010). In addition to the POM, the WFD recommends research and
development of new pollution mitigation measures to achieve the 2015 target.
2.4.
Current water quality status in Ireland
The Irish Environment Protection Agency (EPA) has reported findings based on analyses
of 2,985 sampling locations on 1,151 rivers between 2007 and 2009 (McGarrigle et al.,
2011). Approximately 68.9% of Ireland‘s rivers were unpolluted, 20.7% were slightly
polluted, 10% were moderately polluted and 0.4% were seriously polluted (McGarrigle et
al., 2011). When these rivers were assessed for ecological status, based on the various
8
biological and physico-chemical quality elements, only 52% of water bodies achieved
‗good status‘. Diffuse losses (including those from agricultural and other sources) were
responsible for approximately half of the polluted sites monitored. Similarly, using the
traditional method of assessment, 92.1% of lakes were in an un-enriched, oligotropic
status - similar to that observed for 2004-2006 period. However, according to the
requirements of the WFD, 47.5% were of ‗good status‘. The report also examined
measurements from 211 groundwater monitoring stations: 84.7% of ground water bodies
were in good status, while 15.3% were in poor status. Figure 2.1 shows the decline in
poor status for groundwater. This reduction was attributed to increased rainfall,
reductions in inorganic fertiliser usage, improved organic fertiliser storage, and
implementation restrictions on timing of land applications. The McGarrigle et al. (2011)
report concluded that substantial measures will be required for Ireland to comply with the
objectives of the WFD.
Figure 2.1 Number of ground water monitoring sites with phosphate concentrations from
1995 to 2009 (McGarrigle et al., 2011)
9
2.5.
Impact of agriculture on water quality
Agricultural activities are thought to be responsible for approximately 38% of slightly
polluted rivers, 23% of moderately polluted, and 29% seriously polluted rivers
(McGarrigle et al., 2011). Figure 2.2 shows the number of reported fish kills attributed to
agriculture from 1971 to 2009 (McGarrigle et al., 2011). The impact of agriculture on
water has reduced steadily since 1997; however, further reductions are required to meet
the requirements of the WFD (McGarrigle et al., 2011). It is important to note that
research constantly challenges the accuracy of the estimated contribution which
agriculture makes to pollution of Irish rivers. This contribution is currently being
examined as part of the Agricultural Catchments Programme.
McGarrigle et al. (2011) found that 0.3% of the waterbodies in the Republic of Ireland
were of ‗poor status‘ due to nitrate (NO3), compared to 13.3% due to P. Therefore, in
Ireland future mitigation measures must focus on P losses with emphasis on diffuse losses
from agriculture.
Figure 2.2 Number of reported fish kills attributed to agriculture, industry, local
authority, other and unknown sources (McGarrigle et al., 2011)
10
2.6.
Nutrients loss and pathways during land application of dairy slurry
Throughout the EU and U.S.A. agricultural management has been identified as a
landscape pressure impacting on water quality (Sharpley et al., 2001a, b; Schulte et al,
2006; Stark and Richards, 2008; Kronvang et al., 2009). Transfers of N and P from
agriculture to water can lead to eutrophication and may occur in three ways: (1) as point
source losses from farmyards because of excessive rates of soiled water application
through the use of rotational irrigators; (2) as diffuse losses from soil, which are related to
soil P and N concentrations in excess of crop requirements; and 3) as incidental losses
from direct losses of fertilizer or manures to water during slurry application, or where a
rainfall event occurs immediately after application (Preedy et al., 2001). Diffuse P losses,
specifically incidental and chronic P losses arising from land application of dairy cattle
slurry to grasslands in Ireland, are thus the focus of this study.
2.7.
Phosphorus
Phosphorus is an essential nutrient for plant growth, and land application of organic and
inorganic P fertiliser is needed to maintain profitable animal and crop production
(Sharpley et al., 2003). In concentrated feeding systems such as intensive dairy farms, P
inputs into a farm can exceed P outputs (Tunney, 1990). This can give rise to high STP
soils which pose a risk to water quality. Phosphorus is also of particular importance in
fresh water systems as it is the limiting nutrient for the occurrence of eutrophication
(Correll, 1998; Sharpley and Tunney, 2000). Transfers of P from agriculture to water can
lead to eutrophication of a waterbody (Carpenter et al., 1998). Land application of dairy
slurry can result in incidental and chronic P losses to a waterbody (Buda et al., 2009).
Incidental P losses take place when a rainfall event occurs shortly after slurry application
and before slurry infiltrates the soil, while chronic P losses is a long-term loss of P from
soil as a result of a build-up in STP caused by application of inorganic fertilisers and
manure (Buda et al., 2009). Table 2.2 shows a summary of the results of laboratory and
plot-scale runoff studies examining the effect of land application of dairy cattle slurry on
DRP and TP concentrations in runoff water from grasslands. These results show the
11
importance of timing of rainfall event following slurry application. In addition this table
identifies a need to examine runoff from slurry at lower more realistic rainfall intensities.
Table 2.2 Results of laboratory and plot-scale runoff studies examining the effect of land
application of dairy cattle slurry on P in runoff water from grasslands
Reference
Type
Size
Intensity
WEP
TP
DRP
TP
Time after
------ slurry ------
----- runoff ------
application
m2
mm h-1
kg ha-1
kg ha-1
mg L-1
mg L-1
Days
1 x 0.2
70
14
50
3.2
6.35
3
1.85
3.2
10
1.5
2
24
43
0.35
130a
122
10.9
3
10.3
48
2
3.1
5
5
3.6
4.1
9
7
7*
Runoff
mm
Kleinman and Sharpley
(2003)
Smith et al. (2001c)
Plot
2 x 15
Natural
Elliott et al. (2005)
Box
1 x 0.2
71
Hanrahan et al. (2009)
Box
1 x 0.2
30
Preedy et al. (2001)
a
Box
Plot
3 x 10
41.6
30
Natural
29
5.4
48
Runoff collected for duration of study
2.7.1. Phosphorus in soil
The soil P cycle is shown in Figure 2.3. Phosphorus exists in organic and inorganic
forms, and may be simplified into three types of P: (1) slow inorganic P (2) rapid cycling
organic and inorganic P and (3) slow organic P. This is a dynamic equilibrium system
and transformations between forms occur continuously (Sharpley, 1995). The availability
of P to plants and water in contact with soil is controlled by chemical processes within
the soil (Sharpley, 1995).
2.7.2. Methods used to determine risk of P loss to water
The slow inorganic pool provides P to replenish the solution P pool, and comprises
inorganic P attached to small particles or elements, such as aluminium (Al) and calcium
(Ca), and organic P that is easily mineralised. The rapid cycling of organic and inorganic
P makes up a small proportion of total P in the soil, and is the most available to plants
and to overland and subsurface flow. It is constantly being depleted and replenished from
12
slow organic and inorganic P pools. Microbial P has an important role in short-term
dynamics of organic P transformations and has a significant effect on P availability.
Inorganic manure applications increase microbial activity in the soil, which leads to
increased P availability. The slow organic pool contains compounds that are insoluble
and organic P, which is less liable to mineralisation.
Slow inorganic
Primary P minerals
(Al, Fe and Ca
minerals)
Secondary P
minerals (Al, Fe
and Ca minerals)
Occluded P
Rapid cycling organic and inorganic
Fertiliser
Slow organic
Animal manure
Plants
Plant residues
Solution P
Microbial P
Labile and moderately labile
inorganic P (amorphous
sesquioxides and some
crystalline Al and Fe)
Chemically and
physically
protected organic P
(humic acid)
Labile and moderately
labile organic P
(phosphollpids inositois,
fulvic acid)
Figure 2.3 The soil P cycle: its components and measurable fractions (Steward and
Sharpley, 1987)
Tests were initially developed to measure availability of P for agronomic purposes, with
loss of P to water from soil not considered a priority. Studies found that P losses from soil
were a major water quality concern (Sharpley and Rekolainen, 1997) and water quality
became the focus of soil P testing. Commercial analysis is focused on testing methods
which measure plant available P. However, researchers have found a relationship
between STP and DRP in surface runoff (Regan et al, 2010; Little et al, 2007). Soil test P
has been shown to be the main factor influencing P concentrations in runoff if no
fertilisers have recently been applied (DeLaune et al., 2004; Dougherty et al., 2008).
Different tests for the determination of STP have been adopted internationally depending
on soil types and tradition (Table 2.3).
Studies have shown that the STP in the upper 20 mm of grassland soils tends to be higher
than for the equivalent depth in tillage soils receiving the same manure (Ahuja et al.,
13
1981). This is due to the absence of deep tilling, which ploughs the nutrients into the soil
(Andraski et al., 2003; Sharpley, 2003). It has also been shown that the use of 100 mm
sampling depth (used to determine the Morgan‘s P of the soil) underestimates P loss risk
from soils and grasslands in particular (Humphreys et al.,1999). Mulqueen et al. (2004)
recommended reducing the sampling depth to improve environmental risk prediction;
however, Schroeder et al. (2004) reported that sample depth (2, 5 and 10 cm) had no
effect on the relationship between soil P concentration and P concentration in runoff.
Daly and Casey (2005) conducted an extensive review of sampling depth and concluded
that the sampling depth of 100 mm was best. This was primarily due to the huge
variability with smaller sampling depths. Torbert et al (2002) reported greater variation
when sampling soil to a depth of 25 mm compared to 100 and 150 mm. It was suggested
that this could be a result of a combination of an increased sensitivity of the testing
procedure to ‗hot spots‘ of manure in the field and difficulty in obtaining a consistent
sample.
Table 2.3 Alternative soil test phosphorus analysis methods used around the world
Method
Bray 1 (Bray and Kurtz, 1945)
Soil
Acidic to slightly alkaline (<6 to 7.2)
Countries
UK and Australia
Mehlich 1 and Mehlich 3 (Mehlich
1984)
Olsen P (Olsen et al., 1954)
Acidic to slightly alkaline (<6 to 7.2)
Europe and U.S.A.
Slightly acidic to alkaline (6.0 to >7.2
UK
Morgan‘s P (Morgan, 1941)
Acidic to slightly alkaline (<6 to 7.2)
Ireland
The WEP test was developed to measure the environmental risk posed by P in any soil.
The WEP test is also used to determine the risk of P loss from manures applied to
grassland. In this test, soil is mixed with water to replicate soil and water interactions and
to estimate dissolved P losses from soil. The general procedure is to weigh accurately a
mass of soil into a known volume of distilled water in an un-reactive container and to
shake for a time between 30 and 60 min. After shaking, the solution is centrifuged and
passed through a 0.45 μm filter. Different dilution ratios commonly used are shown in
Table 2.4.
14
Table 2.4 Dilution rates used to determine WEP of soil
Author
Regan et al. (2010)
Pote et al. (2003)
McDowell and Sharpley (2001)
Dilution ratio
1:80
1:25
1:5
1:100
Type of study
Runoff box
Field
Incubation
Schulte et al. (2010b) showed that it may take many years for elevated STP
concentrations to be reduced to optimum levels to reduce risk to water quality. In Ireland,
a P index system is used to quantify risk of P loss from a soil (Table 2.5). There are 4
categories, with Index 1 representing a P deficient soil and Index 4 (STP > 8 mg P L -1)
representing a grassland soil which presents a risk to water quality (Tunney, 2000). While
the onset of reductions in excessive STP levels may be observed within five years, this
reduction is a slow process and it may take up to 20 years for P index 4 soils to complete
the reduction to the boundary Index 3 (a STP of between 5.1 and 8 mg P L-1) (Schulte et
al., 2010b).
Table 2.5 Phosphorus Index system used for Irish grasslands (Schulte et al, 2010b)
Soil P index
Morgan‘s soil P range for
Interpretation
-1
grassland soils (mg L )
1
0.0-3.0
Soil is P deficient; build-up of soil P required. Insignificant
risk of P loss to water
2
3.1-5.0
Low soil P status: build-up of soil P is required for
productive agriculture. Very low risk of P loss to water
3
5.1-8.0
Target soil P status: only maintenance rates of P required.
Low risk of P loss to water
4
>8.0
Excess soil P status: no agronomic response to P
applications. Risk of P loss to water increases within this
index
The STP levels and the difference between available and total P for Irish soils can mostly
be explained by land use, rock and soil type. Table 2.6 shows the average percentage of
soils in each P index for all soil samples tested in Teagasc, Johnstown Castle between
2004 and 2006 (Mark Plunkett pers com, 2009). Phosphorus losses from agricultural soils
15
are generally a result of an increase in STP caused by long-term applications of P
fertilisers (Frossard et al., 2000).
Table 2.6 Average P index of soils tested in Johnstown castle for the period between
2004 and 2006 (Mark Plunkett, pers com, 2009)
Soil P index
1
STP
mg L-1
0.0-3.0
Grassland
%
15
Tillage
%
15
2
3.1-6.0
25
30
3
6.1-10.0
27
23
4
>10.0
33
In 2008 the Phosphorus Index system was amended (Lalor and Coulter, 2008).
2.8.
32
Nitrogen
Nitrogen is the most abundant gas in the atmosphere and can exist in various compounds.
The process by which N is transformed to its various forms is called the N cycle (Figure
2.4) (Ketterings et al., 2011). The major conversion processes which make up the N cycle
are: N fixation, mineralisation, nitrification, denitrification, ammonia volatilisation, and
immobilisation.
Biological N fixation is a process by which soil bacteria and plant roots interact to
convert nitrogen gas (N2) in the atmosphere to proteins. In industrial production, the
Haber-Bosch process is used to combine N2 and hydrogen gas (H2) with a catalyst under
intense heat and pressure for form NH3, which is then used to make fertiliser. Biological
N fixation requires plant energy so if available N exists, the plant will use this before
biological fixation takes place (Ketterings et al., 2011). Mineralisation is the process that
converts organic N in soil, manure and decaying plants to inorganic forms (ammonium
(NH4) and NH3). Nitrification occurs when microbes use enzymes to convert NH4 to
nitrite (NO2) and then NO3 to obtain energy. Warm, moist and aerated conditions favour
nitrification.
16
Figure 2.4 Schematic of the soil N cycle (Ketterings et al., 2011)
Step 1:
NH4 →
NO2
(2.1)
Step 2:
NO2- → NO3
(2.2)
Denitrification is the process by which N is lost from the soil through the conversion of
NO3 to various gaseous forms of N. Significantly, this reaction can produce N2O, which
is a potent GHG. Therefore, treatments such as chemical amendment of dairy cattle slurry
17
which could potentially change the N cycle, and could impact N2O release. Wet, poorly
drained soil favours the occurrence of denitrification.
NO3 → NO2 → NO → N2O → N2
(2.3)
Ammonia volatilisation is the production and release of NH3 from NH4 on the soil
surface. Ammonia losses are greatest in soils with high pH and in dry, warm and windy
weather (Ketterings et al., 2011). Immediately following land application of dairy cattle
slurry, there is an initial peak in NH3 emissions and it is estimated that 60% of ammonical
nitrogen (NH4-N) applied is lost during land spreading of cattle slurry (Hyde et al., 2003).
There exists a state of equilibrium between the NH3 in the slurry/soil interface and the
NH3 in the air immediately above the soil surface (Génermont and Cellier, 1997). The pH
of the slurry/soil combination has also been observed to affect the rate of NH3
volatilisation. Depending on the pH, NH4-N can occur as NH3 gas or the ammonium ion
(NH4+) (Gay and Knowlton, 2005). The relationship between NH4 and NH3 as a function
of pH is shown in Figure 2.5.
Figure 2.5 Relationship between the ammonia/ammonium (NH3/NH4+) ratio and pH
(Gay and Knowlton, 2005)
18
Immobilisation is the reverse of mineralisation and occurs when microbes temporarily
bind available N in soil biomass (Ketterings et al., 2011). Nitrogen can be lost to surface
ground waters (Stark and Richards, 2008) and to the atmosphere in gaseous form
(Ketterings et al., 2011). On a farm, N losses are spatial in nature and occur from the
entire farm, while P losses can be due to small portion of farm (Poinke et al., 2000) called
Critical Source Areas (CSAs). Therefore, measures to reduce P loss that are applied
through a farm may have a greater effect on N loss than P loss.
2.9.
Loss of soluble and particulate nutrients in runoff
Nutrients can be lost to a surface waterbody in particulate and soluble forms. Suspended
Sediment (SS) loss contributes to particulate phosphorus (PP) in runoff from tillage soils
(Regan et al., 2010); however, in grasslands most P loss is in dissolved form with Total
Dissolved Phosphorus (TDP) and DRP making up 69% and 60% of TP load in surface
runoff (Haygarth et al., 1998). Incidental SS losses following slurry application can result
in high concentrations of SS in runoff, resulting in increased PP losses (Preedy et al.,
2001). This PP can be mineralised and become available to algae (Sharpley, 1993).
Withers et al. (2003) examined the results of a number of studies examining P losses
following land application of dairy cattle slurry at different rates and under different
climatic conditions (Smith et al., 2001c; Withers et al., 2001; Withers and Bailey, 2003)
and found that incidental P losses can account for between 50 and 90% of P losses from
land to water. These variations are due to difference site and climatic conditions.
2.9.1. Soluble nutrient loss
The processes involved in transfer of soluble P from soil or slurry to water are similar.
Phosphorus release occurs as a result of the processes of precipitation-dissolution and
adsorption-desorption (Frossard et al., 2000). Soluble P losses dominate P loss from
grasslands (Sharpley et al., 1992). Kleinman et al. (2006) found that concentration of
water soluble P in manure was strongly related to DRP in runoff from three soils
examined.
19
Nitrate is the form of N most available to plants and to runoff, and makes up to
approximately 2% of soil N at any time (Ryan et al., 2008). This NO3 is constantly
replenished if N is lost, and is very soluble and easily taken up from soil by runoff (Ryan
et al., 2008). Although P is the limiting nutrient in freshwater systems (Correll, 1998), N
losses also pose a significant risk to water quality (Johnes et al., 2007; Vitousek et al.,
2009). It is recommended that slurry should be applied in spring time to maximise N
efficiency (Lalor and Schulte, 2008) and to reduce risk of leaching of N to groundwater,
as less NO3 is lost when plants are growing and fertiliser is applied at rates corresponding
to the requirements of the crop being grown (Power and Schepers, 1989). In a lysimeter
study which examined NO3 losses from five different soil types, Ryan and Fanning
(1996) found that winter applications of pig and dairy cattle slurry resulted in higher NO3
losses than spring applications. This is most likely due to uptake of NO3 by plants during
the spring when plants are growing.
2.9.2. Particulate nutrient loss
Erosion of soil or surface runoff of land applied slurry by water occurs predominantly as
a result of the processes of detachment (caused by the impact of the raindrops on the
soil/slurry surface) or by erosion mechanisms such as entrainment and re-entrainment. As
the processes of soil erosion and runoff of land applied slurry are analogous to one
another, the fundamental mechanisms of surface runoff of land applied slurry will be
discussed in the context of soil erosion.
Detachment of the soil particles from the soil surface is due to the impact of the raindrops
falling under gravity on the ground (Figure 2.6). The cohesive bonds between the soil
particles are brittle, and, once broken, the cohesive strength of the soil is lost. Provided
the infiltration rate is greater than the rainfall rate, the soil particles will return to the soil
surface. If rainwater accumulates on the surface, erosion can occur and the detachment
process will continue. The risk of SS and P loss to surface waters in a rainfall event
decreases dramatically with an increase in time from slurry application to start of the
rainfall event (Smith et al., 2007; Allen and Mallarino, 2008; Hanrahan et al., 2009).
20
Figure 2.6 Detachment of soil particles in a rainfall event (Rose, 2004)
The potential for P loss peaks and then declines over time, as P applied in slurry interacts
with the soil (Edwards and Daniel, 1993). The processes for slurry SS loss are similar to
soil erosion processes. Hanrahan et al. (2009) reported that TP and DRP concentrations
were reduced by 89 and 65%, respectively, by delaying rainfall from 2 to 5 d after dairy
cattle slurry application. In addition, McDowell and Sharpley (2002a) found that flow
path length had a significant effect on P fractions in runoff following land application of
dairy swine slurry. Therefore, when examining the effect of changes in slurry
management, these factors must be taken into consideration.
Rose (2004) considered the difference between the rate of detachment and the rate of
sediment deposition to be responsible for the initial development of sediment runoff in
surface water. As P is adsorbed to sediment (Torbert et al., 2002), the settling velocity of
eroded soil particles is of critical importance. Smaller particles will take much longer to
settle and have the potential to travel greater distances than larger particles in the same
21
conditions (Figure 2.7). The distance which these particles can travel is determined based
on Stokes law (Batchelor, 1967).
Figure 2.7 Rate of sediment deposition in surface runoff (Rose, 2004)
The gradual formation of a surface seal under prolonged rainfall and submergence may
cause reduced infiltration rates into the soil and, consequently, may induce increased
erosion in some soils. This phenomenon occurs when the impact of the falling rain
damages the structure of the soil so that the permeability of the soil surface is reduced or
when rain falls on damaged clay soils with very low permeability. This theory suggests
that the soil particles are held together in bundles or aggregates. The action of the rain
falling can break these bundles apart and, in some cases, may cause the pores on the soil
surface to seal (Rose, 2004).
Detachment is the dominant process responsible for sediment erosion in the early stages
of a rainfall event (Rose et al., 1983). As the runoff event increases in magnitude, the
rainwater can no longer infiltrate the soil surface and overland flow occurs. This
phenomenon is also known as capping or infiltration excess (Horton, 1933). Entrainment
is the process which involves the surface runoff eroding the soil particles (Figure 2.8).
The erosion processes for slurry are similar to soil.
22
Figure 2.8 Entrainment and re-entrainment of sediment (Rose, 2004).
The ability of flowing water to erode sediment is related to the stream power, Ω, which is
a function of shear stress and the velocity of the surface runoff (Rose, 2004). Once Ω
exceeds a threshold value, Ωo, sediment is eroded. Detachment processes are less
significant in deep surface flow. However, rain falling on shallow water will increase
turbulence and liberate particles. Particles which are put into suspension after entrainment
are then deposited according to their settling velocity. Over time, these particles
accumulate and begin to rebuild the eroded soil surface. These particles have insufficient
time to gain cohesive strength and are more easily eroded than the original deposited
sediment. This erosion process is known as re-entrainment. Re-entrainment moves the
particles in the general direction of flow by saltation (Figure 2.8). The processes by slurry
particles are moved in surface water are similar.
23
2.10. Gaseous emissions and the importance of considering pollution swapping
when selecting a P mitigation measure
Agricultural activities contribute to the production of NH3 and GHG such as CO2, N2O
and CH4. In particular, land application of dairy slurry can result in the release of NH3
(Amon et al., 2006), N2O (Ellis et al., 1998), and CH4 (Chadwick and Pain, 1997). It is
critical that the potential for pollution swapping is examined when evaluating a potential
technology. In particular, the effects of any proposed treatments on GHG emissions must
be examined. Under the 1997 Kyoto Protocol of the United Nations Framework
Convention on Climate Change (UN, 1998), participating nations agreed to publish
national inventories of anthropogenic emissions of several GHG and to reduce future
emissions below 1990 levels. In Ireland, agricultural activities were responsible for
approximately 26% of total GHG emissions in 2008 (McGettigan et al., 2010) and
account for virtually all NH3 emissions, with animal manure alone responsible for 92% of
NH3 emissions (EPA, 2010). While NH3 is not a GHG, it contributes to acidification of
soils, atmospheric pollution, and the eutrophication of surface and ground water systems
(Goulding et al., 1998). An estimated 5% of global N2O emissions results from the
conversion of NH3 into N2O in the atmosphere (Ferm, 1998).
2.11. Present and emerging P mitigation measures
The general consensus held by researchers in Ireland is that Ireland will not meet its
water quality targets by 2015 (Schulte et al., 2010b; McGarrigle et al., 2011). This failure
to achieve the required improvements in water quality status is a common problem being
faced throughout Europe and in the US. It is largely accepted that supplementary
measures, in particular the development of P mitigating technologies, will be critical to
develop short-term farm management practices which will reduce nutrient losses to
waterbodies (Buda et al., 2010). These mitigation methods, together with best
management practices which are already in place, will enable the achievement of water
quality requirements in shorter time period. This will allow for the development of longterm, sustainable management practices to minimise risk of P loss to water.
24
In Ireland, attempts to reduce diffuse P loss from agriculture have focused on increasing
nutrient efficiency and improving slurry management strategies. To address the time lag
between implementation of these strategies and reduction of STP to the boundary index 3
in high P-index farms (Table 2.6), short-term P mitigation technologies are required.
Current guidelines state that farmers may only apply dairy cattle slurry to high STP soil
in the absence of low STP soil. On such farms, treatment of dairy cattle may be
considered for use in tandem with existing management practice to reduce the solubility
of P during this ‗time lag‘ period. Mitigation methods to reduce incidental P losses
include incorporating slurry into soil immediately after land application (Tabbara, 2003),
increasing length of buffer zones between slurry application areas and drains and streams
(Mayer et al, 2006), enhanced buffers strips (Uusi-Kämppä et al., 2010), timing of slurry
application (Hanrahan et al., 2009), chemical amendment (Dao and Daniel, 2002; Dou et
al., 2003) and diet manipulation (O‘Rourke et al., 2010). The risk of P loss from slurry is
strongly related to the WEP in the slurry (Dou et al., 2003) and amendments which
reduce P solubility should reduce P loss to runoff. In this section, current management
practices, along with new technologies, to treat dairy cattle slurry and to mitigate P losses
from land application of dairy cattle slurry are discussed.
2.11.1. Constructed wetlands
To date, free-water surface (FWS) Constructed Wetlands (CWs) (reed beds) are the most
widely used, low-cost and low-maintenance alternative to land spreading of dairy
wastewaters in Ireland. Constructed wetlands provide an environment for the
physical/physico-chemical retention and biological reduction of organic matter (OM) and
nutrients (Knight et al., 2000). Depending on the organic loading and retention time
(Karpiscak et al., 1999), constructed wetlands can have a significant nutrient removal
capacity. However, due to the effect of varying temperatures, the treatment efficiency of
these systems tends to vary throughout the year (Healy and Cawley, 2002).
Constructed wetlands may be planted with plants found in natural wetlands and lined
with soil to trap nutrients and solids from wastewaters. They may be used to treat runoff
25
from intensively farmed soils in close proximity to sensitive water bodies (Tanner et al.,
2005), or alternatively, to treat wastewaters before water is land applied to reduce
potential for pollution (Healy et al., 2007). There is a long history of use of CWs to treat
municipal wastewaters and they have more recently been adopted to treat dairy waste
water and screened dairy slurry (the liquid portion of dairy cattle slurry following
separation) (Healy et al., 2007).
Guidelines for the design loading of surface-flow wetlands (Healy et al., 2007)
recommend an area loading rate of approximately 5 g of 5-day biological oxygen demand
(BOD5) m-2d-1. Although CWs have been shown to be very effective achieving good
reductions in municipal and dilute dairy waste waters (soiled dairy water etc), the high
solids content and the high nutrient concentrations of agricultural slurries make them
difficult to treat. New Zealand guidelines for the disposal of farm dairy wastewaters
(Tanner and Kloosterman, 1997) recommended that an FWS CWs should only succeed
two waste stabilization ponds (an anaerobic and an aerobic pond, respectively) before
entering the wetland with an organic loading rate not exceeding 3 g BOD5 m-2 d-1. The
anaerobic pond reduces the BOD5 and SS, and the aerobic pond carries out further
biological reductions. Mantovi et al. (2003) suggests that the milking parlour should be
designed to allow parlour washings and washings from the holding room to be separated,
so as the wetland only treats the effluent of lower organic and nutrient content.
The removal of NH4-N from strong waste waters is generally inadequate in most CWs
(Sun et al., 2005; Toet et al., 2005). Inorganic nitrogen removal is also often
unsatisfactory (Luederitz et al., 2001) and in Europe, average percentage removal of
NH4-N during long-term operation is approximately 35%, with a maximum of 50%
(Verhoeven and Meuleman, 1999).
The ability of CWs to retain P is dependent on the P loading rate, the media type,
vegetation, and duration of operation (Healy et al., 2007), although changes in pH and
redox potential could also release P from the system. Healy et al. (2007) reported that
between 65 and 95% of P may be removed at loading rates of less than 5 g TP m-2 yr-1.
26
Phosphorus is removed through short-term or long-term storage, with most removal often
occurring near the inlet initially, before extending throughout the wetland over time as
those sites become P-saturated (Jamieson et al., 2002). Uptake by bacteria, algae and
duckweed (Lemma spp.), and macrophytes provides an initial removal mechanism.
However, this is only a short-term P storage as 35 to 75% of P stored is eventually
released back into the water upon dieback of algae and microbes, as well as plant
residues. The only long-term P storage in the wetland is via peat accumulation and
substrate fixation, the efficiency of which is a function of the loading rate and the amount
of native iron (Fe), Ca, Al, and OM in the substrate. Henry et al. (2003) reported
reductions of total dissolved solids (TDS), NH4-N, TN, and TP were 58%, 83%, 90%,
and 84%, respectively, in the first 3 years of operation. These were above the national
averages for CWs. However, these results indicate that CWs can be effective when
properly managed. Although there is much evidence to support use of CWs, the P
mitigating processes and long-term viability of CWs for P control are not sufficiently
understood to pursue CWs as a potential management decision to control short-term P
surplus. The also perform poorly when it is raining and are susceptible to incidental P
loss during storm events.
2.11.2. Anaerobic digestion
Digestion of organic wastes results in the production of slurry with lower pollution
potential and which is more suitable for use as a fertiliser while producing renewable
energy (Singh et al., 2010a). Anaerobic digestion (AD) is now seen as the best manure
management practice, as it offers the opportunity to reduce gaseous emissions from
manure, increase N availability, produce biogas and reduce GHG emissions (HolmNielsen et al., 2009; Masse et al, 2011). Although AD reduces WEP of slurry without
reducing plant availability of P (Moller and Stinner, 2009), the main benefit of AD in
terms of P mitigation is that the digested slurry can be separated and the solid fraction
exported off-farm for use as a soil conditioner, or further processed into a granular
organic fertiliser, or a combustible fuel which has a commercial value. Anaerobic
digestion reduces gaseous losses from slurry (Amon et al., 2006; Clemens et al., 2006)
27
and increases N availability in slurry (Moller et al., 2008). Amon et al. (2006) reported
that AD reduced N2O losses from dairy cattle slurry by approximately 28% compared to
a slurry-control. Anon et al. (2006) also reported that CH4 losses following land
application of digested dairy cattle are lower and there are no adverse effects on NH3
emissions compared to untreated dairy cattle slurry (Amon et al., 2006; Clemens et al.,
2006). In addition, AD can lower the odour from farm slurries by up to 80% (Pain et al.,
1990), lower survival of pathogens in the slurry (Masse et al, 2010; Cote et al., 2006), and
kill many weed seeds, reducing need for herbicides (Frost and Gilkinson, 2010). There
are extensive AD plants in mainland Europe; however, there are only pilot-scale plants in
Ireland (Anon, 2011). Although AD is not currently considered a P management option,
Gungor and Karthikeyan (2008) reported that AD decreases water soluble P faction by
between 22 and 47% compared to undigested slurry.
Although the advantages of AD are immense, there are some difficulties which have
restricted their adoption in Ireland. The main barriers to their use are the high capital cost
necessary to establish them, the low dry matter (DM) content of slurry on many dairy
farms, the energy requirement to maintain temperatures sufficient for the digester to
operate, and a long hydraulic retention time. This means that a large AD reactor is
necessary for high volumes of slurry (Frost and Gilkinson, 2010). Moller et al. (2007)
examined the feasibility of separating slurry prior to AD and recommended that preseparation may increase yield, but the feasibility depends on the cost of separation and
transportation of slurry from farm to AD plant. Although AD is the most environmentally
sustainable means of treating slurry in the long-term, it is unlikely that AD can be
implemented specifically to mitigate P losses in sufficient time to meet requirements of
the WFD. Many German farmers make a living producing biogas from such operations;
however, their government provides financial supports for such enterprise (Anon, 2011).
In the long-term, with improvements in technology and with the support of government
initiatives, AD may become a management practice in Ireland.
28
2.11.3. Biochar
Biochar is produced when biomass is burnt in the absence of oxygen at temperatures
<700°C (Lehmann and Joseph, 2009). There is growing acceptance that biochar may play
a part in reducing GHG emissions from agriculture (Winsley, 2007). There are two
biochar P mitigation management systems currently being examined for the treatment of
dairy cattle slurry: (1) slurry can undergo pyrolysis and be converted to a biochar, which
can be applied to soils as a soil conditioner and fertiliser and to reduce losses of metals
from soils (Cao and Harris, 2010) and (2) biochar produced from another biomass source
can be used to sequester P and then land applied in another location (Streubel et al.,
2010).
These technologies have the potential for use as part of sustainable manure management
to allow transport of biochar produced from slurry, or biochar enriched with nutrients, to
soils with low STP. Biochar has a much lower volume than slurry used to produce it and
would be much more attractive as a fertiliser and soil conditioner to a wide range of uses
not limited to agriculture. Land application of biochar can restore fertility in degraded
soils (Novak et al., 2010), improve health of the soil (O‘Neill et al., 2009; Van Zwieten et
al., 2010), reduce nutrient leaching (Singh et al., 2010b), reduce GHG losses (Gaunt and
Lehmann, 2008; Rogovska et al., 2011) and improve fertiliser efficiency in some soils
(Van Zwieten et al., 2010).
Streubel et al. (2010) investigated the potential for using biochar produced from pyrolysis
of AD sludge to sequester P from dairy lagoons and found that 50% reduction of soluble
P in dairy slurry lagoon was achieved while the plant available P in the biochar increased
from 4 to 45 mg kg-1 Olsen P. This system allows the nutrients to be trapped and
transported to areas with low P soil where they can be used a soil conditioner and
fertiliser. Although there is excellent potential for GHG emission reduction (Gaunt and
Lehmann, 2008) and potential to reduce P loss from agriculture by transporting saleable
product from areas with P surplus, this technology is not developed sufficiently for
widespread implementation. There are high capital costs and these systems would need to
29
be validated at farm-scale before being recommended for use in Ireland. The low DM of
dairy cattle slurry results in a very high cost of drying slurry and this is one of the main
barriers to the production of biochar from slurry (Xinmin Zhan pers com, 2011). Systems
using biochar to sorb P from slurry lagoons are not as likely to be attractive to farmers in
Europe as in the U.S.A., as slurry lagoons are not as common in Europe. In addition, the
risk of pollution swapping associated with slurry lagoons is a problem. The main barrier
to use of biochar technology is that there is no legislation in place regarding of biochar
for use by agriculture and before biochar can be used as an amendment for soils,
standards need to be established (Kwapinski et al., 2010).
2.11.4. Buffer strips and enhanced buffer strips
Buffer strips have been implemented to reduce P losses from waters entering waterways
(Hoffmann et al., 2009). Buffer-strips are particularly effective at reducing PP and current
best farming practice stipulates a 2.5 m buffer-strip between edges of slurry application
and a stream or drain. This is a natural buffer-strip which acts to reduce risk of P loss to
surface waters. Studies have reported conflicting results (Table 2.7). The consensus is
that buffer-strips are not very effective at trapping DRP (Watts and Torbert, 2009) and
are generally more effective in reducing PP losses (Hoffmann et al., 2009). They are a
cost effective TP and PP mitigation method and offer an attractive means of treating
runoff from high STP soils. However, they are not always effective in storm events.
Many researchers have examined the potential to enhance DRP sorbing potential of
buffer strips using amendments (Dayton and Basta, 2005; Uusi-Kämppä et al., 2010).
Uusi-Kämppä et al. (2010) examined the potential for use of amendments in buffer strips
to increase P retention and found that, while gypsum and CaCO3 did not change DRP and
TP loss to runoff during simulated runoff events, Fe-gypsum and granulated ferric
sulphate increased DRP and TP retention between 74-85 and 47 to 64%, respectively.
Dayton and Basta (2005) enhanced a buffer strip down-slope of soil receiving poultry
litter using WTRs (20 Mg ha-1 WTR). This resulted in a reduction in DRP in runoff by
between 67 and 86% compared to the buffer strip without any WTR incorporated. Watts
30
and Torbert (2009) applied gypsum at 0, 1, 3.2 and 5.6 Mg ha-1 to a 1.52 m-wide bufferstrip down-slope of a soil receiving poultry litter. The unamended buffer-strip reduced
DRP loss by 18%. This increased to 32-40% for all gypsum amended buffer-strips with
the rate of gypsum applied having no significant effect.
Table 2.7 Performance of buffer strips in reducing total and soluble phosphorus in runoff
(adapted from Kay et al., 2009)
Pollutant
Reduction
Reference
Total phosphorus
6% reduction
McKergow et al. (2003)
10 to 98% reduction
Heathwaite et al. (1998)
0 to 97% reduction
Uusi-Kämppäetal. (2000)
31% reduction
Abu-Zreig. (2001)
8 to 97% reduction
Dorioz et al. (2006)
27% decrease to 41% increase
Borin et al. (2005)
16% reduction
Vaananen et al. (2006)
61% increase
McKergow et al. (2003)
17% decrease–475% increase
Borin et al. (2005)
0 to 30% decrease
Dorioz et al. (2006)
Soluble phosphorus
Although these systems mainly use waste products (such as WTR, FGD, etc), they would
be unfeasible on a large-scale due to availability of the waste products and cost of
installing systems on a large-scale. Therefore, these P mitigation technologies are
recommended for use in CSA; areas where pollution due to runoff or leaching is likely to
occur) only.
2.11.5. Composting
Aerobic composting of organic waste is a very effective method of stabilising and
sterilising waste materials. Composting manure reduces water content and reduces
pathogen survival, kills weed seeds, and is easier to land apply (Eghball and Gilley,
1999). Slurry must be separated before it can be composted and this is the major barrier
to their widespread use. Miller et al. (2006) reported that land application of composted
cattle manure, rather than fresh cattle manure, may be a potential management tool to
31
control P and N in surface water. Although composting does not sequester P, it converts
the manure from a high water content, low nutrient concentration odorous material to a
low water content, soil-like material, which is rich in nutrients and can be transported
long distances and be used by farmers, or sold to other industries and households as a
fertiliser. While composting manure reduces GHG emissions effectively (Pattey et al.,
2005), it can cause increases in NH3 emissions (Parkinson et al., 2004).
2.11.6. In-stream and edge of field filters
The alternative to reducing P lost to runoff is to recover P from drainage waters. Instream and edge-of-field filters have been examined by many researchers throughout the
world (Shipitalo et al., 2010a; McDowell et al., 2008; Bryant et al, 2010; Uusi-Kämppä et
al., 2010). Remediation techniques which treat water in-stream include filter socks
(Shipitalo et al., 2010a), backfilling tile-drains with P sorbing material (McDowell et al.,
2008); various reactive barriers placed along field drains and drainage ways (Bryant et
al., 2010; Uusi-Kämppä et al., 2010), reactive materials placed in sub-surface drains
(Penn and McGrath, 2011) and ferric sulphate dispensing units (Narvanen et al., 2008).
Shipitalo et al. (2010a) found that compost-filled socks (Figure 2.9) were ineffective in
reducing P loss from a grassland catchment. In a subsequent study, Shipitalo et al.
(2010b) amended the compost with a nutrient sorbent to improve nutrient retention. This
resulted in a 27% reduction in DRP in drain water after passing through the filter sock.
32
Figure 2.9 Compost filled socks in instrumented drainage channel (Shipitalo et al.,
2010a)
Compost socks are not the most effective P sorbing systems. The initial aim of compost
filter socks was to prevent SS loss and as the focus has shifted to P loss, researchers have
examined more effective P sorbing materials. McDowell et al. (2008) examined the
potential for use of industrial by-products to reduce P loss from tiled drained land. In this
study, backfilling tile drains with a mixture of 90% melter slag and 10% basic slag
33
reduced DRP and TP from 0.33 mg DRP L-1 and 1.20 mg TP L-1 for control to 0.09 mg
DRP L-1 and 0.36 mg TP L-1.
Bryant et al. (2010) used a permeable FGD gypsum barrier to intersect ditch water and to
precipitate soluble P as calcium phosphate. Between 35 to 90 % of the P from ditch flow
that passed through the filter was removed. However, during large flow events, the water
flowed over the barrier and this was identified as the main problem associated with such
P mitigation systems. Figure 2.10 shows the general layout of such edge of field filters.
Figure 2.10 Permeable edge of field barriers (O‘Connor et al., 2010)
The ideal situation would be to use materials which can be replenished. Penn and
McGrath (2011) examined the ability of steel slag and a surface-modified slag to sorb P
in golf course runoff in a flow-through system, and found that both treatments reduced
DRP by approximately 31% with the need to replenish slag when it becomes saturated
with P. Narvanen et al. (2008) designed a ferric-sulphate doser to treat runoff from a CSA
(Figure 2.11). Immediately following chemical treatment, water was passed through a
settling pond and then filtered in a sand bed. This system resulted in reductions in DRP
and TP in runoff from CSA of 95 and 81%.
34
Figure 2.11 Schematic and photo of ferric-sulphate doser in operation in Jokioinen,
Finland (Narvanen et al., 2008)
2.11.7. Sand and woodchip filter systems
Researchers have examined the use of sand (Healy et al. 2004) and woodchip filters
(Ruane et al., 2011) to treat dairy soiled water. Recently, Carney et al (2011) have
examined the effectiveness of wood chip filters in treating the liquid portion of pig slurry
following separation (Figure 2.12). There is potential that such systems could be used to
treat the liquid portion of dairy cattle slurry following separation. While sand and
woodchip filters have been shown to significantly reduce BOD5 and N losses (Healy et
al., 2004; Ruane et al., 2011; Carney et al., 2011), they do not reduce P concentrations
sufficiently to allow release of wastewaters to waterways.
The performance of filters depends on composition of influent and any filter system
would require maintenance and constant monitoring to ensure that system was
performing properly. While further steps could be included at subsequent stages of
treatment to remove P, these systems would require further capital investment.
2.11.8. Slurry separation
The objective of slurry separation is to split the slurry into a liquid with low solids
content and a solid with high DM. There are three main types of separator: brushed
screen separator, decanting separator and screw-press separator. Gilkinson and Frost
35
(2007) carried out a comprehensive study of the brushed screen separator and decanting
separator, and found that there was a strong correlation between DM and TP in slurry.
Their report conduced that mechanical separation may be an option for farmers with a P
and N surplus on farm. Slurry separation requires a significant initial investment and this
is likely to be the biggest barrier to implementation. Slurry separation is the first step in
treatment as the solid portion of the slurry must be further treated and liquid land applied.
Figure 2.12 Pilot scale wood chip filter used to treat the liquid portion of pig slurry
following separation (Carney et al., 2011)
There has been extensive research into separation of slurry in the US. Currently,
approximately 1-2% of dairy farmers in the US use polymers with a flocculent such
AlCl3 to help with solids separation (Philip Moore pers com, 2010). Such systems are
very effective in reducing TP and soluble P in the liquid portion of separated slurry
(Powers et al., 1995; Barrow et al., 1997; Krumpelman et al., 2005). This liquid portion
can be land applied on farm to meet N requirements and the solid portion, which is high
in P, can be transported off-farm. A summary of reductions of WEP and TP in slurry
shown in Table 2.8.
36
Table 2.8 Review of laboratory-scale studies examining chemical aided separation to
reduce P in liquid fraction of separated dairy cattle slurry
Reference
Chemical added
TP
%
Powers et al. (1995)
[0.75g CaCO3 + 0.5 ml Fe2(SO4)3] L-1
[0.75g CaO + 0.5 ml Fe2(SO4)3] L
Krumpelman et al. (2005)
93
-1
62
-1
74
54
-1
77
67
-1
88
89
-1
92
93
804 mg Fe L + 150 ml 225G-PAM
384 mg Al L + 100 ml 225G-PAM
Barrow el al. (1997)
54
-1
[0.5 ml Fe2(SO4)3 + 5 drops polymer] L
SS
%
278 mg Fe L as FeCl3
358 mg Ca L as CaO
2.11.9. Use of P sorbing amendments
Fenton et al. (2008) recommended the addition of amendments to dairy cattle slurry prior
to land spreading as a management practice to reduce P losses arising from land
application of dairy cattle slurry Ireland. In the U.S.A., chemical amendment of poultry
litter has been proven to be effective in reducing P losses from poultry litter and has been
used as best management practice for over 30 years (Moore and Edwards, 2005). There
has been limited work involving chemical amendment of dairy manure (Dao, 1999; Dou
et al., 2003; Kalbasi and Karthikeyan, 2004), however, much more work is needed before
chemical amendment can be recommended for implementation as a management practice
in Ireland. Phosphorus sorbing amendments can be incorporated into soil to reduce
soluble P in soils with high STP (Anderson et al, 1995; Novak and Watts, 2005); or, for
incidental losses, added directly to the manure before land application to control P in
manure being applied (Moore et al., 1999), or applied after manure application to reduce
P losses from applied manure (Torbert et al, 2005).
2.11.9.1.
Amendments applied directly to soil
Addition of chemical amendments to soils has been shown to reduce P solubility in high
P soils and thus the potential to reduce the risk of P loss to waterbodies in surface runoff.
Anderson et al. (1995) amended soils with a history of receiving dairy manure in an
37
incubation experiment with calcium carbonate (with the slurry pH adjusted to 7.5),
gypsum (0 to 100 g kg-1 soil), ferrous sulphate (0 to 1 g kg-1 as Fe) and alum (0 to 1 g kg-1
as Al). Calcium carbonate effectiveness was limited to soils with pH < 7.0 and gypsum
was effective over a broad range of manure loading, pH and redox conditions. Although
Al and Fe amendments to soil increased P retention by 400% relative to an unamended
control, the authors acknowledged elevated costs associated with amendments and
potential biological toxicity. In a laboratory incubation study, Novak and Watts (2005)
incorporated an alum-based WTR into three soils with a Mehlich-3 P (M3) of between
145 mg kg-1 and 371 mg kg-1, and found that the amendment reduced WEP in the soil by
between 45% and 91% after an 84-d incubation period. They also found that WTR was
efficient at reducing M3 of soils with a M3 of between 145 and 235 mg kg-1, but not soil
with a M3 of 371 mg kg-1 soil. Stout et al. (1998) amended soil with flyash at 0.01 kg kg-1
soil in a laboratory incubation experiment, and found that M3 and WEP were lowered by
13% and 71%, respectively. Flue gas desulphurisation by-product, applied at 0.01 kg kg-1
soil, lowered M3 by 8% and WEP by 48%. Table 2.9 shows chemical amendments
studies with manure type, study type and percentage reductions in WEP of slurry and
slurry amended soil.
2.11.9.2.
Amendments to slurry
The present study examines for the first time the effect of chemical amendment of dairy
cattle slurry on P, N and metal (namely Al, Fe and Ca) losses to runoff, whereas most
previous studies only examined the effect of amendments on P solubility (Dao, 1999;
Dao and Daniel, 2002; Dou et al., 2003). Dou et al. (2003) found that technical grade
alum, added at 0.1 kg kg-1 (kg alum per kg slurry) and 0.25 kg kg-1, reduced WEP in
swine and dairy slurry by 80% and 99%, respectively. Dao (1999) amended farm yard
manure with caliche, alum and flyash in an incubation experiment, and reported WEP
reductions in amended manure compared to the control of 21, 60 and 85%, respectively.
Kalbasi and Karthikeyan (2004) applied untreated and amended dairy slurry to a soil and
incubated it for 2 years; alum and FeCl2 were observed to decrease P solubility, while
lime amendments increased WEP.
38
Table 2.9 Results of laboratory and plot-scale chemical amendments studies to date
Reference
Chemical
Rate
Manure type
Study type
% soluble P reduction in:
Runoff
Dao (1999)
Alum
Caliche
Flyash
Dao and Daniel (2002)
Cattle stockpiled
0.1 kg kg-1
Cattle composted
0.1 kg kg-1
Cattle stockpiled
0.1 kg kg
-1
Cattle composted
0.1 kg kg
-1
Cattle stockpiled
0.1 kg kg
-1
Cattle composted
21
50
Laboratory
85
93
Dairy slurry
Laboratory
FeCl3
0.01 kg kg
-1
Dairy slurry
Laboratory
0.01 kg kg
-1
Dairy slurry
Laboratory
44
Dairy
Laboratory
99
-1
66
0.1 kg kg
Flyash
400 g kg-1
Dairy
50-60
-1
Dairy
50-60
Lefcourt and Meisinger
(2001)
Alum
0.4% (w/w)
McFarland el al. (2003)
Alum
Dairy slurry
Laboratory
0.78 kg m-2
Dairy effluent
Plot
-2
97
Gypsum
0.78 kg m
Dairy effluent
Plot
Meisinger et al. (2001)
Alum
6.25% (w/w)
Dairy slurry
Laboratory
Novak and Watts (2005)
Al-WTR
1-6% (v/v)
None
Incubation
Smith et al. (2001a)
Alum
215 mg Al L-1
Swine
Plot
Flyash
90
52
45-91
33
430 mg Al L-1
84
215 mg Al L
-1
45
430 mg Al L
-1
0.01 kg kg-1
84
None
Laboratory
71
FGD
Zhang et al. (2004)
Flyash
82
75
2.5% (w/w)
AlCl3
63
18
Alum
400 g kg
WEPsoil+waste
60
83
Laboratory
0.01 kg kg-1
FGD
Stout et al. (1998)
WEPwaste
Laboratory
Alum
Flyash
Dou et al. (2003)
0.1 kg kg-1
48
0.4 kg kg
-1
-1
Dairy manure
Laboratory
Laboratory
50-60
Fenton et al. (2009)
Ochre
50 g L
Dairy effluent
Torbert et al (2005)
Lime
3:1 metal to P
Dairy slurry
99
Gypsum
3:1 metal to P
0
FeSO4
3:1 metal to P
66
0
A limited number of runoff studies have been carried out with chemical amendment of
dairy cattle slurry (Elliot et al, 2005; Torbert et al, 2005) and swine slurry (Smith et al,
2001a). Torbert et al. (2005) amended landspread composted dairy manure with lime (3:1
metal-to-TP ratio) immediately prior to a 40-min rainfall event (overland flow equivalent
to a rainfall intensity of 12.4 cm h-1). Lime amendments increased DRP loss. In a plot
study, Smith et al. (2001a) amended swine manure with alum and AlCl3 at two
stoichiometric ratios (0.5:1 and 1:1 Al: TP). Dissolved reactive phosphorus reductions for
39
alum and AlCl3 at the lower ratio were 33% and 45%, respectively, with 84% for both
amendments at the higher ratio.
Chemical amendments of slurry using Al, Fe, or Ca based compounds reduce P solubility
in manure (Dao, 1999; Dou et al., 2003; Kalbasi and Karthikeyan, 2004) and reduce P in
runoff from plots receiving alum amended poultry litter (Moore and Edwards, 2005) with
negligible effect on metal loss (McFarland et al., 2003). Chemical amendments reduce
incidental P losses by a combination of the formation of stable metal-phosphorus
precipitates (such as Al-P phosphates in the case of alum) and flocculation of the particles
in the slurry to form larger particles, which are less prone to erosion (Tchobanoglous et
al., 2003). Previous studies have found that there was no risk of increased metal release
posed by chemical amendment of poultry litter (Moore et al., 1998), dirty water
(McFarland et al., 2003), or horse manure (Edwards et al., 1999).
2.12. Recommendations and knowledge gaps
In Ireland, point source pollution caused by agriculture has been overcome by
infrastructural investment on farms and by the removal of point sources in catchments.
Attempts to reduce diffuse P loss from agriculture have focused on increasing nutrient
efficiency and improving slurry management strategies. In order to meet our water
quality obligations, it is becoming apparent that (1) the efficacy of the Nitrates Directive
(Ireland‘s agricultural POM) will need time to be assessed and (2) further investigation of
mitigation measures (supplementary measures within the WFD), such as those outlined
within the EU COST 869 project (coming to a conclusion in October 2011), will be
necessary.
This review has identified a need for a short-term, cost effective management practice,
which can be implemented to reduce the solubility of P in slurry and reduce the risk of
incidental and chronic P losses. It is critical that the P mitigation measure selected can
mitigate both of these losses. In the long-term, it is likely that a wide range of these
technologies will be harnessed in parallel with land application of slurry.
40
In the short-term, however any P mitigation measure must have the ability to be quickly
implemented within the existing farm slurry management structure, be cost effective and
capable of being used in strategic locations for maximum effect. Chemical amendment of
dairy cattle slurry was chosen for further investigation in the present study. Specifically,
there have been limited studies involving chemical amendment of dairy cattle slurry and
such studies have not considered the feasibility of using amendments at farm-scale, or the
changes to the hydrology of a system through their use, pollution swapping and the longterm effects on STP. This is the first study to examine a range of potential chemical
amendments for mitigation of P losses from dairy cattle slurry in Ireland.
The following knowledge gaps were identified in the present review:
1. There have been no studies conducted to evaluate the effectiveness and feasibility
of potential chemical amendments in Ireland. There is a need for such a study if
amendments are to be considered for implementation in Ireland.
2. There is a need for a study to examine the effect of chemical amendment of dairy
cattle slurry on metal loss to runoff.
3. The effect of chemical amendment of dairy cattle slurry on pollution swapping, in
particular N loss to runoff and GHG emissions, needs to be examined
4. The effect of chemical amendment of dairy cattle slurry prior to application to soil
on long-term soil WEP and STP.
5. To examine the effect of soil type on the solubility of P in soil following
application of amended slurry to soil.
6. To investigate the role chemical amendments may have in mitigation of P losses
from dairy cattle slurry in Ireland.
7. To examine conditions in which they work and discuss limitations in use.
41
Chapter 3
3.1.
Evaluation of chemical amendments to control
phosphorus losses from dairy slurry
Overview
Land application of dairy slurry can result in incidental losses of P to runoff in addition to
increased loss of P from soil as a result of a build up in STP. A novel agitator test was
used to identify the most effective amendments to reduce DRP loss from the soil surface
after land application of chemically amended dairy cattle slurry.
3.2.
Introduction
Batch experiments, although allowing quick determination of adsorption capacities of
amendments, are unrealistic when considering nutrient losses in runoff following manure
application. These small-scale tests do not account for the interaction between applied
slurry and soil, and the effect of infiltration and skin formation on the release of P to
surface runoff. An ‗agitator test‘, wherein an intact soil core, placed in a beaker, is
overlain with continuously-stirred water (Mulqueen et al., 2004), enables achievement of
batch experiment results, but also simulates the situation in which slurry is applied to soil,
allowed to dry, and then subjected to overland flow (Figure 3.1). The test provides
standardised conditions for assessment of the effectiveness of various amendments to
slurry at reducing the release of P that may relate to land-applied slurry.
The objectives of this study were to: (1) use a laboratory agitator test to identify the most
effective chemical amendments to reduce P loss from the soil surface after land
application of amended dairy cattle slurry (2) identify optimum amendment application
42
rates for a similar P reduction in different amendments (3) estimate the cost of each
treatment, and (4) discuss the feasibility of using treatments in a real on-farm scenario.
Figure 3.1 Beakers placed in flocculator during agitator test
3.3.
Materials and methods
3.3.1. Soil preparation and analysis
Soil samples were collected from a dry stock farm (53°21‘ N, 8°34‘ W) in Galway,
Republic of Ireland. 120-mm-high, 100-mm-diameter Al coring rings were used to collect
undisturbed soil core samples.
Soil samples (n=3) – taken from upper 100 mm from the same location - were air dried at
40 °C for 72 h, crushed to pass a 2 mm sieve and analysed for P using M3 extracting
solution (Mehlich, 1984) and Morgan‘s P using Morgan‘s extracting solution (Morgan
43
1941). Soil pH (n=3) was determined using a pH probe and a 2:1 ratio of deionised
water-to-soil. Shoemacher-McLean-Pratt (SMP) buffer pH was determined and the lime
requirement (LR) of the soil was calculated after Pratt and Blair (1963). The particle size
distribution (PSD) was determined using a sieving and pipette method (B.S.1377-2; BSI,
1990a) and the organic content of the soil was determined using the loss of ignition test
(B.S.1377-3; BSI, 1990b).The soil used was a poorly-drained, silty loam topsoil, with
15% sand, 72% silt, 13% clay, and an OM content of 16.2±0.2%. The soil texture was
classified using the US Department of Agriculture (USDA) soil texture triangle (Figure
3.2). The soil had a M3 concentration of 50±2.8 mg P kg-1 dry soil, Morgan‘s P of
4.6±0.49 mg L-1 (Index 2) and a soil pH of 5.6±0.1. The soil SMP buffer pH was 6.1±0.2
and the LR was 9.9±1 t ha-1.
Figure 3.2 United States Department of Agriculture (USDA) soil texture classification
triangle used to determine soil texture
44
3.3.2. Slurry sampling and analysis
Cattle slurry from dairy replacement heifers was taken from a dairy farm (53°18‘ N,
8°47‘ W) in Galway, Republic of Ireland. The storage tanks were agitated and slurry
samples were transported to the laboratory in 10 Litre drums. Slurry samples were stored
at 4°C. Slurry pH was determined using a pH probe (WTW, Germany) at 0 h and 24 h;
the latter time corresponded with the time the slurry was interacting with the soil in the
beaker before being saturated with water. The WEP of slurry was measured at 24 h as
suggested by Kleinman et al. (2007). The TP of the dairy cattle slurry was determined
after Byrne (1979). Potassium and magnesium (Mg) were analyzed using a Varian
Spectra 400 Atomic Absorption instrument, and analyses for N and P were carried out
colorimetrically using an automatic flow-through unit. The slurry had a TN concentration
of 3982±274 mg L-1, TP of 811±37 mg L-1, total K (TK) of 4009±482 mg L-1, and a pH
of 7.3±0.5.
3.3.3. PSM sourcing and analysis
The Al-WTR was provided by Galway City water treatment plant (53°17‘ N, 9°03‘ W).
Coal combustion by-products were provided by the Electricity Supply Board. The pH of
the PSM was measured using 2:1 deionised water: dry amendment ratio. It was possible
to measure the pH of the Al-WTR sludge with a pH probe. Dry matter content was
determined by drying at 40°C for 72 h. Total metal and P of the PSM was measured by
‗aqua regia‘ digestion using a Gerhard Block digestion system (Cottenie and Kiekens,
1984), which is described by Fenton et al. (2009). The WEP of the PSM was determined
after Dayton and Basta (2001).
The characteristics of all Al-WTR-1, Al-WTR-2, flyash and FGD are presented in Table
3.1. Al-WTR-1 and Al-WTR-2 had respective Al contents of 11.1% and 5.3% (Table
3.1). Flyash contained 5.6% Al, 4.9% Ca, 2.5% Fe, 12,200 mg kg-1 Mg and 5,460 mg kg-1
TP. FGD contained 20% Ca, 2,950 mg kg-1 Mg and trace amounts of Fe (0.1%) and Al
(0.1%). The composition of the commercial grade alum used is also shown. Analytical
45
grade aluminium chloride (13% Al), ferrous chloride (18% Fe) and lime (54% Ca) were
used in the experiment.
3.3.4. Agitator test
The agitator test comprised 10 different treatments: a grassed sod-only treatment; grassed
sod receiving dairy cattle slurry at a rate equivalent to 40 kg TP ha-1 (the study control),
and grassed soil receiving 8 different chemically-treated slurries (Table 3.2) applied at a
rate equivalent to 40 kg TP ha-1. Amendments were added to slurry in a beaker and mixed
for 10 min using a jar test flocculator set at 100 rpm. Each of the 8 amendments were
applied at 3 different rates (high, medium and low) in triplicate (n=3). All agitator tests
were carried out within 21 d of sample collection. These rates were based results of batch
test (Appendix B).
Prior to the start of the agitator test, the intact soil samples - at approximately field
capacity - were cut to approximately 45 mm depth and transferred from the sampling
cores into beakers. This depth of soil in the beakers was considered sufficient to include
the full depth of influence on release of P to overland flow (Mulqueen et al., 2004). The
chemically-amended slurry was applied to the soil with a spatula (t=0 h), and was then
allowed to interact for 24 h prior to saturation of the sample. After 24 h (t=24 h), samples
were saturated by gently adding deionised water to the soil sample at intermittent time
intervals until water pooled on the soil surface (over 24 h). Immediately after saturation
was complete (t=48 h), 500 ml of deionised water was added to the beaker. The agitator
paddle was then lowered to mid-depth in the overlying water and rotated at 20 rpm for 24
h, as an attempt to (Figure 3.3).
46
Table 3.1 Characterisation of PSMs and alum used in the agitator test (mean ± standard
deviation) tests carried out in triplicate
Amendment
pH
WEP
mg kg-1
Al
Al-WTR-1
Al-WTR-2
(2 mm)
(sludge)
7.9± 0.1
6.9± 0.2
<0.01
Flyash
FGD
Alum
(Al2(SO4)3nH2O)
11.2± 0.04
8.6± 0.0
1.25
<0.01
<0.01
0
4.23
11± 0.0
5.3± 0.2
5.7± 0.2
0.1± 0.0
1.3± 0.1
0.11
4.9± 0.2
20± 0.3
Fe
0.2± 0.0
0.01
2.2± 0.1
0.1± 0.0
K
0.03± 0.0
<0.01
0.1
0.03
As
6.2±1.1
<0.01
13± 0.6
<0.01
1
Cd
0.16± 0.0
<0.01
0.6± 0.0
0.2± 0.02
0.21
Co
0.5± 0.3
<0.01
33± 1
0.3± 0.1
Cr
3.8± 0.21
0.3± 0.02
88± 2
3± 0.1
31.7± 1.5
0.6± 0.03
32.7±1.5
37± 13
165± 33
3.2± 1.7
12,200± 610
2,950± 58
Mn
79± 1
6.9± 0.1
347± 160
31± 0.6
Mo
0.47± 0.2
<0.01
7.7± 0.5
0.73± 0.3
Na
611± 180
65± 14
1370± 610
660± 93
Ni
4.8± 0.06
0.6±0.2
44± 1
11± 0.6
P
234± 5.3
18.7± 1.6
5460± 630
65± 20
Pb
1.2± 0.8
<0.01
30± 2
0.74± 0.4
V
3± 0.2
0.2± 0.01
155± 5
49± 2
Zn
17
0.8± 0.1
75± 31
9.4± 2
Ca
Cu
Mg
%
mg kg-1
<0.01
2.1
1.4
2.8
WEP-water extractable phosphorus; Al-WTR-alum-based water treatment residual; FGD-flue gas
desulphurisation product.
47
Figure 3.3 Schematic diagram of soil sample in agitator
Eight amendments were examined in an agitator test to control diffuse incidental P losses
in runoff from slurry applied to permanent grassland. The amendments were divided into
commercially available products (chemical amendments) including: industrial grade
liquid alum (Al2(SO4)3.nH2O) containing 8% aluminium oxide (Al2O3); laboratory grade
aluminum chloride (AlCl3.6H2O); FeCl2 and burnt lime (Ca(OH)2); and P sorbing
materials (PSM): aluminium-based water treatment residuals, sieved to less than 2 mm
(Al-WTR-1); Al-WTR homogenised sludge (Al-WTR-2); flyash; and FGD.Chemical
amendments were applied based on Al:TP stoichiometric rate, and PSM were applied
based on a kg kg-1 weight basis (slurry DM). The pH of the amended slurry was
measured prior to application at t=0 h. Samples were taken to determine DM and WEP of
the amended slurry (Kleinman et al., 2007). Slurry and amended slurry were applied to
the surface of the grassed soil at a rate equivalent to 40 kg TP ha-1 (50 m3 ha-1 slurry). For
each treatment, slurry samples (n=3) - with the same volume as applied to the grassed
sample in the agitator test - were spread at the bottom of another beaker to allow pH and
WEP to be measured at 24 h without disturbing the sample used in the agitator test.
48
Table 3.2 Table showing amendments in order of effectiveness score, breakdown of costsa, cost/m3 slurryb, cost for 100 cow farm,
percentage reduction in DRP in overlying water and WEP of slurry at 24 h
Chemicalc
Effectiveness
score
Costd
Rate
€ tonne-1
kg m-3
250
12
5:1 Fe: P
10:1 Fe: P
Addition rate
Spreading
Agitation
Total
€ m-3
Cost
watere
€ m-3
€ m-3
100 cow
farm
€ farm-1
€ m-3
0.00
2.92
1.58
0.33
0.00
1.91
1010
1.57
0.34
0.00
4.82
2550
88
29
1.7± 0.27
36
7.29
1.60
0.34
0.00
9.23
4870
90
0.2± 0.06
72
58
14.59
1.64
0.35
0.00
16.58
8750
99
0.5± 0.02
81
17
4.76
1.58
0.34
0.00
6.67
3520
87
2.06± 0.06
21
19
5.23
1.58
0.34
0.00
7.15
3770
92
1.43± 0.02
46
37
10.45
1.61
0.35
0.00
12.41
6550
99
0.16± 0.02
94
19
2.82
1.60
0.34
0.00
4.76
2520
83
0.51± 0.01
81
1.22:1 Al: P
24
3.53
1.59
0.34
0.00
5.46
2880
94
0.27± 0.07
90
2.44:1 Al: P
47
7.07
1.62
0.35
0.00
9.04
4770
99
0.03± 0.0
99
150
2.03
3.23
0.69
2.14
8.09
4270
72
0.09± 0.0
97
300
4.05
4.90
1.05
4.28
14.28
7540
89
0.05± 0.0
98
400
5.40
5.84
1.26
5.45
17.95
9480
91
0.04± 0.0
99
150
2.03
2.50
0.54
1.07
6.13
3240
43
0.92± 0.14
65
4.2 kg kg-1
300
4.05
3.62
0.78
2.37
10.82
5710
72
0.24± 0.08
91
5.6 kg kg-1
400
5.40
4.25
0.92
3.09
13.66
7210
81
0.22± 0.04
92
Control
FeCl2
1
(FeCl3)
AlCl3
2
(PAC)
2:1 Fe: P
0.98:1 Al: P
280
1.22:1 Al: P
2.44:1 Al: P
Alum
FGD
3
4
0.98:1 Al: P
1.33 kg kg-1
2.65 kg kg
150
14
-1
3.5 kg kg-1
Flyash
Ca(OH)2
Al-WTR-1
5
6
7
(<2 mm)
Al-WTR-2
(sludge)
8
2.1 kg kg-1
1:1 Ca: P
14
312
Cost
amendment
DRP
WEP (t=24h)
WEP
%P
mg kg-1
%
2.64± 0.15
2
0.48
1.55
0.33
0.00
2.37
1250
0
2.43± 0.06
9
5:1 Ca: P
8
2.40
1.56
0.34
0.00
4.30
2270
74
1.52± 0.02
42
85
10:1 Ca: P
15
4.81
1.57
0.34
0.00
6.72
3550
81
0.4± 0.0
0.28 kg kg-1
20
-
-
-
-
-
-
31
2.49± 0.06
6
0.69 kg kg-1
50
-
-
-
-
-
-
77
1.73± 0.02
34
1.4 kg kg-1
100
-
-
-
-
-
-
74
0.93± 0.02
65
0.28 kg kg
-1
63
0.31
1.65
0.35
0.00
2.31
1220
0
1.13± 0.05
57
0.69 kg kg-1
5
156
0.78
1.88
0.40
0.13
3.20
1690
71
0.28± 0.01
89
1.4 kg kg-1
313
1.56
2.52
0.54
0.72
5.34
2820
67
0.07± 0.0
97
DRP-dissolved reactive P; WEP-water extractable P; Al-WTR-alum-based water treatment residual; FGD-flue gas desulphurisation product; aCalculations based on a dairy farm with 100 cows,
or equivalent stocking rate, with a 18-wk winter; bSlurry properties: TP = 811 mg L-1 and 7.2% DM; cWhere analytical grade products were used, cost was estimated using the most similar
commercial product on the market (in brackets); dCost includes delivery of material and addition of material to slurry in storage tank; eAddition of some amendments resulted in DM >10%water addition needed for spreading.
49
3.3.5. Water sampling and analysis
Water samples (4 ml) were taken from mid-depth of the water overlying the soil at 0.25,
0.5, 1, 2, 4, 8, 12 and 24 h after the start of each test (i.e after the 500 ml was added). All
samples were filtered immediately after sample collection using 0.45 μm filters and
placed in a freezer (APHA, 1995) prior to being analysed colorimetrically for DRP using
a nutrient analyser (Konelab 20, Thermo Clinical Labsystems, Finland). The DRP
concentrations were used to calculate the mass of DRP in the water overlying the soil
samples in the beaker, taking into account the water volume reduction as the test
progressed. All water samples were tested in accordance with standard methods (APHA,
1995). Figure 3.4 shows the P classification system used in this study (adapted from
APHA).
3.3.6. Statistical Analysis
Proc
Mixed
(SAS,
2004)
was
used
to
model
the
factorial
structures
(amendment*application rate; and amendment*application rate*time) in the experiment
in order to allow for heterogeneous variance across treatments. A group variable was
fitted to allow comparisons between the control treatments and the factorial
combinations. A multiple comparisons procedure (Tukey) was used to compare means.
3.3.7. Cost analysis
The cost of chemical amendment was calculated based on the estimated cost of chemical,
chemical delivered to farm, addition of chemical to slurry, increases in slurry agitation,
and slurry spreading costs as a result of increased volume of slurry due to the addition of
the amendments. Slurry spreading costs were estimated based on data from Lalor (2008)
and slurry agitating costs were estimated based on data from Anon (2008). The cost of
water required to maintain DM at less than 10% was included, as DM must be less than
10% for ease of handling (Stan Lalor pers com, 2010). The feasibility of amendments
50
was determined based on effectiveness, rate, potential barriers to use and cost of
implementation.
Runoff water sample
↓
DRP (Dissolved
reactive P)
TDP (Total
dissolved P)
←
↓
→
Filtered (0.45 μm
filter)
Unfiltered
↓
↓
Persulphate
digestion
Persulphate
digestion
←
DUP (Dissolved unreactive P) = TDP-DRP
→
TRP (Total
reactive P)
TP (Total P)
PP (Particulate P) = TP-TDP
Figure 3.4 Phosphorus classification system used in this study (APHA, 1995)
3.4.
Results
3.4.1. Results of agitator test
The amendments that were most effective at reducing DRP in overlying water were:
FeCl2 (99%), AlCl3 (99%), alum (99%), FGD (91%), flyash (81%), lime (81%), AlWTR-1 (71%) and Al-WTR-2 (77%). Figure 3.5 shows the mass of DRP in overlying for
each treatment at each rate is shown in Figure 3.6. The amendments are ranked in
decreasing order of effectiveness in Table 3.3. The irregularity between the 0.69 and 1.4
kg kg-1 amendment rates for Al-WTR-1 and Al-WTR-2 treatments were consistent across
sieved and sludge treatments. However, this was not statistically significant. The overall
statistical analysis showed that there was a significant interaction between treatment and
application rate, but that the interaction effects were small compared to the main effects.
Optimum application rates were determined based on achieving a similar level of P
reduction for each of the amendments, while applying the minimum amount of metals to
land, thus reducing risk due to land spreading of metals. Based on this criterion, optimum
amendment rates were: FeCl2 (2:1 (Fe:P)), AlCl3 and alum (0.98:1 (Al:P)), FGD (1.33 kg
kg-1), flyash (4.2 kg kg-1), lime (5:1 (Ca:P)), Al-WTR-1 and Al-WTR-2 (0.69 kg kg-1).
51
Slurry-control
Grass
800
12
10
8
6
4
2
0
600
400
200
0
Aluminium chloride
12
10
8
6
4
2
0
600
200
0
FeCl2
Lime
800
12
10
8
6
4
2
0
600
400
200
0
Al-WTR-1
Al-WTR-2
800
12
10
8
6
4
2
0
600
400
200
0
FGD
Flyash
800
12
10
8
6
4
2
0
600
400
200
0
0
4
8
12
16
20
0
4
8
12
Time from start of agitator test (hours)
16
Figure 3.5 Mass of DRP and DRP concentration in overlying water
52
20
C
Mass P released in overlying water at time t (mg m-2)
400
Concentration of dissolved reactive P in overlying water (mg L-1)
Aluminium sulphate (alum)
800
Linear regression showed a strong relationship between percentage reduction in slurry
WEP and DRP in water overlying the soil for alum (R2=0.95), AlCl3 (R2=0.99), AlWTR-2 (R2=0.94), flyash (R2=0.96), FGD (R2=0.83); and a smaller relationship for FeCl2
(R2=0.60), lime (R2=0.75) and Al-WTR-1 (R2=0.67). Only three rates were examined and
there were insufficient points to quantify any relationship.
100
80
10
60
AlCl2 (PAC)
FeCl2
40
Ca(OH)2
5
Al-WTR-2
FGD
20
Flyash
Al2(SO4)
0
0
0
5
10
15
Percentage reduction in DRP release to overlying
water (%)
Reduction in DRP released from soil
( kgha-1)
15
20
Total cost of chemical amendment of slurry (euro t-1)
Figure 3.6 Total cost of chemical amendment of dairy cattle slurry plotted against the
reduction in dissolved reactive phosphorus (DRP) lost to overlying water and the
percentage reduction in DRP release to overlying water
3.4.2. Cost and feasibility analysis
The estimated cost of addition of amendments and increases in spreading and agitation
costs due to amendments are presented in Table 3.2. The effects of amendments on slurry
viscosity or handling were not considered in the cost analysis. It was assumed that
53
amendments would be added upon delivery, so storage cost on site was excluded from the
analysis. For analytical grade products, the cost was estimated using the most similar
commercial product available on the market. Starting with the cheapest, the amendments
were ranked as follows: Al-WTR-2 (€3.20 m-3); Ca(OH)2 (€4.30 m-3); alum (€4.76 m-3);
FeCl3 (€4.82 m-3); poly aluminium chloride (€6.67 m-3); FGD (€8.10 m-3) and flyash
(€10.80 m-3).
Table 3.3 Feasibility of amendments
Chemical
Feasibility
score
Addition
rate
Total
cost
€ m-3
Reduction
in DRP
%P
Notes
Alum
1
0.98:1 Al: P
4.76
83
Risk of effervescence
Risk of release of H2S due to anaerobic
conditions and reduced pH
Cheap and used widely in water treatment
AlCl3(PAC)
2
0.98:1 Al: P
6.67
87
No risk of effervescence (Smith et al, 2004)
AlCl3 increased handling difficulty
Expensive
FeCl2(FeCl3)
3
2:1 Fe: P
4.82
88
Potential for Fe bonds to break down in
anaerobic conditions
Potential increased release of N2O
Ca(OH)2
4
5:1 Ca: P
4.30
74
Risk of increased NH3 loss
Strong odour
Hazardous substance
Al-WTR-2
(sludge)
5
0.69 kg/kg
3.20
71
Waste product
Risk of release of H2S
Composition varies with location and time
Risk of P deficiency if over applied
High application rates required
Limited supply
FGD
6
1.33 kg/kg
8.10
72
High pH and therefore risk of increased NH3
loss
Strong odour
Large application rates required
Settles quickly
Potentially toxic
Flyash
7
4.2 kg/kg
10.80
72
Al-WTR-1
(<2 mm)
8
0.69 kg/kg
-
77
Contains heavy metals
Huge volume of water required
Settles quickly
Potentially toxic
Excluded from cost analysis
The effect of amendments on slurry pH is a potential barrier to their implementation, as it
affects P sorbing ability (Penn et al., 2011) and NH3 emissions from slurry (Lefcourt and
54
Meisinger, 2001). Slurry pH results are shown in Figure 3.7.The acidifying additives
(alum, AlCl3, FeCl2) lowered the pH of the slurry. Lime and flyash addition increased the
pH to 10.3 (p<0.0001) and 9.3 (p<0.0001), respectively. The use of these high pH
amendments is likely to result in an increase in NH3 emissions to the atmosphere from
slurry. Risk of increased metal concentrations in overland flow is a significant barrier to
the use of these amendments. No analysis of metals in the overlying water was
undertaken in this experiment; therefore, feasibility considerations for metal application
rates were based on the principal of applying the minimum metals necessary to reduce
DRP in the overlying water. In addition, flyash was deemed unsuitable due to high
concentrations of heavy metals contained within it.
12
Slurry/amended slurry pH
10
8
6
4
2
Ca(OH)2
Al-WTR-1 Al-WTR-2
-1
Flyash
1..33 kg kg
-1
2.65 kg/kg
-1
3.5 kg kg
-1
2.1 kg kg
-1
4.2 kg kg
-1
5.6 kg kg
FeCl2
-1
2:1 Fe:P
5:1 Fe:P
10: 1 Fe:P
PAC
0.28 kg kg
-1
0.69 kg kg
-1
1.4 kg kg
0.98:1 Al:P
1.22:1 Al:P
2.44: Al:P
Alum
0..28 kg kg
-1
0.69 kg kg
-1
1.4 kg kg
0.98:1 Al:P
1.22:1 Al:P
2.44: Al:P
Slurry
1:1 Ca:P
5:1 Ca:P
10: 1 Ca:P
Control
Rate
-1
0
FGD
Figure 3.7 Histogram of slurry pH at time of amendment/application (clear box) and pH
of slurry after 24 h (hatched box)
55
3.5.
Discussion
Chemical amendment is an attractive means of mitigating against both incidental P losses
from slurry and elevated P release from soil resulting from the increase in soil P due to
slurry and chemical fertiliser application. It could be used in strategic areas for protection
of a waterbody while allowing farmers to utilise other nutrients in slurry on farms with
high STP. Ferric chloride, AlCl3 and alum were the most effective amendments at
optimum rates. Aluminium water treatment residuals, flyash and FGD are not feasible
due to the large application rates needed and the risk of over-application of metals.
Although chemical amendments are expensive, they are widely available and more
efficient than PSM, and lower metal application rates are required to achieve adequate P
reductions at optimum application rates.
The results for FeCl2, AlCl3, alum, and lime were in agreement with other studies.
Lefcourt and Meisinger (2001) reported a 97% reduction in DRP of dairy cattle slurry
when 2.5% by weight of alum was added in a laboratory batch experiment. The Al-WTR
used in the present study was less effective than those observed in other studies. Penn et
al. (2011) reported an 80% reduction in WEP of dairy slurry when slurry was amended at
a rate equivalent to 0.2 kg kg-1 (compared to 71% observed in this study at 0.69 kg kg-1).
The results for the coal combustion by-products differed to previous studies. Dou et al.
(2003) found that adding flyash to dairy manure at 0.4 kg kg-1 (manure DM) lowered
soluble P by between 50 and 60% compared to 43% at 2.1 kg kg-1 in the present study.
Penn et al. (2011) found that FGD was ineffective in treating dairy slurry when applied at
0.2 kg kg-1, which was in contrast to the results of the present study (72% at 1.33 kg kg-1).
This difference could be due to the difference in composition of flyash. The mass of P
released and DRP of the overlying water at any time for the duration of the experiment
are shown in Figure 3.5. Throughout this study, an initial high rate of DRP release was
followed by a period of slower release and, after 12 h, an approximate equilibrium DRP
concentration was reached with the exception of the highest application rate of Al-WTR
and all FGD treatments.
56
The stability, and thus the effectiveness, of different amendments over longer time spans
(months, years) depends on farm management systems, drainage, and soils to which they
are applied. For example, Al-P bonds are most stable in acidic soils, while Ca-P bonds
are more stable in calcareous conditions (Wild, 1988). The effect of treatment on slurry
pH at the time of application affects P sorption capacity of PSM containing Ca
compounds, and NH3 emissions from slurry. Changes in pH may reduce the pathogen
load in slurry and subsequently pathogen transport to soil and runoff. Application of AlWTR and FGD did not significantly change slurry pH. The soil used had optimum STP
and only required P inputs sufficient to maintain P levels for future agronomic needs.
Slurry amendment type (treatment), rate of amendment addition (rate), and their
interaction had an effect on DRP in runoff (p< 0.0001; R2=0.96). This strong relationship
between slurry WEP and overlying water DRP would suggest that for this particular soil
with this STP, soil type and STP had a minimum impact on results; in addition, any effect
of STP would be constant across all treatments. Sharpley and Tunney (2000) reported
that STP had little impact on the release of P to runoff for up to 14 d after dairy cattle
slurry application.
There have been many reports of human and animal deaths from the release of the toxic
hydrogen sulphide gas when slurry is being agitated on farms. The addition of chemicals
such as alum that can lead to acidification of slurry and are likely to increase the release
of toxic hydrogen sulphide gas and great care should be taken when adding acidifying
chemicals to slurry on the farm.
Public and stakeholder opinion is the main obstacle for the use of chemical amendments.
This study examined the feasibility of the amendments based on effectiveness, optimum
rates and cost of treatment. Future work must address public concerns and examine the
impact of amendments on gaseous emissions and metal build-up in the soil. If
amendments to slurry are to be recommended (and adopted) as a method to prevent P
losses in runoff, the impact of such applications on slurry-borne pathogens, as well as
pathogen translocation to the soil and release in surface runoff, needs to be addressed.
The long-term effects on microbial communities in soil must also be examined.
57
There is no provision for a licence to landspread any of these amendments in Ireland
(lime is land applied in acidic soils to optimise soil pH for production) and if chemical
amendment were to be used to mitigate P losses, a licensing system would have to be
introduced by the Department of Agriculture in Ireland and relevant bodies in other
countries.
3.6.
Conclusions
The findings of this chemical amendment study are:
1. All amendments, when added to slurry, greatly reduced WEP of the slurry and
DRP in water overlying soil.
2. Even at optimum amendment rates, the cost of slurry treatment increases slurry
handling cost (between 250 and 560%) with the exception of Al-WTR, which is
unfeasible due to high rates required, concerns over variation in composition, and
limited supply.
3. These treatments currently seem to be expensive. However, they may be feasible if
used strategically to mitigate P loss from dairy slurry in CSA within a farm, or as
an alternative to applying slurry to high P soils.
4. Chemical amendments may have a role to play as part as P mitigation strategy
3.7.
Summary
This chapter has determined the most effective amendments at reducing DRP release
from land applied slurry to runoff. Chapter 4 details a runoff-box experiment designed to
develop an understanding of the performance of chemical amendments under more
realistic conditions. In addition to examining DRP, Chapter 4 examines how amendments
affect SS, PP and TP losses. Chapter 4 also examines the effect of amendments on
incidental loss of metals (Al, Ca and Fe) to runoff.
58
Chapter 4
4.1.
Laboratory-scale rainfall simulation experiment
Overview
The agitator test identified amendments with great potential to reduce P solubility. A
runoff box experiment was designed to develop our understanding of the performance of
amendments under more realistic conditions.
4.2.
Introduction
Chemical amendments of slurry using Al, Fe, or Ca based compounds reduce P solubility
in manure (Dao, 1999; Dou et al., 2003; Kalbasi and Karthikeyan, 2004) and reduce P in
runoff from plots receiving alum amended poultry litter (Moore and Edwards, 2005) with
negligible effect on metal loss (McFarland et al., 2003). Chemical amendments reduce
incidental P losses by a combination of the formation of stable metal-phosphorus
precipitates (such as Al-P phosphates in the case of alum) and flocculation of the particles
in the slurry to form larger particles, which are less prone to erosion (Tchobanoglous et
al., 2003). Previous studies have found that there was no risk of increased metal release
posed by chemical amendment of poultry litter (Moore et al., 1998), dirty water
(McFarland et al., 2003), or horse manure (Edwards et al., 1999).The present study
examines for the first time the effect of chemical amendment of dairy cattle slurry on
both P and metal (namely Al, Fe and Ca) losses to runoff, whereas most previous studies
only examined the effect of amendments on P solubility (Dao, 1999; Dao and Daniel,
2002; Dou et al., 2003).
59
4.3.
Materials and Methods
4.3.1. Soil sample collection and analysis
Intact grassed-soil samples, 70 cm-long by 30 cm-wide by 10 cm deep, were collected
from a dairy farm in Athenry, Co. Galway (53°21‘N, 8°34‘ W). A second set of soil
samples, taken to a depth of 10 cm below the ground surface from the same location, was
air dried at 40 °C for 72 h, crushed to pass a 2 mm sieve, and analysed for Morgan‘s P
(the national test used for the determination of plant available P in Ireland) using
Morgan‘s extracting solution (Morgan, 1941). Soil pH (n=3) was determined using a pH
probe and a 2:1 ratio of deionised water-to-soil. Particle size distribution was determined
using B.S.1377-2:1990 (BSI, 1990a). Organic content of the soil was determined using
the loss of ignition test (B.S.1377-3; BSI, 1990b). The soil was a poorly-drained sandy
loam (58% sand, 27% silt, 15% clay) with a Morgan‘s P of 22±3.9 mg P L-1, a pH of
7.45±0.15 and an OM content of 13±0.1%. The soil had a sandy loam texture, which
points to moderate drainage on site. However, medium permeable subsoil limits drainage.
Historic applications of organic P from an adjacent commercial-sized piggery have led to
high STP in the soil used in this study.
4.3.2. Slurry collection and analysis
Cattle slurry from dairy replacement heifers was taken from a farm (53°18‘ N, 8°47‘ W)
in County Galway, Republic of Ireland in Winter (February), 2010. The storage tanks
were agitated and slurry samples were transported to the laboratory in 10-L drums. Slurry
samples were stored at 4°C. Slurry and amended slurry pH was determined using a pH
probe (WTW, Germany) and the WEP of slurry was measured at the time of land
application after Kleinman et al. (2007). Dry matter content was determined by drying at
105 °C for 16 h. The TP of the dairy cattle slurry was determined after Byrne (1979).
Total potassium, TN and TP were carried out colorimetrically using an automatic flowthrough unit (Varian Spectra 400 Atomic Absorption instrument). Ammoniacal nitrogen
of slurry and amended slurry was extracted from fresh slurry by shaking 10 g of slurry in
60
200 ml 0.1 M HCl on a peripheral shaker for 1 h and filtering through No 2 Whatman
filter paper.
4.3.3. Slurry amendment and runoff set-up
The results of a laboratory micro-scale study (Chapter 3) (Data shown in Appendix C)
were used to select chemical amendments to be examined in the present study. In addition
to a grassed soil-only treatment, five treatments were examined: (1) slurry-only (the study
control) (2) industrial grade liquid alum (Al2(SO4)3.nH2O), comprising 8% aluminium
oxide (Al2O3) applied at a rate of 1.11:1 (Al:TP) (3) industrial grade liquid polyaluminium chloride hydroxide (PAC) (Aln(OH)mCl3n-m) comprising 10% Al2O3 at a rate
of 0.93:1 (Al:TP) (4) analytical grade FeCl2 at a rate of 2:1 (Fe:TP), and (5) burnt lime
(Ca(OH)2) at a rate of 10:1 (Ca:TP). The rates used were based on the results of Chapter
3.
A batch experiment was also conducted using a range of amendment concentrations to
construct a multi-point Langmuir isotherm (McBride, 2000):
P
x/m
=
1 + P
ab
b
(4.1)
where P is the concentration of P in solution at equilibrium (mg L-1), x/m is the mass of P
adsorbed per unit mass of amendments (g kg-1) at P, a is a constant related to the binding
strength of molecules onto the amendments, and b is the theoretical amount of P adsorbed
to form a complete monolayer on the surface. This provided an estimate of the maximum
adsorption capacity of the amendments (g kg-1). These results are shown in Figure 4.1.
The amendments were added at a range of rates to 500 g slurry samples and mixed
rapidly for 10 min at 100 rpm using a jar test flocculator. The samples were incubated at
11°C for 24 h. Following incubation, 50 g of slurry/amended slurry was mixed with 250
ml of distilled water. The slurry-water solution was then placed on a reciprocating shaker
for 1 h. Samples were centrifuged at 14,000 rpm for 5 min to separate the solids from the
61
solution before being passed through a 0.45 µm filter and the P extract was determined
using a Konelab nutrient analyser (Konelab 20, Thermo Clinical Labsystems, Finland).
1
0.6
0.8
0.6
0.4
0.4
Alum, a = 1
b = 1 g P kg-1 alum
0.2
0.2
PAC, a = 1
b = 0.52 g P kg-1 PAC
P/(x/m) (mg L-1)
0
0
1
2
3
4
0
5
0
6
6
5
4
3
2
1
0
5
4
3
2
FeCl2, a = 0.7
b = 11.2 g P kg-1 FeCl2
1
0
0
1
2
3
4
1
5
2
3
4
5
Ca(OH)2, a = 0.35,
b = 9.2 g P kg-1 Ca(OH)2
0
1
2
3
4
5
P (mg L-1)
Measured data
Modelled data
Figure 4.1 Langmuir isotherm fitted to phosphorus in amended slurry data
The equilibrium P concentration (EPC0) (i.e. the point where no net desorption or
sorption occurs) was derived using the following formula (Olsen and Watanabe, 1957):
S‘ = kdP-S0
(4.2)
where S‘ is the mass of P adsorbed from slurry (mg kg-1), P is the final P concentration of
the solution, kd is the slope of the relationship between S‘ and P, and S0 is the amount of
P originally sorbed to the amendment (mg L-1). The EPC0 was determined graphically
(Figure 4.2).
62
A slurry sample (from the same storage tank as used in the surface runoff experiments)
with a DM of 6%, TP of 550 mg L-1 and WEP of 2.26 g kg-1 was used for the isotherm
study. An approximate metal: soluble P ratio for each amendment was calculated using
the b term from the Langmuir isotherm and WEP of the slurry. The isotherm results
indicated that lower application rates should be sufficient to bind P in slurry. However, as
the experiment detailed in Chapter 3 was considered to best replicate runoff, it was
decided to base the application rates on the results of Chapter 3 and not the batch test
used to develop the Langmuir isotherm. As one of the main aims of the present study was
to investigate the effect of amendments on metal release, it was considered to be
reasonable and conservative to use results from Chapter 3.
1200
1000
800
800
600
600
400
400
200
Alum, EPC0 = ~0
200
0
0
S‘ (mg kg-1)
PAC, EPC0 = ~0
0
10
0
20
10
20
12000
10000
8000
8000
6000
6000
4000
4000
FeCl2
2000
2000
Ca(OH)2
0
0
0
2
4
0
6
5
10
15
20
-1
P (mg L )
Figure 4.2 Phosphorus sorption isotherms for amended slurry data
A laboratory runoff box study was chosen over a field study as it was less expensive and
allowed testing under standardized conditions. Such studies are a widely used tool in P
transport research to compare treatments (Hart et al., 2004). This experiment used two
63
laboratory runoff boxes, 200-cm-long by 22.5-cm-wide by 5-cm-deep with side walls 2.5
cm higher than the soil surface, and 0.5-cm-diameter drainage holes located at 30-cmcentres in the base (after Regan et al., 2010). Cheese cloth was placed at the base of each
runoff box before placing the sods to prevent soil loss. Intact grassed sods from the study
site were transported to the laboratory and stored at 11°C in a cold room prior to testing.
All experiments were carried out within 14 d of sample collection and tests were
conducted in triplicate (n=3). Immediately prior to the start of each runoff box
experiment, new sods were trimmed and placed in the runoff box; each slab was butted
against its adjacent slab to form a continuous surface. Molten candle wax was used to
seal any gaps between the soil and the sides of the runoff box, while the joint between
adjacent soil samples did not require molten wax.
The packed sods were then saturated using a rotating disc, variable-intensity rainfall
simulator (after Williams et al., 1998), comprising a single 1/4HH-SS14SQW nozzle
(Spraying Systems Co., Wheaton, IL) attached to a 450-cm-high metal frame, and
calibrated to achieve an intensity of 11.5±1 mm h-1 and a droplet impact energy of 26 kJ
cm-1 ha-1 at 85% uniformity. The sods were then left to drain for 24 h before the
experiment commenced; the grassed sods were then assumed to be at an approximate
‗field capacity‘ (Regan et al., 2010). Amendments were added to the slurry and mixed
rapidly (10 min at 100 rpm) using a jar test flocculator immediately prior to land
application. Slurry and amended slurry were applied directly to the surface of the intact
grassed soil in runoff boxes at a rate equivalent to 33 m3 slurry ha-1 (26 kg TP ha-1), the
rate most commonly used in Ireland (Coulter and Lalor, 2008). Figure 4.3 shows soil sods
before and after slurry application.
During each rainfall simulation event, rain was applied until runoff water flowed
continuously and then for 1 h while runoff water samples were collected. The drainage
holes on the base of the runoff boxes were sealed to better replicate field conditions and
to ensure that overland flow occurred. Figure 4.4 shows the laboratory setup.
64
a
b
Figure 4.3 Runoff box immediately (a) before and (b) after slurry application
65
Runoff box cleaned prior to each
Muslin cloth cut to length to
Runoff box ready for soil to be
rainfall simulation
prevent soil loss and aid drainage
placed
Soil sample trimmed
Soil samples placed in flume
View of runoff box with one sod
immediately prior to placement
starting at lower end
Figure 4.4 Photographs showing soil sod preparation and placement methodology
The first rainfall simulation (RS1) commenced 48 h after slurry application, then after a 1
h interval the second rainfall simulation (RS2) commenced. The drainage holes at the
bottom of the runoff box were opened for a 24 h interval and then closed when the third
rainfall event (RS3) commenced. As the soil samples were taken from the mid-slope of a
field with a slope of approximately 5%, it would have been unrealistic to allow the soil to
remain water-logged for 24 h between RS2 and RS3. All of the surface runoff was
collected at 5-min intervals once runoff began. The source for the water used in the
rainfall simulations had a DRP concentration of less than 0.005 mg L-1, a pH of 7.7±0.2
66
and an electrical conductivity (EC) of 0.435 dS m-1. Runoff water pH and EC were
measured immediately prior to each event using a pH and EC meter.
4.3.4. Sample handling and analysis
Runoff samples were collected in 1 L containers (covered to prevent rain water entering
container) at the bottom of the runoff box. Immediately after collection, a subsample of
the runoff water was passed through a 0.45µm filter and a sub-sample was analysed
colorimetrically for DRP using a nutrient analyser (Konelab 20, Thermo Clinical
Labsystems, Finland). A second filtered sub-sample was analysed for TDP using
potassium persulfate and sulfuric acid digestion (HACH LANGE, Germany). Unfiltered
runoff water samples were also collected and TP was measured using the method used for
TDP analysis. Particulate P was calculated by subtracting TDP from TP. The DRP was
subtracted from the TDP to give the DUP.
Suspended sediment were determined for all samples by vacuum filtration of well-mixed,
unfiltered runoff water through Whatman GF/C (pore size: 1.2 µm) filter paper. All water
samples were tested in accordance with standard methods for the examination of water
and wastewater (APHA, 1995). In order to address the concern of metal release from
amendments, identified by Fenton et al. (2008), it was decided to measure Al, Ca and Fe
as these were the active metals in the chemical amendments added to slurry. The metal
content was determined using an ICP (inductively coupled plasma) VISTA-MPX
(Varian, California). The limit of detection for Al and Fe was 0.01 mg L-1 and 1 mg L-1
for Ca.
4.3.5. Statistical analysis
The structure of the experiment was a one-way classification with the rainfall events
being repeated measures on each experimental unit. Proc Mixed of SAS (2004) was used
to analyse the concentrations of DRP, DUP, PP, TP, SS, Al, Ca and Fe with a covariance
structure to account for correlations between the repeated measures. An unstructured
67
covariance model was used for most variables and the outcome was interpreted as a
factorial of treatment x event. In all cases, the treatment by event interactions were
examined. The data for Al and Fe were censored by a limit of detection and PROC
NLMIXED of SAS was used to fit a censored Normal-based model while accounting for
the correlations by inducing a compound symmetry structure with a random effect.
4.4.
Results
4.4.1. Slurry and amended slurry analysis
The results of the slurry analysis are shown in Table 4.1. The slurry sample was typical of
slurry found on farms in Ireland (SI 610 of 2010) with a high DM on the upper limit for
land application (Stan Lalor pers com, 2011). The slurry TP and TK remained relatively
constant. At the rates used in this study, all of the amendments examined reduced the
WEP of dairy cattle slurry by approximately 99% compared to the slurry-control
(p<0.001). Alum addition reduced slurry pH from approximately 7.5 (control) to 5.4,
PAC reduced pH to 6.4 and FeCl2 to 6.7 (p<0.001), while lime addition increased slurry
pH to 12.2 (p<0.001). Chemical amendment also changed the appearance of slurry
(Figure 4.5)
Table 4.1 Stoichiometric ratio at which the amendments were applied and slurry dry
matter (DM), pH and average concentrations of NH4- N, water extractable phosphorus
(WEP), total nitrogen (TN), total phosphorus (TP) and total potassium (TK) (n=3)
Rate
DM
pH
%
Slurry
NH4-N
WEP
TN
TP
TK
mg L-1
g kg-1 DM
mg L-1
mg L-1
mg L-1
10.5 (0.04)
7.47 (0.1)
1760 (123)
2.22 (0.34)
4430 (271)
1140 (76)
4480 (218)
Alum
1.1:1 [Al:TP]
9.4 (0.16)
5.40 (0.1)
1770 (21)
0.002 (0.0004)
4570 (176)
1140 (69)
4360 (84)
PAC
0.93 [Al:TP]
9.6 (0.28)
6.37 (0.1)
1760 (143)
0.0013 (0.0003)
4750 (448)
1180 (165)
4680 (448)
Lime
10:1 [Ca:TP]
8.2 (0.29)
12.2 (0.1)
1320 (141)
0.0056 (0.0003)
3190 (263)
1140 (96)
4810 (227)
FeCl2
2:1 [Fe:TP]
10.1 (0.22)
6.7 (0.1)
1700 (11)
0.0022 (0.0006)
4340 (372)
1120 (51)
4720 (386)
(standard deviation in brackets)
68
Lime
FeCl2
Alum
PAC
Slurry-control
Figure 4.5 Photographs of slurry and amended slurry immediately after application to
grassed soil in boxes
4.4.2. Water quality analysis
The average flow-weighted mean concentrations (FWMC) of DRP, DUP and PP in
runoff for the three rainfall events are shown in Figure 4.6. Alum (114 μg DRP L-1) and
PAC (89 μg DRP L-1) were more effective at reducing DRP concentration than lime (200
μg DRP L-1) and FeCl2 (200 μg DRP L-1). At the rates used, all of the treatments
69
examined resulted in DRP concentrations in runoff greater than the MAC for surface
waters. However, the buffering capacity of water means that the concentration of a
surface waterbody will not be as high as the concentration of runoff, provided runoff
from slurry flows over soil which has not received dairy cattle slurry (McDowell and
Sharpley, 2002b).
The average concentrations of P in runoff water for the 3 rainfall simulation events were
171 µg DRP L-1, 91 µg DUP L-1 and 373 µg TP L-1 for grassed soil-only treatment
compared to 655 μg DRP L-1, 1,290 μg DUP L-1 and 8,390 μg TP L-1 for the slurrycontrol. Incidental DRP and TP concentrations in runoff water following land application
of dairy cattle slurry were 5 and 14 times greater than those from grassed-soil. In the
present study, alum (p<0.001), PAC (p<0.001), lime (p<0.05) and FeCl2 (p<0.05)
reduced DRP losses significantly compared to the slurry-control with reductions similar
to those observed in Chapter 3. The results of both studies are tabulated in Table 4.2. The
average FWMC of TDP was significantly reduced compared to the slurry-control. The
difference between grass-only, alum and PAC treatments was not significant and the
difference between lime and FeCl2 was also not significant. The average FWMC of DUP
was also significantly reduced for all treatments compared to slurry-control.
70
14
PP
Phosphorus (mg L-1)
12
DUP
DRP
2
1
10
8
6
4
2
0
1
2
3
1
Slurry
2
3
1
Alum
2
3
1
PAC
2
3
1
Lime
3
FeCl2
2
3
Grass
Phosphorus (mg L-1) (Log scale)
100
PP
DUP
DRP
2
1
10
1
0.1
0.01
1
2
Slurry
3
1
2
Alum
3
1
2
3
PAC
1
2
Lime
3
1
FeCl2
3
2
3
Grass
Figure 4.6 The average flow-weighted mean concentration of dissolved reactive
phosphorus (DRP), dissolved unreactive phosphorus (DUP) and particulate phosphorus
(PP), which comprise total phosphorus (TP) in runoff from three rainfall simulation
events.
71
Table 4.2 Results from Chapter 3 and 4, showing cost of treatments and total phosphorus
(TP) lost from runoff box
Chapter 3
DRP
reduction
stoichiometric
ratio
DRP
reduction
Cost per m3
slurry
metal: TP
%
metal: TP
%
€ m-3
87
88
74
88
1.11:1
0.93:1
10:1
2:1
83
86
69
67
1.90
7.40
8.80
10.20
7.00
Slurry
Alum
0.98:1
PAC
0.98:1
Lime
5:1
FeCl2
2:1
a
Taken from Chapter 3.
b
Chapter 4
stoichiometric
ratio
TP lost as %
TP applied
7.70
0.46
1.05
1.16
2.20
Cost per kg
P reduction
P lost
€ kg P-1
kg P ha-1
66.70
91.10
111.00
61.00
2.90
0.17
0.40
0.44
0.19
The cost m-3 and cost effectiveness have been updated from Chapter 3 to reflect the slight change in ratio
of metal:TP in the present runoff box study.
c
Laboratory grade aluminium chloride (Al2(SO4)3.nH2O) was used in Chapter 3. Commercially available
commercial grade liquid poly-aluminium chloride was used in the present study.
Note: All treatments were found to be significantly different to the control (p<0.001) in the Chapter 3
study. However, these were not significantly different to each other. In this study, all treatments were
significantly different to the slurry-control. Alum and AlCl3 were significantly different to lime and FeCl2,
but not to each other. (€1.00 is approximately equal to $1.37 or £1.59)
There was no significant difference between TP in runoff water from grass-only (373 μg
L-1) and alum treatments (506 μg L-1). However, there was a significant difference
between grass-only and PAC (1,150 μg L-1) (p< 0.001), lime (1,270 μg L-1) and FeCl2
(2,400 μg L-1) treatments for TP (p< 0.001), with a less significant difference between
grass-only and PAC (790 μg L-1) and Fe (1,730 μg L-1) for PP (p< 0.001). Therefore,
alum was the best amendment at reducing TP and PP loss to runoff. Table 4.2 shows the
TP lost in the runoff expressed as a percentage of the slurry applied. The TP losses from
the control were in agreement with Preedy et al. (2001), who reported that between 6 and
8% of TP applied was lost to runoff. The TP in runoff from the grass-only treatment
comprised approximately 47% DRP compared to 69% reported by Haygarth et al. (1998).
This difference may be a result of scale effects or differences in experiment design. While
chemical amendment of dairy slurry significantly reduced DRP, DUP, PP and TP in
runoff water, the proportions of each fraction in runoff from alum, PAC and FeCl2
treatments were similar to the slurry-control (Figure 4.7).
72
100%
80%
PP
60%
DUP
40%
DRP
20%
0%
Slurry
Alum
PAC
Lime
FeCl2
Grass
Figure 4.7 The average % of dissolved reactive phosphorus (DRP) dissolved unreactive
phosphorus (DUP) and particulate phosphorus (PP), which comprise total phosphorus
(TP) in runoff after three rainfall simulation events
Suspended sediment was 162 mg L-1 for the grass-only treatment compared to 3,030 mg
L-1 for the slurry-control (Figure 4.8). Alum resulted in the greatest reduction in SS (an
average of 88% for the three rainfall events compared to the slurry-control) (p<0.001).
There was no statistical difference in average FWMC of SS between alum, PAC (83%
reduction) and lime (82%). All of the treatments resulted in SS concentrations in the
runoff which were significantly greater than the grass-only treatment (p<0.005).
4.4.3. Metals in runoff water
The average FWMC of Al, Ca and Fe for the 3 rainfall simulation events are shown in
Figures 4.9, 4.10 and 4.11. The average concentrations of metals tested in runoff water
for the 3 rainfall simulation events were greater for the slurry-control than the grass-only
treatment. Aluminium concentrations increased from 60 to 91 µg Al L-1 (not statistically
significant), Ca from 84 to 108 mg L-1 (p<0.01), and Fe increased from 71 to 151 µg L-1
(p=0.02, RS2).
73
5000
Suspended sediment (mg L-1)
4500
4000
3500
3000
2500
2000
1500
1000
500
0
1
2
Slurry
3
1
2
Alum
3
1
2
3
PAC
1
2
Lime
3
1
2
FeCl2
3
1
2
3
Grass
Figure 4.8 Average flow-weighted mean concentrations of suspended sediment in runoff
The FWMC of Al decreased for all treatments compared to the slurry-control (Figure
4.9). There was a significant treatment x event interaction (p<0.001) and differences
between events within treatments and between treatments within events were tested.
After multiple comparison adjustments, there were no statistically significant differences
between treatments. There were some significant decreases to the RS3 event compared to
RS1 and RS2 for the lime and slurry-control treatments (p =0.03 and p =0.006). The
FWMC of Ca in runoff from all chemically amended slurry treatments was significantly
greater than from the slurry-control and the grass-only treatment (p<0.01) (Fig. 4.10).
The treatment by event interaction was significant and while no treatments were
statistically different across all events, there were some differences between the grass
treatment and both alum (p=0.02, RS1) and the slurry-control (p=0.02, RS2), and also
between the FeCl2 and the slurry-control (p=0.02, RS2).
74
Flow weighted mean concentration of
aluminium (Al) in runoff water (μg L-1)
250
200
150
100
50
0
1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3
Slurry
Alum
PAC
Lime
FeCl2
Grass
Source
Figure 4.9 Average flow-weighted mean concentrations of Al in runoff and rain water
Flow weighted mean concentration of
calcium (Ca) in runoff water (μg L-1)
300
250
200
150
100
50
0
1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3
Slurry
Alum
PAC
Lime
FeCl2
Grass
Source
Figure 4.10 Average flow-weighted mean concentrations of Ca in runoff and rain water
75
Flow weighted mean concentration of iron
(Fe) in runoff water (μg L-1)
400
350
300
250
200
150
100
50
0
1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3
Slurry
Alum
PAC
Lime
FeCl2
Grass
Source
Figure 4.11 Average flow-weighted mean concentrations of Fe in runoff and rain water
4.5.
Discussion
4.5.1. Slurry and amended slurry analysis
The amendments examined significantly reduced WEP in amended slurry compared to
the control. This was in agreement with previous studies (Dao, 1999; Dou et al., 2003).
Lefcourt and Meisinger (2001) reported a 97% reduction in WEP of dairy cattle slurry
when 2.5% by weight of alum was added in a laboratory batch experiment. Dao and
Daniel (2002) added alum (810 mg Al L-1) and ferric chloride (810 mg Fe L-1) (compared
to 1250 mg Al L-1 and 2280 mg Fe L-1 in this study) to dairy slurry and observed that
slurry WEP was reduced by 66 and 18%, respectively. At higher application ratios of
metal-to-TP, this study showed that greater reductions in WEP are achievable.
The amendments also changed the pH of the slurry. Lime addition increased slurry pH
significantly, resulting in a 25 and 30% reduction in NH4-N and TN of slurry following
amendment and mixing (Table 4.1). This was similar to findings of a study by Molloy
76
and Tunney (1983), who reported an increase in pH to 7.8 and a 50% increase in NH3
loss when CaCl2 was added to dairy slurry. This loss in NH4-N was most likely due to
NH3 volatilisation, as depending on the pH of a solution, NH4-N can occur as NH3 gas or
the ammonium ion (NH4) (Gay and Knowlton, 2005). This reduces the fertiliser value of
the slurry and increases NH3 emissions from slurry. Addition of alum, PAC and FeCl2 to
dairy cattle slurry significantly reduced the pH, as expected. This phenomenon has been
reported by a number of studies examining the use of amendments to reduce NH3 losses
from dairy cattle slurry (Meisinger et al., 2001; Shi et al., 2001). Meisinger et al. (2001)
reported a 60% reduction in NH3 loss from dairy cattle slurry when 2.5% by weight of
alum was added in a laboratory batch experiment. In a field study, Shi et al. (2001)
reported a 92% reduction in NH3 loss. Moore and Edwards (2005) have shown that
chemical amendment improves yields due to increased N efficiency. Chapter 5 examines
the impact of amendments on gaseous emissions and the risk of ‗pollution swapping‘,
which must be considered when evaluating amendments for possible recommendations to
legislators.
4.5.2. Water quality
The DRP and TP concentrations in runoff water from grass only treatment was well in
excess of the MAC of 30 μg DRP L-1 (Flanagan, 1990) and 25-100 μg TP L-1 (USEPA,
1986) for fresh waterbodies.
This study reinforced the results of a micro-scale study (Chapter 3) at meso-scale and
demonstrated that PAC is the most effective chemical amendment to reduce incidental
DRP losses, with alum being most effective at reducing DUP, PP, TP and SS losses
arising from land application of dairy cattle slurry. A limited number of runoff studies
have been carried out with chemical amendment of dairy cattle slurry (Elliot et al, 2005;
Torbert et al., 2005) and swine slurry (Smith et al., 2001a). Torbert et al. (2005) amended
landspread composted dairy manure with ferrous sulphate, gypsum and lime (each at 3:1
metal-to-TP ratio) immediately prior to a 40-min rainfall event with overland flow
equivalent to a rainfall intensity of 124 mm h-1. Ferrous sulphate reduced DRP loss by
77
66.3%, while gypsum and lime amendments increased DRP loss compared to control.
Lime and gypsum were effective for a short time at the beginning of the event and the
authors recommended that lime could be used in areas with infrequent and low volume
runoff events. In the Torbert et al. (2005) study, amendments were surface applied to
slurry immediately after slurry application and just before the first rainfall simulation
event occurred. The differences between the results are likely due to a combination of the
shorter contact time with lime before the first rainfall event and less mixing due to
different amendment application methods used in each study. In a plot study, Smith et al.
(2001a) amended swine manure with alum and AlCl3 at two stoichiometric ratios (0.5:1
and 1:1 Al: TP). Dissolved reactive phosphorus reductions for alum and AlCl3 at the
lower ratio were 33 and 45%, respectively, with 84% for both amendments at the higher
ratio, which was similar to reductions observed in the current study.
The reductions in P losses in the present study were similar to the percentage reductions
obtained in other incidental P loss mitigation studies. Hanrahan et al. (2009) reported that
incidental TP and DRP losses were reduced by 89 and 65%, respectively, by delaying
rainfall from 2 to 5 d after dairy cattle slurry application. This was in agreement with
results of O‘Rourke et al. (2010). In a plot study, McDowell and Sharpley (2002b)
applied dairy cattle slurry at 75 m3 ha-1 to the upper end of plots with lengths varying
from 1 to 10 m. Increasing the distance from the location where dairy slurry was applied
to the runoff water collection point was shown to reduce incidental P concentrations in
overland flow by between 70 and 90% when plots were subjected to simulated rainfall
with an intensity of 70 mm h-1. Therefore, as there are less expensive methods which can
achieve similar reductions in incidental P losses, in future the focus of chemical
amendment studies must be to find amendments to bind P in soil with the aim of reducing
long-term P losses.
In order to minimise the effect of the larger variation in the study control than in runoff
from grass-only and amended slurry runoff boxes and to detect differences between
treatments, the slurry-control was excluded from the statistical analysis of TP and PP.
The reduction in TP and PP losses when alum, PAC and FeCl2 was added to slurry was a
78
result of a combination of precipitation and floc formation, which led to a decrease in SS
loss in runoff water. In the case of lime addition, the reductions were a result of the
formation of Ca-P precipitates. The average FWMC of TP for the slurry-control during
the three rainfall simulation events was 8,390 μg L-1. This was similar to 7,000 μg L-1
reported by Preedy et al. (2001) in a rainfall simulation study to examine incidental P loss
from dairy slurry.
Measures such as increasing the time between slurry application and the first rainfall
event are as effective as chemical amendment at reducing incidental losses of P.
Chemical amendment immobilises soluble P in slurry applied to soil and could therefore
be included as a low capital cost management tool to reduce farm P status and chronic P
losses. The cost of chemical amendments in comparison to other treatment methods (e.g.
transporting to other farms, AD, separation and composting) is likely to be the most
significant factor in the future implementation of chemical amendments. Economies of
scale were not considered in this study and this could considerably reduce costs. The cost
of amendment, calculated after results of Chapter 3, based on the estimated cost of
chemical, chemical delivered to farm, addition of chemical to slurry, increases in slurry
agitation, and slurry spreading costs as a result of increased volume of slurry due to the
addition of the amendments to slurry, is shown in Table 4.2. At the scale of the present
study, alum and ferric chloride provide the best value in reducing on TP loss from slurry.
These are preliminary estimates and if the cost of using these amendments as a mitigation
measure is to be accurately calculated, then the optimum dosage for each amendment at
field-scale needs to be determined.
4.5.3. Metals in runoff water
Previous studies (Moore et al., 1998; Edwards et al., 1999) have reported that chemical
amendment of poultry litter posed no significant risk of increased metal release to runoff
water. The findings of the present study also validate this for chemical amendment of
dairy cattle slurry. Moore et al. (1998) associated an increase in Ca release from alum
treatment to a displacement of Ca in Ca-P bonds by Al. This is also likely to be the cause
79
for PAC and FeCl2 with Ca displaced by Al and Fe. The increase in Ca from the lime
treatment was expected as a high rate of lime was applied. The FWMC of Fe (Figure
4.11) decreased for all treatments except alum, which increased Fe loss by 30% compared
to the slurry-control; this was most likely a result of pH effect of alum, which increased
the Fe solubility leading to higher Fe losses. There are acute (acute concentrations being
short-term concentration and chronic being a long-term concentration) MAC (750 μg L-1)
and chronic MAC (87 μg L-1) for Al in runoff (USEPA, 2009). The Al concentrations
observed in the present study were below all MAC with the exception of slurry-control
during RS2 and grass-only treatment in RS2, which exceeded chronic MAC. There is no
MAC for Ca in water. Iron concentrations in runoff were all below the chronic MAC of
1,000 μg L-1 (USEPA, 2009).
From previous studies, adverse effects are not expected due to alum amendment to
manure. In a plot study, Moore el al. (1998) amended poultry litter with alum to examine
the effect of alum amendment on runoff concentrations of metals. Alum treatment
significantly reduced Fe in runoff. Runoff Al concentrations were not affected by
treatment and Ca concentrations increased after treatment. Moore et al. (2000) also found
Al loss from a small-scale catchment was unaffected by alum treatment. In order to
determine the effect of long-term additions of alum to poultry litter, Moore and Edwards
(2005) began a 20-yr study in 1995. The most significant findings of this study were that
long-term land application of alum-amended poultry litter did not acidify soil in the same
way as NH4-N fertilisers and that Al availability was lower from plots receiving alumtreated poultry manure than NH4-N fertiliser. McFarland et al. (2003) incorporated alum
into soil prior to application of dairy dirty water and reported no difference in Al
concentrations in runoff between control and alum amended plots.
4.6.
Conclusions
The results of this study demonstrate that chemical amendment was very successful in
reducing incidental losses of DRP, TP, PP, TDP, DUP and SS from land-applied slurry.
The results of the study demonstrate that PAC was the most effective amendment for
80
decreasing DRP losses in runoff following slurry application, while alum was the most
effective for TP and PP reduction. Incidental loss of metals (Al, Ca and Fe) from
chemically amended dairy cattle slurry was below the MAC for receiving waters. Future
research must examine the long-term effect of amendments on P loss to runoff, gaseous
emissions, plant availability of P and metal build-up in the soil. If amendments to slurry
are to be recommended and adopted as a method to prevent P losses in runoff, the impact
of such applications on slurry-borne pathogens, as well as pathogen translocation to the
soil and release in surface runoff, needs to be addressed. The long-term effects on
microbial communities in soil must also be examined. The results of this study show that
even with chemical amendment, P concentration in runoff was above the MAC.
Therefore, amendments may not be the best option for minimising incidental P losses, as
timing of applications may be just as effective at controlling incidental P losses, and may
be much more cost effective. However, chemical amendment immobilises soluble P in
slurry and has the potential to reduce chronic P losses. The use of chemical amendments
in combination with other mitigation methods such as grass buffer strips would likely
increase the effectiveness of the measures. Future work should focus on using
amendments to reduce P solubility in slurry to decrease P loss from high P soils by
binding P in slurry once it is incorporated into the soil, thereby allowing farmers to apply
slurry to soil without further increasing the potential for P loss.
4.7.
Summary
The agitator test (Chapter 3) identified amendments with the best ability to reduce P
solubility in dairy cattle slurry. Chapter 4 has shown that these amendments can
effectively reduce all forms of P in runoff in realistic conditions. The next step is to
examine these amendments at field-scale. However, before these amendments are
examined at field-scale, there is a need to examine their impact on GHG and potential
pollution swapping. Chapter 5 details the results of an experiment designed to examine
GHG and pollution swapping. These results allow feasibility discussion (Chapter 3) to be
developed further to include GHG and pollution swapping.
81
Chapter 5 Effect of chemical amendment of dairy cattle
slurry on greenhouse gas and ammonia emissions
5.1.
Overview
The previous two chapters examined the effectiveness and feasibility of amendments in
reducing P solubility. This chapter considers the effect of chemical amendment of dairy
cattle slurry on gaseous losses which, together with their impact on surface runoff, are
critical in selecting most feasible amendments for recommendation to legislators.
5.2.
Introduction
Organic manure is a valuable fertiliser resource in terms of N, P, K and micronutrients.
Losses of N and P to both groundwater and the atmosphere not only act as significant
sources of pollution, but can represent significant losses in terms of fertiliser value (Lalor,
2008). Whilst the efficacy of the various slurry amendments on P sequestration efficiency
is well quantified (Dao, 1999; Lefcourt and Meisinger, 2001; Dao and Daniel, 2002; Dou
et al., 2003; Chapters 2 and 4), there is less information on their effects on gaseous
emissions and pollution swapping. This study will allow the feasibility ranking to be
further refined to take account of GHG emissions and pollution swapping. An experiment
was designed to facilitate the measurement of NH3, N2O, CH4 and CO2 emission
following land application of dairy cattle slurry (Figure 5.1). Charcoal was included as an
additional treatment as there is a large body of work involving biochars being carried out
at present and there is the potential in their use for P mitigation and GHG control.
82
1
Air stripped of ammonia
before entering dynamic
chamber after Misselbrook
et al. (2005)
2
Sealed dynamic chambers
with air flowing
continuously
3
Acid traps used to measure
ammonia volatilisation after
Misselbrook et al. (2005)
4
Flow meters used to
measure and regulate flow
throughout the study
5
Pump used to create
vacuum to draw air over
slurry in dynamic chambers
Figure 5.1 Photograph of dynamic chamber apparatus
5.3.
Materials and Methods
5.3.1. Soil sample collection and analysis
Intact soil samples were collected from a dairy farm in Athenry, Co. Galway (53°21‘N,
8°34‘ W). 120-mm-high, 100-mm-diameter Al coring rings were used to collect
undisturbed soil core samples (n=18). Soil samples, taken to a depth of 100 mm below
the ground surface from the same location, were air dried at 40°C for 72 h, crushed to
pass a 2 mm sieve, and analysed for Morgan‘s P using Morgan‘s extracting solution
(Byrne, 1979). Soil pH (n=3) was determined using a pH probe and a 2:1 ratio of
deionised water-to-soil. Soil texture was determined by PSD (B.S.1377-2:1990a).
Organic matter content of the soil was determined using the LOI test (B.S.1377-3; BSI,
1990b). The soil was a poorly-drained sandy loam (58% sand, 27% silt, 15% clay) with a
Morgan‘s P of 22±3.9 mg P L-1, a pH of 7.45±0.15 and an OM content of 13±0.1%.
83
Historic applications of organic P from an adjacent commercial sized piggery led to high
STP in the soil used in this study.
5.3.2. Dairy slurry collection and analysis
Cattle slurry from dairy replacement heifers was taken from a dairy farm (53°21‘ N,
8°34‘ W) in County Galway, Republic of Ireland. Before sample collection, the storage
tanks were agitated. Samples were transported to the laboratory in 10-L drums and stored
at 4°C. Slurry and amended slurry pH was determined using a pH probe (WTW,
Germany) and the WEP of slurry was measured at the time of land application after
Kleinman et al. (2007). The TP of the dairy cattle slurry was determined after Byrne
(1979). Potassium and Mg were analyzed using a Varian Spectra 400 Atomic Absorption
instrument and analyses for N and P were carried out colorimetrically using an automatic
flow-through unit. Ammoniacal nitrogen of slurry and amended slurry was extracted
from fresh slurry by shaking 10g of slurry in 200 ml 0.1 M hydrochloric acid (HCl) on a
peripheral shaker for 1 h and filtering through a No 2 Whatman filter paper.
5.3.3. Chemical amendment of slurry
The six treatments examined in this study, selected based on results of Chapter 3 and 4,
were: slurry-only (the study control) and slurry amended with (1) industrial grade alum
(8% Al2O3, Al2(SO4)3.nH2O) (2) industrial grade PAC (3) analytical grade FeCl2 (4) lime
(Ca(OH)2) and (5) charcoal. With the exception of charcoal (analytical grade activated
charcoal used as biochar can vary depending on material from which it is made), the
amendments were applied at the following stoichiometric rates determined from Chapter
3: alum 1.11:1 (Al: TP); PAC 0.93:1 (Al:TP); FeCl2 2:1 (Fe:TP); and lime 10:1 (Ca: TP).
Charcoal was applied at a rate equivalent to 3.96 m3 ha-1. This corresponded to a rate
above which DM of slurry would become too high to allow landspreading without adding
water (Stan Lalor pers com, 2010). The amendments were added to the slurry and mixed
rapidly using a blender immediately before simulated land application. A grass only
background was also examined but values measured were very low compared to
84
emissions from slurry treated soil cores so these were excluded. Slurry and amended
slurry were applied directly to the surface of the intact grassed soil at a rate equivalent to
26 kg TP ha-1 (33 m3 slurry ha-1). Immediately after application, the chambers were sealed
and the air flow through the system was started and maintained for 168 h.
5.3.4. Measurement of ammonia
The dynamic chamber used in this experiment was based on a design used by
Misselbrook et al. (2005). Eight chambers were connected in parallel (Figure 5.2). Air
was drawn through the system via a vacuum pump, with air flow through each chamber
regulated at 5.1 L min-1. This was to ensure that the number of headspace exchanges per
minute was such that the emission of NH3 would not be affected by small differences in
flow rates between chambers (Kissel et al., 1977).
Figure 5.2 Diagram of apparatus used to measure ammonia emissions
85
Prior to entering each chamber, the ammonia contained in the ambient air was
immobilised using an acid trapping method. The air was drawn over the soil surface using
a vacuum pump (VTE 10 VACCUM PUMP, Irish Pneumatic Service LTD, Ireland) and
gas mass flow meters were used to regulate and measure air flow (Cole-Parmer, Hanwell,
UK).
The chambers comprised the same 200-mm-diameter Al cores used to collect the grassed
soil samples, fitted with a polypropylene lid and base (Figure 5.3). The samples were
saturated for 48 h and then allowed to drain for 48 h. During this time, the surfaces were
covered to avoid evaporation losses. After approximate field capacity was achieved, the
chambers were sealed at the base using silicon grease to ensure an air-tight seal. Each
treatment was applied to the grassed-soil surface and a lid was fitted to each chamber.
Each chamber had four inlet and outlet ports to ensure good mixing of air within the
chamber (after Misselbrook et al., 2005). During the dynamic phase, the cores were
attached to the dynamic chamber for 168 h. During this time, air was drawn through the
chambers over the surface of the treated soil and through acid traps, which were used to
measure NH3.
Figure 5.3 Dynamic chamber
86
5.3.5. Measurement of CH4, N2O and CO2
Air samples were drawn from the head space of the ammonia volatilisation chamber
(AVC) and analysed for CH4, CO2 and N2O using a photo-acoustic-analyser (PAA;
INNOVA 1412, Lumasense Inc, Denmark) (Figure 5.4). The majority of NH3
volatilisation arising from spreading of slurry occurs in initial 48 h after spreading (Gary
Lanigan pers com, 2011), while N2O and CH4 losses take place over a much longer time
period (Gary Lanigan pers com, 2011). Therefore, it was only necessary to use the AVC
for the first 168 h and then continue CH4, CO2 and N2O sampling for a further 10 d.
During the first 168 h (during which time NH3 was measured), the chamber was
disconnected from the AVC apparatus and the inlet and outlets were connected to the
PAA for 6 min at t= -1 (1 h before treatment), 0, 2, 6, 24, 48, 72, 96, 144, 168. After 168
h, NH3 measurement was discontinued and the Al cores, containing intact soil samples,
were removed from the apparatus and incubated in the laboratory. During this time, a
portable cap was fitted to each chamber and the PAA was used to measure fluxes at t = 9,
11, 13, 15 and 17 d. The mass of the sample, and therefore water content, was kept
constant throughout the experiment by periodically adding deionised water to the surface
of the soil samples.
5.3.6. Statistical analysis
Data (Appendix D) were checked for normality and homogeneneity of variance by
histograms, qq plots, and formal statistical tests as part of PROC UNIVARIATE
procedure of SAS (SAS, 2004). The data were analysed using the PROC GLM procedure
(SAS, 2004). The linear model included the fixed effects of treatment and, with the
exception of slurry pH, CH4 and CO2, data were logarithmically transformed prior to
analysis. A multiple comparisons procedure (Tukey) was used to compare means.
87
Figure 5.4 Photograph of PAA during carbon dioxide, methane and nitrous oxide
measuring period
5.4.
Results
5.4.1. Slurry and amended slurry results
The slurry had TN of 4430±271 mg L-1, TP of 1140±76 mg L-1, TK of 4480±218 mg L-1
and a pH of 7.5±0.05. The slurry TP and TK remained relatively constant, while the WEP
was lowered significantly by all chemical amendments (Table 5.1). Alum, FeCl2 and
PAC addition reduced slurry pH from approximately 7.5 to 5.4, 6.7, and 6.4, respectively
(p<0.005). The pH of alum-amended slurry was significantly different to all other
treatments, while FeCl2 and PAC were not significantly different to each other. Addition
88
of lime increased slurry pH to 12.2 (p<0.001), while charcoal did not have a significant
effect on slurry pH.
Table 5.1 Dairy cattle slurry and amended dairy cattle slurry properties
Treatment
DM (%)
Slurry-control
10.5 (0.04)
Alum
9.4 (0.16)
Lime
8.2 (0.29)
FeCl2
10.1 (0.22)
PAC
9.6 (0.28)
Charcoal
12.57 (0.45)
(Standard deviation in brackets)
pH
7.5 (0.05)
5.4 (0.12)
12.2 (0.12)
6.7 (0.06)
6.4 (0.05)
7.3 (0.4)
WEP (g/kg DM)
1.81 (0.112)
0.008 (0.002)
0.014 (0.001)
0.017 (0.001)
0.011 (0.002)
1.78 (0.23)
5.4.2. Ammonia
Alum (p<0.001), FeCl2 (p<0.005), PAC (p<0.005) and charcoal (p<0.01) reduced NH3
emissions by 92, 54, 65 and 77% compared to the slurry-control, while lime increased
emissions by 114% (p<0.001). Lime amendment resulted in the loss of 84% of TAN
applied. Alum, PAC, FeCl2 and char were not statistically different to each other. The
NH3 emissions from untreated and chemically amended slurry, expressed as a percentage
of TN and NH4-N in the applied slurry, are shown in Figure 5.5.
Ammonia release from slurry for all treatments followed a Michaelis-Menten response
curve, with the majority of emissions occurring within the first six hours following
application. With the exception of the lime treatment, chemical amendment of slurry
prior to land application increased the time for half of ammonia losses to occur (T0.5).
Alum (p<0.005), FeCl2 (p<0.05), PAC (p<0.006) and charcoal (p<0.05) increased T0.5,
compared to the slurry-control, from 1.5 to 4.1, 3.5, 4.3 and 3.4 h, respectively (p<0.05).
The T0.5 of lime-amended slurry was not significantly different to the slurry-control.
Cumulative ammonia release from untreated slurry was 40% of TAN.
89
Ammonia emission, % of total N applied
60
Slurry
Alum
FeCl2
Lime
PAC
Charcoal
50
40
30
20
10
0
0
30
60
0
30
60
90
Time (hours)
120
150
120
150
Ammonia emission, % of NH4-N
100
90
80
70
60
50
40
30
20
10
0
90
Time (hours)
Time after slurry application (hours)
Figure 5.5 Cumulative ammonia emissions from untreated and chemically amended
slurry expressed as a percentage of total nitrogen in slurry and ammoniacal nitrogen in
slurry
90
5.4.3. Nitrous oxide
Cumulative N2O emissions of dairy cattle slurry increased when amended with alum
(p<0.2) and FeCl2 (p<0.2) by 202 and 154 % compared to the slurry-control. Lime
(p<0.5), PAC (p<0.01) and charcoal (p<0.01) resulted in a reduction of 44, 29 and 63% in
cumulative direct N2O loss compared to the slurry-control.
In this study, nitrous oxide emissions following land application of dairy cattle slurry
were observed to increase from 0.18 g N2O-N ha-1 h-1 to a peak of 4 g N2O-N ha-1 h-1 at
24 h post application (Figure 5.6). Emissions of N2O from alum were similar in
magnitude and temporal dynamics to those from the slurry-control. Ferric chloride
addition resulted in no increase in N2O emissions until the 72 h sampling event, and a
peak flux of 4.7 g N2O-N ha-1 h-1 was measured at 96 h. Lime, PAC and charcoal addition
resulted in much lower emissions, with peak emissions occurring after 24-48 h.
5.4.4. Carbon dioxide
In general, addition of amendments to slurry did not significantly affect soil CO2 release
during the study (Figure 5.7), with cumulative emissions for the period ranging from 320
– 380 kg CO2 ha-1 (Figure 5.8). However, significant reductions in CO2 efflux were
observed upon charcoal addition, with an 84% reduction in cumulative CO2 emissions
observed (p<0.05).
Immediately following land application of dairy cattle slurry and chemically amended
slurry, there was generally a peak in CO2 emissions followed by a steady release for the
duration of the study. The lime amended slurry behaved differently to the other
treatments and the slurry-control, and acted as a CO2 sink immediately after land
application. However, the cumulative emissions were similar to PAC and FeCl2 treated
slurry.
91
13
Slurry only
Alum
Ferric chloride
Lime
11
9
7
5
3
1
-1
-3
N2O g (N2O-N ha-1 h-1)
13
11
9
7
5
3
1
-1
-3
13
PAC
Charcoal
11
9
7
5
3
1
-1
-3
-50
50
150
250
350
-50
50
150
250
350
Time from land application of dairy cattle slurry (hours)
Figure 5.6 Nitrous oxide emissions from slurry and amended slurry in chambers (Mean ±
standard error)
92
14
Slurry only
12
Alum
Ferric chloride
Lime
PAC
Charcoal
CO2 (kg CO2-C ha-1 h-1)
10
8
6
4
2
0
-2
-4
-50
0
50
100
150
200
250
300
350
400
Time from land application of dairy cattle slurry (hours)
Figure 5.7 Carbon dioxide emissions from slurry and amended slurry in chambers.
(Mean ± standard error)
1000
Global warming potential ( kg CO2-eq ha-1)
Methane
Carbon dioxide
800
600
400
200
0
-200
Slurry only
Alum
Ferrous
Lime
PAC
Charcoal
Treatment
Figure 5.8 Cumulative carbon dioxide emissions from chambers for duration of study.
(Mean ± standard error)
93
5.4.5. Methane emissions
Methane emissions increased from -0.18 g CH4-C ha-1 h-1 to 94 g CH4-C ha-1 h-1 upon
application of dairy cattle slurry (Figure 5.9). These levels decreased rapidly to
approximately 7 g CH4-C ha-1 h-1 by 48 h and remained relatively constant until the 312 h
sampling event. Following this, methane losses were much more variable. There was a
similar trend for all of the amended slurries applied with an initial increase in losses
followed by a rapid decrease and then steady release for the duration of the study. All of
the amendments examined reduced the initial peak in CH4 emissions compared to the
slurry-control (p<0.0001). Lime (p<0.05), PAC (p<0.08) and FeCl2 (p<0.09) reduced
cumulative CH4 emissions compared to the slurry-control by 134, 121 and 99%,
respectively. Alum, charcoal and the slurry-control were not significantly different to
each other.
120
Slurry only
Alum
Ferric chloride
Lime
PAC
300
350
Charcoal
100
80
CH4 g CH4-C ha-1 h-1
60
40
20
0
-20
-40
-60
-50
0
50
100
150
200
250
400
Time from land application of dairy cattle slurry (hours)
Figure 5.9 Methane emissions from slurry and amended slurry in chambers. (Mean ±
standard error)
94
5.4.6. Impact of amendments on global warming potential
Chemical amendment of dairy cattle slurry has been proposed as a possible P mitigation
measure for the control of P solubility in dairy cattle slurry (Chapters 3 and 4). In order to
access the pollution swapping potential of the treatments, all emissions were expressed in
CO2 equivalents. Cumulative direct and indirect N2O emissions from slurry and amended
slurry in the chambers during the study are shown in Figure 5.10.
Global warming potential (CO2 equivalents)
1000
900
800
700
600
500
Indirect nitrous oxide
400
Nitrous oxide
300
200
100
0
Slurry only
Alum
Ferrous
Lime
PAC
Charcoal
Treatment
Figure 5.10 Nitrogen cumulative emissions (Nitrous oxide and indirect emissions
resulting from ammonia losses) expressed in CO2 equivalents. (Mean ± standard error)
Indirect N2O emissions were calculated based on the assumption that all the NH3 would
be re-deposited within a 2 km radius of the point of application, which allowed use of an
emission factor of 1% (IPCC, 2006). Alum, FeCl2, lime and PAC have no significant
effect on the sum of the cumulative direct and indirect N2O emissions, while charcoal
reduced total N2O emissions from by 69% compared to the slurry-control (p<0.01). The
total N2O emissions from charcoal treated slurry – with the exception of PAC - were
95
statistically different to slurry (p<0.01), alum (p<0.01), FeCl2 (p<0.001), lime (p<0.001)
treatments. Cumulative carbon dioxide and methane emissions are shown in Figure 5.8.
Charcoal reduced total cumulative CO2 and CH4 emissions compared to the control
(p<0.001) and was significantly different to alum (p<0.001), FeCl2 (p<0.05), lime
(p<0.01) and PAC (p<0.05). All gases measured have been expressed in CO2 equivalents
and are plotted in Figure 5.11. Amendment of slurry with charcoal significantly reduces
greenhouse warming potential (GWP) following land application of dairy cattle slurry
(p<0.001). In this study, there was no significant effect of any amendment of slurry on
GWP caused by land application of dairy cattle slurry, with the exception of charcoal.
Global warming potential (CO2 equivalents)
1400
1200
Carbon dioxide
Indirect nitrous oxide
Nitrous oxide
Methane
1000
800
600
400
200
0
-200
Slurry only
Alum
Ferrous
Lime
PAC
Charcoal
Figure 5.11 Cumulative carbon dioxide (CO2), indirect nitrous oxide (N2O), direct N2O
and methane (CH4) measured during the study expressed in CO2 equivalents. (Mean ±
standard error)
96
5.5.
Discussion
5.5.1. Ammonia emissions
Ammonia volatilisation from dairy cattle slurry following land application is controlled
by: humidity, temperature, wind speed at the time, method of application, and the degree
of infiltration of the slurry into the soil (Søgaard et al., 2002, Sommer et al., 2003,
Sommer et al., 2006). In addition, slurry pH, DM and TAN content greatly influence the
rate and amount of NH3 volatilisation (Smith et al., 2000; Misselbrook et al., 2000;
Meisinger et al., 2001). It is estimated that between 60-80% of TAN applied can be lost
during broadcast land spreading of cattle slurry, particularly during the first 12 h post
application (Pain et al., 1989, Hyde et al., 2003). In the present study, cumulative NH3
loss from land applied dairy cattle slurry was 22.6 kg NH3-N ha-1, with approximately
39% of NH4-N applied lost in initial 24 h; this was equivalent to 15% of TN applied.
With the exception of lime, all amendments used reduced NH3 losses compared to the
slurry-control. This reduction was expected as chemical amendments, such as alum, have
been used extensively in the USA to reduce NH3 emissions from poultry litter (Moore et
al., 1999) and from dairy cattle slurry (Table 5.2). Meisinger et al. (2001) reported a 60%
reduction in NH3 loss from dairy cattle slurry when 2.5% by weight of alum was added in
a laboratory batch experiment. In a field study, Shi et al. (2001) reported a 92% reduction
in NH3 loss. The results of the present study were in agreement with previous findings for
alum, PAC and FeCl2, and the ammonia abatement by alum, PAC and FeCl2 was
primarily due to reductions in pH (ie. N was held in the ammonium form).
The large reductions in ammonia emissions associated with charcoal addition (74%) may
have been due to both ammonia gas and ammonium ion adsorption, as biochar can act as
a cation exchange medium (Asada et al., 2002). During pyrolysis of woody material for
biochar production, thermolysis of lignin and cellulose occurs, exposing acidic functional
groups, such as carboxyl groups. This has been shown to result in an 80-100% removal
efficiency for ammonia gas (Oya and Iu, 2002; Iyobe et al., 2004). Biochar addition
97
during the composting of poultry litter reduced ammonia losses by 64%, even though pH
increased (Steiner et al., 2010). As a result, the mechanism was thought to be due to the
adsorption of ammonium ions as opposed to the immobilization of ammonia (Steiner et
al., 2008). In addition, biochar has also been found to reduce N leaching by 15% due to
adsorption of the ammonium ion predominantly by cation exchange (Ding et al., 2011).
Table 5.2. Summary of amendments used to reduce ammonia emissions in previous
studies
Reference
Meisinger et al.
(2001)
Kai et al. (2007)
Chemical
Amount added
Slurry
Study
% NH3
pH
to slurry
type
type
reduction
slurry
alum
2.5% (w/w)
Dairy
Lab
60
4.5
zeolite
6.25% (w)
55
7.8
H2SO4
5 kg m-3
70
6.3
Swine
Field
Comments
Simulated storage experiment
Farm scale storage and
application
Smith et al. (2001a)
Alum
0.75% (v/v)
Swine
Plot
52
6-week study
Molloy and Tunney,
FeSO4
0.8 g to 25 g
Dairy
Batch
81
Batch scale experiment
MgCl2
0.8 g to 25 g
23
CaCl2
0.8 g to 25 g
50
7.8
Alum
4500 kg ha-1
92
5.98a
CaCl2
4500 kg ha-1
71
6.99a
HCL
240 m Eq
CaCl2
300 m Eq
(1983)
Shi et al. (2001)
Husted et al. (1991)
a
Dairy
Field
Dairy
Applied to surface of feedlot
90
Lab
15
pH referred to is the pH of soil and slurry mixture
Lime increased slurry pH to 12.2 and increased the NH3 loss compared to the slurrycontrol. Molloy and Tunney (1983) reported an increase in pH to 7.8 and a 50% decrease
in NH3 loss when CaCl2 was added to dairy cattle slurry. This suggests that, although
there may be potential to reduce NH3 loss using Ca-compounds such as lime, it is not
feasible at application rates high enough to reduce P solubility in dairy cattle slurry.
There was a linear relationship between slurry pH at time of application and NH3 loss
from slurry and amended slurry in this study (R2=0.86) (Figure 5.12). This would indicate
that the change in slurry pH was the main process responsible for the reduction in NH3
loss from dairy cattle slurry. In addition, there was a significant relationship (R2=0.98)
between slurry pH at the time of application and the log of the T0.5 (Figure 5.12). This
98
would indicate that if large NH3 losses do not occur in the short-term after land
spreading, the potential for loss is significantly reduced i.e. chemical treatments are not
just delaying NH3 loss, but mitigating it completely.
In addition to environmental problems caused by NH3 losses, such losses reduce the
nutrient value of the fertiliser and increase NH3 emissions from slurry. The value of N
lost via ammonia and N2O emissions from the slurry-control for the duration of the study
amounted to approximately €0.63 per m3 slurry applied based on cost of €1.10 per kg N
(Stan Lalor pers com, 2011). Alum, FeCl2, PAC and charcoal increased the fertiliser
value of slurry by €0.56, €0.32, €0.41 and €0.48 per m3 of slurry compared to the slurrycontrol.
1.2
y = 6.9236x - 36.497
R² = 0.8593
50
40
1
Log10 T0.5
Cumultive NH3 emissions
60
30
20
10
0.6
y = 0.05x + 0.4857
R² = 0.985
0.4
0.2
0
-10
0.8
0
0
5
10
15
0
5
10
15
Slurry pH
Slurry pH
Figure 5.12 Relationship between slurry and amended slurry pH at time of application
and (a) cumulative NH3 emissions and (b) and log of time for half of ammonia emissions
to occur (T0.5)
5.5.2. Nitrous oxide
Land application of agricultural wastes results in an increase in N2O emissions from soil
(Velthof and Oenema, 1997). Nitrous oxide is of environmental importance as it
contributes to global warming and the depletion of the ozone layer. It is produced by
nitrification and denitrification processes. Nitrous oxide emissions are influenced by: soil
99
moisture status, soil temperature; soil nitrate content and organic carbon content (Velthof
et al., 2002). It was hypothesised that any reduction in NH3 loss would result in a
concomitant increase in N2O in soil due to higher soil N available for
nitrification/denitrification. Alum amendments were shown to double cumulative N2O
losses compared to the slurry only treatment, whilst lime addition resulted in a decrease
in N2O emissions. Although N2O emissions of the treatments examined were not
significantly different to the control, alum and charcoal were significantly different to
each other (p<0.01). The low direct N2O losses associated with lime addition were
merely due to the fact that most of the available mineral N had been already lost during
volatilisation. Ammonia volatilisation can also lead to indirect N2O emissions as the
majority of ammonia volatilised in the field is re-deposited within 2 – 5km via wet and
dry deposition, and a proportion (1%) is re-emitted as N2O (IPCC, 2006). When these
indirect losses were calculated, lime addition accounted for an increase in indirect N2O
emissions from 283 g N2O ha-1 for the slurry-control to 606 g N2O ha-1. These results
highlight the need to account for all gaseous N losses as an analysis of ammonia or N2O
in isolation would give skewed results.
In terms of abating total N emissions, biochar was the most effective amendment
reducing total N2O losses by 63%. There is currently sparse information on the effect of
biochar on N2O emissions. Some laboratory studies have indicated that biochar may
reduce N2O by increasing soil aeration and hence reduce water-filled pore space (Yanai et
al., 2007). Alternatively, if pH is increased upon charcoal addition, this may induce a
shift towards total de-nitrification to N2, thus reducing N2O (Clough and Condron, 2010).
5.5.3. Carbon emissions
The majority of amendments had little effect on soil CO2 respiration, demonstrating that
the amendments neither stimulated nor retarded soil microbial processes. The reduction
in CO2 emissions associated with charcoal was surprising considering that a C source was
added. Previous studies on charcoal application to organic manures have shown an
100
increase in C emissions in the short-term (Steiner et al., 2010), while biochar addition to
soils have also indicated a simulation of soil microbial respiration (Wardle et al. 2008).
After land application, CH4 emissions are of minor importance compared to NH3 and
N2O emissions (Wulf et al., 2002a, b). Methane is produced mainly by microbial
decomposition of OM under anaerobic conditions. The highest efflux was for untreated
slurry and alum, immediately post manure application would indicate CH4 formation
during manure storage, as there would not be sufficient time for its formation in the soil.
It is produced during slurry storage and shortly after slurry application, after which time
the OM is oxidised to CO2 and H2O as aerobic conditions prevail. Initial CH4 emissions
in the following few hours most likely originate from CH4 contained in the manure
diffusing from the viscous layer, while subsequent emissions were likely to be produced
during the degradation of labile carbon compounds (Chadwick et al., 2000; Sherlock et
al., 2002). Kasimir-Klemedtsson et al. (1997) reported similar base-line CH4 soil
emission levels of 1.1 kg CH4-C ha-1 day-1 (3.01 g CH4-C ha-1 day-1) from Swedish cereal
cropped soils, while Rodhe et al. (2006) recorded similar peak CH4 emissions of
approximately 75 g CH4-C ha-1 day-1 immediately post application of cattle slurry to
grassland. Chadwick and Pain (1997) also reported high emission levels following pig
and dairy manure application to grassland soil in laboratory experiments.
5.5.4. Impacts of pollution swapping
Chemical amendment of dairy cattle slurry provides an opportunity to immediately
reduce P solubility in dairy cattle slurry and could be included as a low capital cost
management tool to reduce P solubility in manure and reduce farm P status in the shortterm, as other management practices come into effect. This study allows for the effect of
chemical amendment on gaseous emissions to be incorporated into the feasibility analysis
of Chapter 3. The ranking system, determined in Chapter 3, was based on effectiveness,
efficiency, potential barriers to use and cost of implementation. A new feasibility analysis
was developed to include the results of this study and to give recommendations for the
best amendment to mitigate DRP losses with the least potential for pollution swapping.
101
The results of this feasibility analysis are shown in Table 5.3. Charcoal was excluded as
there is insufficient data on P sequestration potential to date. In order of decreasing
feasibility, the amendments were ranked from best to worst as follows: PAC, alum, FeCl2
and lime. Therefore, the amendments selected for recommendation for further study are,
from best to worst: PAC, alum and lime. Ferric chloride was excluded due to risk of
stability of Fe-P bonds in soil. Although there are similar concerns with lime, it is
currently added to soil in Ireland to reduce acidity in soils and for this reason, it was
decided to recommend lime over FeCl2.
Table 5.3 Summary of feasibility of amendments (Adapted from Chapter 3). Marks for
feasibility and pollution swapping are from 1 to 5. 1 = best 5 = worst.
Chemical
Alum
Ratio used
Chapter 3
Feasibility
score P
Pollution
swapping
Combined
feasibility
0.98:1 Al: P
1
5
6
Notes
Risk of effervescence
Risk of release of H2S due to anaerobic
conditions and reduced pH
Cheap and used widely in water treatment
AlCl3
(PAC)
0.98:1 Al: P
2
2
4
Reduced ammonia emissions
No risk of effervescence (Smith et al.,
2004)
AlCl3 increased handling difficulty
Expensive
FeCl2
(FeCl3)
2:1 Fe: P
3
4
7
Reduced ammonia emissions
Potential for Fe bonds to break down in
anaerobic conditions
Increased release of N2O
Reduced ammonia emissions
Ca(OH)2
5:1 Ca: P
4
3
7
Increased NH3 loss
Strong odour
Hazardous substance
Charcoal
1
Potential to reduce P solubility limited
work to date
Improve soil microbial health
Reduced GHG emissions
Reduced ammonia emissions
5.6.
Conclusions
This study showed that P mitigating amendments can result in pollution swapping. The
amendments selected for recommendation for further study are, from best to worst, PAC,
102
alum and lime. Charcoal has excellent potential to reduce GHG losses caused by the land
application of dairy cattle slurry. There is a need to develop biochars which are efficient
in sorbing P and can improve soil quality and reduce GHG emissions. In addition, at the
current cost of treatment, the increase in fertiliser value of the slurry due to some
treatments is not sufficient to offset the cost of treatment. In this study, there was no
significant effect of any amendment of slurry on GWP caused by land application dairy
cattle slurry, with the exception of charcoal
5.7.
Summary
It is critical that when evaluating the feasibility of these amendments, ‗pollution
swapping‘ is considered. This study has identified the need for a field study to examine
the effect of the amendments on gaseous losses. In addition, there is a need to examine
the effect of amendments using different soil types and wetting and drying regimes.
Chapter 6 details the results of a runoff study following the landspreading of chemically
amended slurry at field-plot scale and Chapter 7 examines the impact of chemically
amended slurry on soil properties over a 9-mo study duration.
103
Chapter 6
6.1.
Plot-scale rainfall simulation study
Overview
This plot-scale runoff experiment was designed to develop an understanding of the
performance of amendments under more realistic conditions. In this experiment, natural
drainage occurred, which did not occur in the runoff box experiments. The plot and
runoff characteristics such as soil volumetric water content, time to runoff and runoff
volume were also measured to investigate potential adverse effects of amendments on
runoff at a larger scale.
6.2.
Introduction
The present study examines the effect of chemical amendment of dairy cattle slurry with
alum, PAC and lime on both P and N losses to runoff, whereas plot and runoff-box
experiments which have examined chemical amendment of dairy cattle slurry to date
have focused almost entirely on P losses. Although P is the limiting nutrient in freshwater
systems (Correll, 1998), N losses also pose a significant risk to water quality (Johnes et
al., 2007; Vitousek et al., 2009). When chemical amendments are used to reduce P losses,
it is important that the effects of amendments on N losses through runoff, leaching and
volatilisation are also examined to ensure that ‗pollution swapping‘ does not occur.
The experimental set-up of the present study tested the efficacy and feasibility of using a
variety of chemical amendments in the field, but still under controlled conditions. The
objectives of this study were to investigate the effect of chemical amendment of dairy
cattle slurry on: (1) average FWMC of DRP, DUP, PP and TP (2) average FWMC of
104
NO3, NO2 and NH4-N; and (3) plot and runoff characteristics such as soil volumetric
water content, time to runoff and runoff volume.
6.3.
Materials and Methods
6.3.1. Study site
This study was conducted on a 0.6 ha isolated plot on a beef farm located at Teagasc,
Johnstown Castle, Environmental Research Centre (latitude 52º 17‘N, longitude 6º
29‘W), in the southeast of Ireland (Figure 6.1). This area has a cool maritime climate, a
mean annual precipitation of 1002 mm (effective rainfall from between 400 to 500 mm),
and a mean annual temperature of 9.6°C (Ryan and Fanning., 1996). The location of 25
experimental plots within the 0.6 ha site was determined by: topography/slope, soil
texture/drainage, depth to watertable and soil analysis. For textural analysis, 100 mmdeep soil samples (n=3) were taken from a 1 m2 area at the top, middle and bottom of the
plot (Figure 6.1). Soil texture was determined using PSD analysis after B.S.1377-2:1990
(BSI, 1990a). An electromagnetic conductivity and resistivity survey was also used to
infer textural and drainage characteristics.
The site had undulating topography with a 6.7% slope along its length and an average
slope of 3.6% across the site. The topsoil was classified as a Haplic Stagnosol (Rachel
Creamer pers com, 2011). Combining PSD and geophysical data together, textural classes
ranged from a fine loam-to-clay loam within the plot. The top of the plot comprised
gravelly clay with pockets of silty/clayey gravel underlain by silt/gravel (20 to 26 mSm-1)
and was relatively well-drained compared to the lower part of the site, which comprised
silt/clay and was poorly drained (>26 mS m-1). The median perched watertable depth in
three piezometers (top, middle and bottom) was 0.6 m below ground level (bgl) on site.
The nutrient status of the soil at these locations was determined using Morgan‘s P
extractant (Morgan, 1941) and, together with K and Mg, are presented in Table 6.1. The
soil was classified as P index 3 (>5.1 mg L-1 for grassland soils in accordance with SI 610
of 2010) throughout the site, meaning that it represented minimum risk of P loss to water.
105
Soil pH (n=3) was determined using a pH probe and a 2:1 ratio of deionised water to soil
(Table 6.1).
Figure 6.1 Map of study site showing ground elevation, topography, slope, soil
conductivity, groundwater flow direction, location of subplots and of groundwater wells.
The location selected was of uniform topography, soil classification, texture and drainage
characteristics. In addition, it was in the location of the site with the highest water table
106
and had relatively constant soil nutrient status. Once the study location was selected, each
plot was isolated and instrumented with a runoff collection channel (Figure 6.1).
Table 6.1 Soil pH, Morgan‘s extractable P, K and Mg, sand silt, clay fractions, and
textural class of soil used in this study. The location of the piezometers is illustrated in
Figure 6.1
Position
a
Piezometer
No.
pH
Morgan‘s
P
mg L-1
P indexa
K
Mg
Sand
Silt
Clay
mg L-1
mg L-1
%
%
%
Textural Class
Lower
1
5.8
2.6
2
173
171
52
30
18
Sandy Loam
Middle
2
5.9
3.2
3
140
195
47
36
18
Sandy Silt Loam
Upper
Average
Std dev
3
6.1
5.9
0.2
3.6
3.1
0.5
3
96
136
38.6
151
172
22
44
47.7
4
36
34.0
3.5
21
19.0
1.7
Clay Loam
P index is the classification system used in Ireland to classify soil P status of soils (Schulte et al, 2010b)
The treatments were randomly assigned to twenty-five plots (0.9 m by 0.4 m) which were
orientated along a line. Composite soil samples (100 mm) were taken from each plot and
WEP was determined (n=3). Soil pH and Morgan‘s P were determined, and the slope of
each plot was surveyed. Soil pH (5.96±0.22) was consistent across the 25 plots (Table
6.2). Soil test P (4.95±1.75 mg P L-1) and WEP (7.24±4.52 mg P kg-1) appeared to vary
across the site, with lower values observed close to the location of the piezometers.
Figure 6.2 shows photographs of site setup, plot installation and runoff collection troughs.
6.3.2. Slurry analysis
Cattle slurry was taken from the dairy farm at the Teagasc, Environmental Research
Centre, Johnstown Castle, in August of 2010. The storage tanks were agitated and slurry
samples were transported to the laboratory in 25-L drums. Slurry samples were stored at
4°C prior to land application. Slurry pH was determined using a pH probe (WTW,
Germany). The TP of the dairy cattle slurry was determined after Byrne (1979). Total
potassium, TN and TP were carried out colorimetrically using an automatic flow-through
unit (Varian Spectra 400 Atomic Absorption instrument). The WEP of slurry and
amended slurry was measured at the time of land application after Kleinman et al. (2007),
and NH4-N of slurry and amended slurry was extracted by shaking 50 g of slurry in 1 L
107
of 0.1 M HCl on a peripheral shaker for 1 h and filtering through No. 2 Whatman filter
paper at the time of application. The results of the slurry analysis are shown in Table 6.3.
The slurry sample was typical of slurry found on farms in Ireland (SI 610 of 2010). The
slurry TN, TP, NH4-N and TK were constant with the exception of the lime-treated
slurry, which had high TN, TP and TK. The WEP of slurry was lowered significantly by
all alum and PAC amendments. Alum addition reduced the slurry pH from approximately
7.1 to 6.5, while lime addition increased the slurry pH to 8.8.
Table 6.2 The average slope for each block, soil pH, water extractable phosphorus
(WEP), Morgan‘s extractable P, potassium (K), and magnesium (Mg) before application
of treatments.
Block
Slope
pH
WEP
%
g kg
P
-1
K
mg L
-1
mg L
Mg
-1
mg L-1
1
4.7 (1.5)
6.1 (0.22)
5.5 (2.3)
3.25 (0.82)
49.6 (5.7)
123 (4.5)
2
3.2 (1.8)
5.9 (0.14)
7.5 (3.3)
4.9 (1.9)
55.2 (8.2)
150 (5.7)
3
2.3 (1.9)
6.06 (0.26)
11.4 (5.9)
6.9 (0.83)
59.5 (7.8)
184 (6.7)
4
3.3 (1.7)
6.02 (0.22)
6.8 (5.1)
6.07 (0.85)
58.4 (6.57)
230 (1.2)
5
4.4 (1.1)
5.77 (0.16)
5 (3.6)
3.59 (0.72)
60.8 (4.5)
218 (5.7)
Average
3.58
5.97
7.24
4.94
56.7
181
Std deviation
0.97
0.13
2.53
1.6
4.5
45
(Standard deviations in brackets)
Table 6.3 Slurry DM, pH, water extractable phosphorus (WEP), total nitrogen (TN), total
phosphorus (TP) and total potassium (TK) and average concentrations of NH4- N (n=5)
Treatment
DM
Slurry
9.1 (0.54)
Alum
9.6 (0.58
PAC
9.42 (0.64)
Lime
9.4 (0.38)
Average
9.38
Std dev
0.2
(Standard deviations in brackets)
pH
7.1 (0.62)
6.5 (0.44)
6.9 (0.47)
8.8 (0.67)
7.325
1.01
WEP
TN
TP
TK
NH4+-N
g kg-1
mg L-1
mg L-1
mg L-1
mg L-1
3.19 (0.37)
0.0028 (0.001)
0.0074 (0.008)
2.48 (0.99)
1.4
1.7
3960 (741)
4410 (590)
3980 (1280)
5010 (725)
4340
492
1240 (145)
1260 (190)
1200 (270)
1390 (150)
1270
82.2
5170 (870)
5210 (640)
4330 (1290)
5610 (840)
5080
538
1200 (260)
1160 (270)
1180 (290)
1210 (300)
1190
22.2
108
Grass cut and plots isolated
Plot during micro-plot installation
Plot isolation
Runoff collection. Shield removed to allow
photo to be taken
Figure 6.2 Plot set up and runoff collection photograph
6.3.3. Treatments
The five treatments examined in this study were: (1) grassed soil-only, (2) slurry-control
(3) industrial grade liquid alum (Al2(SO4)3.nH2O), comprising 8% Al2O3 (4) industrial
grade liquid poly-aluminium chloride hydroxide (PAC) (Aln(OH)mCl3n-m) comprising
10% Al2O3 and (5) lime (Ca(OH)2). Amendments were added to the slurry and mixed
rapidly by shaking in 2-L containers immediately prior to land application. Two days
109
before the first rainfall simulation, slurry and amended slurry were applied directly to the
surface of the grassed soil. Slurry application rates were equivalent to 33 m3 slurry ha-1
(42 kg TP ha-1), the rate most commonly used in Ireland (Coulter and Lalor, 2008).
Amendments were applied at stoichiometric ratios determined in Chapter 3. Alum was
applied at a rate of 1:1 (Al: TP); poly-aluminium chloride at a rate of 0.85:1 (Al: TP); and
lime at a rate of 3.9:1 (Ca: TP). Appendix E shows photographs of amended slurry.
6.3.4. Rainfall simulation
Two identical portable multi-drop ‗Amsterdam type‘ rainfall simulators, described by
Bowyer-Bower and Burt (1989), were used in this study. These rainfall simulators have
been used on similar permanent grassland sites and soil types (Kurz et al, 2006; Kramers
et al., 2009; O‘Rourke et al, 2010). The rainfall simulators were designed to distribute
rainfall over a surface area of 0.5 m2 and were calibrated to deliver rainfall at an intensity
of 11 mm h-1. In order to ensure the absence of edge effects, the study plots – each
measuring 0.36 m2 in area - were positioned directly under the rainfall simulator. The
plots were isolated using 2.2 m-long, 100 mm-deep rigid plastic sheets, which were
pushed 50 mm into the soil to isolate three sides of the plot. The runoff collection channel
was placed at the bottom of the slope (Figure 6.1). Plots were orientated with longest
dimension in the direction of the slope (average 3.6 %). The runoff collector comprised a
polypropylene plastic U-shaped channel piece, which was cut in half and wedged against
the soil at a depth of approximately 25 mm below the soil surface (Figure 6.1).
A 400 mm-wide edging tool was used to ensure a good seal between soil and collector.
The plots were left uncovered for two weeks prior to first rainfall simulation to allow
natural rainfall to wash away soil disturbed by inserting the isolators. The grass on all
plots was clipped to a height of 50 mm two days prior to the first simulated rainfall event.
Figure 6.3 shows one of the rainfall simulators used in this study. Land application of
treatments was staggered over three days and applied in blocks to allow for the first
rainfall event (RS1) two days after land application of slurry. The second event (RS2)
was 10 d after the original application (t = 12 d) and the third (RS3) after 28 d (t = 30 d).
110
Rainfall simulations were carried out between 17th September 2010 and 18th October
2010 (Figure 6.4).
Wind shield used to prevent rain from blowing
View of rainfall simulator before rainfall starts
rain
Figure 6.3 Photographs of rainfall simulator
The allocation of the rainfall simulators was randomised between blocks and alternated
for treatments. Runoff was judged to occur once 50 ml of water was collected from the
runoff collection channel and the time from start of rainfall simulation to runoff of 50 ml
being the time to runoff (TR). Samples were collected every 5 min for RS1, and every 10
min for RS2 and RS3. Surface runoff was collected for 30 min once runoff commenced
to allow the FWMC to be calculated (Kurz et al., 2006). Rainfall simulator input water
had the following average concentrations: 0.05 mg NH4-N L-1, 4.61 mg NO3-N L-1, 0.001
mg DRP L-1 and 0.004 mg TP L-1; 0.00 mg NH4-N L-1, 4.53 mg NO3-N L-1, 0.004 mg
DRP L-1 and 0.00 mg TP L-1; 0.00 mg NH4-N L-1, 4.51 mg NO3-N L-1, 0.00 mg DRP L-1
and 0.00 mg TP L-1 for RS1, RS2 and RS3 respectively.
111
Figure 6.4 Natural rainfall and average depth of simulated rainfall received by the plots
for each event
The volumetric water content of soil in each plot was measured immediately prior to each
rainfall simulation event using time domain reflectrometry (Delta-T Devices Ltd.,
Cambridge, UK) (Figure 6.5), which was calibrated to measure resistivity in upper the 50
mm of the soil in each plot. Three readings were taken in each plot and the average was
calculated.
112
Figure 6.5 Photo of the measurement of volumetric water content of soil using time
domain reflectrometry
Immediately after collection, runoff water samples were filtered through 0.45µm filter
paper and a subsample was analysed colorimetrically for DRP, total oxidized nitrogen
(TON), NO2-N and NH4-N using a nutrient analyser (Konelab 20, Thermo Clinical
Labsystems, Finland). Nitrate was calculated by subtracting NO2-N from TON. A second
filtered sample was analysed for TDP using acid persulphate digestion. Unfiltered runoff
water samples were analysed for TP with an acid persulphate digestion. Particulate
phosphorus was calculated by subtracting TDP from TP. The DRP was subtracted from
the TDP to give the DUP. All samples were tested in accordance with the Standard
Methods (APHA, 1995).
6.3.5. Statistical analysis
The structure of the data (Appendix F) set was a blocked one-way classification
(treatments) with repeated measures over time (events). The analysis was conducted
using Proc Mixed in SAS software (SAS, 2004) with the inclusion of a covariance model
to estimate the correlation between events. A large number of covariates were recorded,
including measurements on the simulators. For each analysis, this set of covariates was
screened for any effects that should be included in an analysis of covariance. The
113
interpretation was conducted as a treatment x time factorial. Comparisons between means
were made with compensation for multiple testing effects using the Tukey adjustment to
p-values. Significant interactions were interpreted using simple effects before making
mean comparisons. In order to ensure that STP variation did not affect the experiment,
STP was included as a variable in the statistical analysis. Slurry concentration, which was
of much greater significance in terms of P concentrations in runoff following slurry
application, was uniform within each block.
6.4.
Results
6.4.1. Phosphorus (FWMC of DRP, DUP, PP and TP)
The average FWMC of DRP, DUP and PP, which comprise TP in runoff, are shown in
Figure 6.6. During RS1, alum (p<0.05) and PAC (p<0.001) reduced DRP in runoff water
compared to the slurry-control by 95 (0.13 mg P L-1) and 98% (0.05 mg P L-1),
respectively. Alum and PAC, at p<0.02 and p<0.01, also reduced TP concentrations in
runoff from the plots during RS1 by 92 (0.61 mg P L-1) and 83% (1.37 mg P L-1),
respectively, compared to the slurry-control. None of the amendments examined reduced
FWMC of DRP or TP losses to below the MAC during the study.
The FWMC of TP and DRP for the alum-amended plots did not show any discernable
trend, although the average reduction in FWMC, compared to the slurry-control, over the
three rainfall events, for TP and DRP was 81 and 77%, respectively. Comparatively, the
FWMC of TP continued to reduce over the three rainfall events for the PAC-amended
plots, although the DRP concentrations were still over the MAC for all runoff events.
Alum-treated slurry and PAC-treated slurry were not significantly different to each other
throughout the study. However, there was a significant difference in FWMC of TP in
runoff during RS1 between soil-only (p<0.05), alum (p<0.05) and PAC (p<0.01)
compared to the slurry-control.
114
12
PP
DUP
DRP
10
TP (mg L-1)
8
6
4
2
0
1
2
3
1
Slurry
2
3
1
Alum
2
3
1
PAC
2
3
1
Lime
10
2
3
Soil
PP
DUP
DRP
TP (mg L-1) (Log scale)
1
0.1
0.01
1
2
Slurry
3
1
2
3
1
Alum
2
3
PAC
1
2
Lime
3
1
2
3
Soil
Treatment
Figure 6.6 Average flow-weighted mean concentrations of dissolved reactive phosphorus
(DRP), dissolved un-reactive P (DUP) and particulate P (PP) comprising total P (TP) for
three rainfall simulation events, and maximum allowable concentrations (MAC) in
waterways.
115
The addition of lime increased the average FWMC of DRP and TP over the three rainfall
events, compared to the slurry-control, by 82 and 38%, respectively. This increase in P
loss as a result of lime amendment may be due to the pH of the lime-amended slurry.
Penn et al (2011) found that in order for Ca-phosphate bonds to remain stable, the pH
must remain in a range of 6.5 to 7.5. The average pH of the soil on the site was 5.97 and
the pH of the lime-amended slurry was 8.8 at the time of application. Chapter 3 showed
that the pH of lime-amended dairy cattle slurry increased in the first 24 h following land
application. The slurry pH was too high for Ca-P bonds to be stable during RS1 and when
the slurry and soil interacted and reached equilibrium, the soil pH was lower than the
optimal pH for the formation of Ca-P bonds. This may be why reductions were not
observed during RS2 and RS3.
6.4.2. Nitrogen
The average FWMC of NO3-N, NO2-N and NH4-N in runoff water for grassed soil-only
plots for the three simulated rainfall events were 3.98 mg NO3-N L-1, 0.03 mg NO2-N L-1
and 0.22 mg NH4-N L-1 compared to 3.6 mg NO3-N L-1, 0.02 mg NO2-N L-1 and 0.82 mg
NH4-N L-1 for the slurry-control (Figure 6.7). The NO3-N and NO2-N concentrations in
runoff water from soil only plots were not in excess of the MAC of 11.3 mg NO3-N L-1
(EEC, 1988) and 0.1 mg NO2-N L-1 (OJEC, 2006) for salmonidal rivers. The addition of
amendments had no significant effect on NO3 concentration in runoff water. Ammonium
concentrations in runoff from plots receiving alum-amended dairy cattle slurry, averaged
across the rainfall events, were in excess of lower drinking water standards of 0.2 mg
NH4-N L-1, but below the upper limit of 4 mg NH4-N L-1 (EEC, 1989).
The alum amendment increased NH4-N in runoff by 84% from 2.4 mg NH4-N L-1 in the
slurry-control to 4.3 mg NH4-N L-1 during RS1, while PAC reduced NH4-N in runoff by
80% (0.4 mg NH4-N L-1) compared to slurry-control during RS1. Lime had no significant
effect on NH4-N concentrations in runoff water. The peak in NH4 loss during RS1 was a
result of the application of dairy cattle slurry, which was high in NH4.
116
12
NO3
10
NO2
NH4-N
N (mg L-1)
8
6
4
2
0
1
2
Slurry
3
1
2
Alum
3
1
2
3
PAC
1
2
3
1
Lime
2
3
Soil
Treatment
Figure 6.7 Average flow-weighted mean concentrations of ammonium nitrate (NH4-N),
nitrite (NO2-N) and nitrate (NO3-N) for three rainfall simulation events, and maximum
allowable concentrations (MAC) in waterways.
6.4.3. Time to runoff, soil volumetric water content and runoff volume
The rainfall intensity, volume of runoff (converted to equivalent depth), time from start of
rainfall application to start of runoff event, and volumetric water content of the soil at the
start of each rainfall simulation are shown in Figure 6.8. Almost 90% of all rainfall
applied drained away or leached through the soil, with 7.8% of water applied to soil-only
being collected as runoff from the upper 25 mm of the soil surface, 9% for the slurrycontrol, 9.4% for alum-amended slurry, 15% for PAC-amended slurry and 14.3% for
lime-amended slurry. The runoff volumes were not statistically different to each other.
117
6
RS3
15
10
5
0
Soil Slurry Aum
140
Time to runoff (min)
RS2
Runoff volume (mm)
RS1
120
RS2
RS3
3
2
1
0
Soil Slurry Aum PAC Lime Mean
60
RS3
RS2
4
PAC Lime Mean
RS1
RS1
5
Volumetric water content
(%)
Intensity (mm hr-1)
20
RS1
RS2
RS3
50
100
40
80
30
60
20
40
10
20
0
Soil Slurry Aum PAC Lime Mean
0
Soil Slurry Aum
PAC
Lime Mean
Figure 6.8 Average rainfall intensity, runoff volume, time to runoff and soil volumetric
water content for the first (RS1), second (RS2) and third (RS3) rainfall events.
There was no statistical evidence of any effect of rainfall simulator on the experimental
outcome. The average intensity for each rainfall simulation event for the two simulators
was 10±1.8 mm h-1 and 10.7±1.93 mm h-1, respectively. Rainfall intensity and soil water
content did not have a significant effect on TR, runoff volume, or P and N losses.
Covariate analysis of the logarithmic of the TR showed that event (p<0.001) and slope
(p<0.01) of plots affected TR.
118
6.5.
Discussion
6.5.1. Phosphorus (FWMC of DRP, DUP, PP and TP)
Throughout the study, the DRP concentrations in runoff water from soil-only plots were
in excess of the MAC of 0.03 mg DRP L-1 for surface waterbodies in Ireland (Flanagan,
1990). The average FWMC of TP for the soil only treatment was in excess of water
quality limit of 0.025-0.1 mg TP L-1 (USEPA, 1986) for surface water in the USA. The
concentrations in runoff from the slurry-control plots were also all in excess of the MAC
for DRP and TP for the duration of the study. However, the buffering capacity of water
means that the concentration of the water in a surface waterbody will not be as high as the
concentration of runoff, provided runoff from slurry flows over soil which has not
received dairy cattle slurry (McDowell and Sharpley, 2002b).
The results of the present study show that chemical amendments can be used to reduce P
solubility in dairy cattle slurry and thus reduce P loss to a surface waterbody. Alum and
PAC reduced P losses significantly compared to the slurry-control. Possible reasons for
this failure to achieve runoff concentrations below the MAC may be insufficient chemical
amendment of slurry, rainfall intensity and insufficient contact time to achieve adsorption
of P. Incidental P losses accounted for the majority of P losses from the slurry-control
plot during the study, with approximately 75% of DRP, 72% of DUP, 94% of PP and
83% of TP losses, measured over the three rainfall events, occurring during RS1. While
incidental losses were significantly reduced in the alum and PAC-amended plots, the
effect of amendments on chronic loss of P from the plots was not clear as differences in
runoff concentrations during RS3 and were not statistically significantly to slurry control.
The results show that even in low P Index soils, there is risk of DRP concentrations,
which are in excess of the MAC in runoff, entering drains. In a similar plot study with
simulated rainfall applied at 25 mm h-1, Kruz et al. (2006) observed an average FWMC of
DRP of 0.99 mg L-1 from soil with a Morgan‘s P varying between 5 mg P L-1 and 7 mg P
L-1. These concentrations are all similar to the soil only treatment in this study.
119
The results in this study were similar to previous work (Preedy et al., 2001; Kleinman and
Shapley, 2003; Hanrahan et al., 2009). Kleinman and Sharpley (2003) applied dairy cattle
slurry to grassed runoff boxes at 50 kg TP ha-1. Runoff boxes were subjected to simulated
rainfall at 70 mm h-1 three days after application, and DRP in runoff was 3.2 mg DRP L-1.
We have therefore shown that even when slurry was applied within guideline application
rates, concentrations of P in runoff were still in excess of limits. In practice, runoff from
fields receiving slurry will pass through a buffer area and undergo dilution before it
enters a waterway. This means that the concentrations measured in this paper were higher
than the actual concentration of the water that would enter the waterway if these
treatments were used in practice. Timing of slurry application and incorporation of slurry
may be a much more feasible way to reduce incidental P losses.
6.5.2. Nitrogen
On a low permeability soil, infiltration of N is unlikely and at this location N will
predominantly be lost in runoff to rivers. Dairy cattle slurry is high in NH4-N, which may
explain the high NH4-N in runoff during RS1. The reduction in NH4 concentrations in
runoff between RS1 and RS2 across all treatments, including the slurry-control, was
likely due to nitrification occurring in the soil following slurry application, and
interaction with the soil. Nitrification occurs when microbes use enzymes to convert NH4
to NO2 and then NO3 to obtain energy (Ketterings et al., 2011). This also explains why
there was so little NO2 in the runoff water in comparison to NO3.
Land application of dairy cattle slurry resulted in an increase in NH4-N compared to soil
only. Smith et al. (2001b) reported similar findings. Smith et al. (2001b) added dairy
cattle slurry at a rate 75 m3 ha-1 to grassed plots and reported soluble N (NH4-N+NO3-N)
concentrations ranging from 2 mg L-1 to 14 mg L-1, which was comparable to the average
FWMC of soluble N observed in this study (6.3 mg L-1). Nitrite losses were not
significant and were equivalent to approximately 1.9% of NO3 for most samples. Land
application of dairy cattle slurry did not have a significant effect on NO3 loss to runoff
water; this was in agreement with results from Smith et al. (2001b). Alum increased NH4-
120
N loss during first rainfall event, while PAC reduced NH4-N loss compared to the slurrycontrol. These results indicate that chemical amendments could potentially increase N in
runoff from dairy cattle slurry.
It is critical that the potential for ‗pollution swapping‘ is examined when evaluating
chemical amendment of dairy cattle slurry. In particular, the effects of any amendments
on GHG emissions must be examined. Under the 1997 Kyoto Protocol of the United
Nations Framework Convention on Climate Change (UN, 1998), participating nations
agreed to publish national inventories of anthropogenic emissions of several GHG and to
reduce future emissions below 1990 levels. In Ireland, agricultural activities were
responsible for approximately 26% of total GHG emissions in 2008 (McGettigan et al.,
2010) and account for virtually all NH3 emissions, with animal manure alone responsible
for 92% of NH3 emissions (EPA, 2010). While NH3 is not a GHG, it contributes to
acidification of soils, atmospheric pollution, and the eutrophication of surface and ground
water systems (Goulding et al., 1998). An estimated 5% of global N2O emissions results
from the conversion of NH3 into N2O in the atmosphere (Ferm, 1998). In addition to
gaseous N losses (Amon et al., 2006), agricultural activities, such as land application of
dairy cattle slurry, contribute to the production of NH3 and GHG, such as CO2, N2O (Ellis
et al., 1998) and CH4 (Chadwick et al., 2000). Therefore, any chemical amendments
which alter slurry properties may have an effect on GHG emissions.
6.5.3. Rainfall intensity, soil volumetric water content, time to runoff and runoff
volume
Land spreading of dairy cattle slurry at high rates may result in sealing of the soil surface
by slurry solids. Smith et al. (2001b) reported a 16% increase in runoff volume compared
to soil-only control when dairy cattle slurry was applied to the soil surface at 40 m3 ha-1.
This is similar to an 11.5% increase in runoff volume observed in the present study, this
increase was not, however, statistically significant. Chemical amendments of slurry
appeared to increase runoff volume compared to the slurry-control, but the differences in
runoff volume were not statistically significant. The rainfall simulation event was found
121
to have the greatest impact on runoff volume (p<0.05). There was a difference between
plots, but the differences were not statistically significant.
There was no statistically significant effect of treatment on runoff or TR. This indicated
that the effect of amendment on any surface sealing which may have occurred was
minimal. However, the lack of a relationship between soil water content and runoff
properties may be a result of scale effects. The soil around the plots received no rainfall;
this may also have resulted in an artificially high TR. In a similar plot study, Kleinman et
al. (2006) examined the role of rainfall intensity and hydrology in nutrient transport via
surface runoff and observed that despite significant differences in runoff generation
processes (volume of runoff and TR), the concentrations of DRP in runoff were related to
the STP of the grassed soil. Similar results were observed in the present study, however
the DRP concentrations were dependent on the WEP of the slurry applied and not STP of
the soil.
Although amendments increased runoff at plot-scale, the effect of such an increase at
field-scale cannot be fully known. There is potential that if runoff increased at a larger
scale, increased erosion and loss of PP could occur. The variation observed in runoff has
significant implications for comparing the results of this work with field-scale studies.
Potential scale effects which must be considered include: (1) dilution due to different
runoff volumes and TR (2) differing soil texture/permeability in between plots and (3)
length of collection period, as the FWMC of the various measured water quality
parameters may be artificially high since the water samples were not collected after
rainfall stopped.
6.5.4. Outlook for future implementation of chemical amendment of dairy cattle
slurry as a management practice for high P soils
This study demonstrated that PAC was the most effective chemical amendment to reduce
incidental DRP losses from dairy cattle slurry, with alum being most effective at reducing
DUP and TP losses. Alum and PAC significantly reduced P losses, particularly in RS1,
122
while lime resulted in increased P losses and is not a suitable amendment at the rates
examined in this study.
The estimated cost of chemical amendment, calculated in Chapter 3, and based on the
estimated cost of chemical, chemical delivery to farm, addition of chemical to slurry,
increases in slurry agitation, and slurry spreading costs as a result of increased volume of
slurry, increases the cost of land application from approximately Є1.90 m-3 for slurry
only to Є6.5 m-3 for alum-, Є7.60 m-3 for PAC-, and 4.90 m-3 for lime-amended slurry.
The TP lost from slurry-control plots during the study period had an approximate P
fertiliser value of Є5.48 ha-1 compared to Є0.82 ha
PAC reduced the value of P lost to Є1.45 ha
-1
-1
lost from grass-only. Alum and
and Є2.50 ha -1, respectively, while lime
increased the value of TP lost to Є14.7 ha -1. The value of TP applied to plots receiving
dairy cattle slurry and un-amended slurry was Є82.7 ha-1.
Chemical amendment could be used in strategic areas (e.g. on farms with surplus P) to
reduce P solubility in manure and P transfer to a surface and ground waters, whilst
allowing farmers to utilise other nutrients in slurry on farms with high STP. In certain
U.S states (Arkansas, Alabama, Tennessee and South Carolina), alum amendment of
poultry litter is used as a standard conservation practice (Moore and Edwards, 2005). At
present, there is no provision for a licence to landspread any of these amendments in
Europe and if chemical amendment were to be used, a licensing system would have to be
introduced by the relevant bodies. The plant availability of P in chemically amended
manure is a major concern for stakeholders. Moore and Edwards (2005) has shown that
chemical amendment improves yields due to increased N efficiency. In addition, in this
study, chemical amendment is proposed for use to reduce P solubility where farmers have
a short-term P surplus, and is recommended for strategic use within a catchment.
Therefore, it should not be used in a site with low STP. Further work is required to access
the long-term availability of P bound in Al bonds and if STP would decline as a result of
chemical amendment of dairy cattle slurry prior to land spreading.
123
6.6.
Conclusions
The results of this plot-scale study validated results from micro-scale and meso-scale
studies conducted in the laboratory. Treatment was not found to have a significant effect
on time to runoff or volume of runoff. When compared to the slurry-control, alum and
PAC reduced DRP by 95 and 98%, respectively, in runoff following RS1. Alum and PAC
also reduced TP losses during RS1 by 85 and 92%, respectively. Lime increased P losses
compared to the slurry-control. Addition of amendments had no significant effect on
NO3-N in runoff water. Alum and lime increased the FWMC of NO2-N in runoff by 120
and 114% compared to the slurry-control. Alum amendment increased NH4-N in runoff
by 84% compared to the slurry-control, while PAC reduced NH4-N in runoff by 80%
compared to the slurry-control. Lime had no effect on NH4-N concentrations in runoff
water. Alum amendment significantly increased average FWMC of NH4-N in runoff
water during the first rainfall event after slurry was applied. This indicates that
amendment on a large scale could increase soluble N losses and that large scale disposal
to land may pose a problem.
6.7.
Summary
At the scale of the present study, alum and PAC provide the best value in reducing the TP
loss from slurry; however, they are still very expensive. The next step is to examine the
effects of long-term use of these amendments at field-scale and to quantify their effect on
plant availability of P and GHG emissions. In addition, there is a need for a much greater
examination of pollution swapping of N, with a focus on transfer of N to groundwater via
leaching. Chapter 7 will examine the impact of chemically-amended slurry on soil WEP,
plant available P and soil pH over a study with duration of 9 months.
124
Chapter 7 The long-term impact of the addition of chemically
amended dairy slurry on phosphorus content and pH of five
soil types
7.1.
Overview
In this chapter, the impact of chemically amended dairy slurry application to land on soil
WEP, plant available P and soil pH was examined across 5 different soil types in Ireland.
7.2.
Introduction
A number of studies have examined the effect of chemical amendments on reducing P
solubility in slurry (Dao, 1999), reducing P solubility in soil and slurry mixtures (Dao and
Daniel, 2002), and reducing P in runoff from soils receiving amended slurry (Chapter 4).
With the exception of Kalbasi and Karthikeyan (2004), there has been little research on
the effect of chemical amendments on long-term P dynamics in soil following application
of chemically amended dairy cattle slurry. Kalbasi and Karthikeyan (2004) examined
three silt loam soils with different STPs in an incubation experiment conducted over a 24mo period. Kalbasi and Karthikeyan (2004) amended the soils with either untreated dairy
manure, alum-treated dairy manure, ferric chloride-treated dairy manure, or lime-treated
dairy manure. Results showed the effect of chemical amendment depended on treatment
type, P application rate and background STP. Kalbasi and Karthikeyan (2004) concluded
that more work was needed to investigate the effects of soils varying in physical and
chemical characteristics.
125
7.3.
Materials and methods
7.3.1. Soil collection and analysis
Soils were selected from the upper 100 mm of 5 sites to represent some common soil
types used in dairy farming in Ireland (Figure 7.1). The 5 soils collected were in the
optimum range (5.1-8 mg L-1) of STP for productive grasslands with the exception of soil
from Site C (Table 7.1), which was P deficient, and the peaty soil (soil E), which had a
high STP. The peat soil was included as there is a particular risk of P loss from peat soils
as they have poor capacity to store P (Cummins and Farrell, 2003) and could represent a
critical source if P was applied in excess of agronomic requirements of crops. Fay et al.
(2007) reported that 50% of mineral and organic soils had respective STPs lower than 6.4
mg L-1 and 9.3 mg L-1 in the upper 100 mm. Soils with different texture, OM, and pH
were selected to test the effectiveness of the amendments in a variety of conditions. The
selected soils give an indication of the stability of metal-phosphate bonds formed as a
result of chemical amendment in a wide variety of conditions.
Laboratory analysis was conducted to characterise the soil used in this study. The soil
was air dried and crushed to pass a 2 mm sieve. Sub-samples were taken, dried at 40 °C
for 72 h, and analysed for Morgan‘s P using Morgan‘s extracting solution (Morgan,
1941). Soil WEP (100:1 deionised water: soil) was determined after McDowell and
Sharpley (2001). Soil pH (n=3) was determined using a pH probe and a 2:1 ratio of
deionised water-to-soil. Particle size distribution was determined using B.S.1377-2:1990
(BSI, 1990a) and OM of the soil was determined using the LOI test (B.S.1377-3; BSI,
1990b). The results are presented in Table 7.1. Soil pH (n=3) was determined using a pH
probe and a 2:1 ratio of deionised water-to-soil.
7.3.2. Slurry collection and analysis
Dairy cattle slurry from dairy replacement heifers was taken from a farm (53°18‘ N,
8°47‘ W) in County Galway, Republic of Ireland, in Summer (June), 2010. The storage
126
tanks were agitated and slurry samples were transported to the laboratory in 10-L drums.
Slurry samples were stored at 4°C prior to testing. Slurry pH was determined using a pH
probe (WTW, Germany). The TP of the dairy cattle slurry was determined after Byrne
(1979). Total potassium was analyzed using a Varian Spectra 400 Atomic Absorption
instrument, and analyses for TN and TP were carried out colorimetrically using an
automatic flow-through unit. The slurry application used in this experiment was based on
an application rate of 33 m3 ha-1, which is common practice in Ireland (Coulter and Lalor,
2008). In order to facilitate randomisation, the same slurry application rate was selected
for all soils. Amendment application rates to reduce soluble P in slurry were based on the
results of Chapter 3.
Figure 7.1 Site locations shown on map of Ireland
127
The slurry characterisation is shown in Table 7.2. The pH of slurry decreased for each of
the acidifying amendments and increased for lime. The slurry sample was typical of
slurry found on farms in Ireland (SI 610 of 2010). The slurry TN, TP, NH4-N and TK
were relatively constant with the exception of the lime-treated slurry, which had high TN,
TP and TK. Alum, PAC and FeCl3 addition reduced the slurry pH from approximately
7.2 to 5.1, 5.7 and 5.4 (p<0.001), respectively, while lime addition increased slurry pH to
12 (p<0.001).
7.3.3. Incubation experiment
This 9-mo incubation study comprised six treatments, conducted in triplicate (n=3), at a
fixed temperature of 11°C on: (1) soil only (to take account of the effects of incubation)
(2) soil mixed with dairy cattle slurry (the study control); and soil mixed with dairy cattle
slurry, which was amended with either (3) alum (4) lime (5) PAC, or (6) FeCl3 (In this
study FeCl3 was used instead of FeCl2 as FeCl3 is the most commercially available form).
First, 100 g samples of air dried soil, passed through a 2 mm sieve, were placed in 0.5-L
containers. A volume of deionised water required to achieve 50% approximate field
capacity was added and mixed with the soil using a spatula. Soil container capacity (CC),
which is an approximate measurement of field capacity, was determined for each soil
after Bond et al. (2006). To determine approximate field capacity, 100g of air-dried soil
was placed in a container (with holes in the bottom) and saturated with deionised water.
The container was then covered with para-film (perforated to allow air to circulate) and
allowed to drain for 48 h through the drainage ports in the bottom of the container. It was
then dried at 105° C and reweighed. This difference in weight was the CC (kg water kg-1
soil).
128
Table 7.1 Soil physical and chemical properties.
Site
Soil A
Soil B
Soil C
Soil D
Soil E
Coordinates
52°07' N,8°16' W
52°17' N,6°31' W
52°17' N,6°31' W
53°21'N, 8°34' W
54°04' N,8°52' W
Location
Cork
Wexford
Wexford
Galway
Sligo
Soil texture
Sandy loam
Clay loam
Clay loam
Silty loam
Peat soil (na)
Sand content
%
56.2 (1.1)
51.8 (4.2)
37.8 (1.1)
15 (1.4)
-
Silt content
%
25.8 (1.3)
28.1 (4.9)
31.1 (1.0)
72 (1.1)
-
Clay content
%
18 (2.4)
20.1 (2.2)
31.1 (2.1)
13 (1.2)
-
7.2 (1.2)
6.2 (2.1)
2.7 (0.9)
3.2 (1.5)
42.5 (4.5)
7.9 (0.6)
7.8 (0.26)
6.7 (0.5)
13.3 (0.23)
77.4 (0.2)
Water extractable phosphorus
mg kg
Organic matter content
%
-1
Soil pH
Potassium
Magnesium
Lime requirement of soil
6.1 (0.85)
5.7 (0.08)
6.5 (0.02)
5.1 (0.04)
5.6 (0.05)
mg L-1
136 (5.4)
248 (2.9)
106 (1.1)
102 (6.1)
126 (6.4)
-1
217 (9.1)
377 (19.4)
225 (2.1)
124 (2.9)
527 (48.7)
2 (0.6)
5 (0.3)
XLS
3 (0.3)
12 (0.3)
5.8 (0.34)
5.7 (0.1)
2.6 (0.2)
5.1 (0.42)
24.6 (0.2)
3
3
1
3
4
675 (32)
634 (12)
539 (8)
825 (43)
2110 (59)
1.29
1.15
1.08
0.93
0.27
mg L
t ha
-1
Soil test phosphorus (Morgan‘s)
mg L
P Indexa
Indexa
Container capacity
Soil bulk density
-1
kg water kg soil
-3
kg m
-1
(Standard deviations in brackets), XLS: no lime requirement; aP Index: soils in Ireland ranked based on risk of P loss (Index 1 being low risk and 4 being the highest);
129
Table 7.2 Slurry properties
Treatment
Rate
metal to TP
Slurry
DM
pH
%
TN
mg L
TP
-1
mg L
TK
-1
mg L-1
10.45 (0.78)
7.2 (0.34)
4860 (425)
1140 (93)
3110 (254)
Alum
1.5:1 (Al:TP)
10.1 (0.35)
5.1 (0.35)
4660 (201)
1120 (19)
2840 (167)
Lime
16:1 (Ca:TP)
13.8 (0.17)
12 (0.25)
3590 (459)
944 (79)
2620 (430)
PAC
1.4:1 (Al:TP)
9.9 (0.35)
5.7 (0.4)
5320 (379)
1280 (154)
3060 (617)
FeCl3
1.5:1 (Fe:TP)
11.4 (0.69)
5.4 (0.1)
5020 (283)
1180 (84)
3100 (153)
(Standard deviation in brackets)
The bulk density of each soil used in this study was determined based on the volume of
100g of sieved soil occupied in a container after field capacity was achieved (Table 7.1).
Following this, slurry, or amended slurry, was added and mixed thoroughly (using a
spatula) before being compacted to volume which was determined based on bulk density
of soil and volume of slurry applied and water added. A packer was custom made (Figure
7.2) to compress soil to the approximate height. This height was determined based on soil
bulk density, volume of water added and volume of slurry added (if added).
First, the soil, slurry and deionised
water were mixed in the container.
The height of the stop blocks
required to achieve appropriate
bulk density was selected and
placed beside the container
The mixture was then compacted
to an appropriate bulk density.
The packer was then removed
and cleaned using deionised
water and drying paper before
being used again.
Figure 7.2 Schematic of packer used to achieve approximate bulk density
130
The amendments were applied at a stoichiometric rate based on the TP of the slurry
(Table 7.2). The mineral soils examined have a mean bulk density of 1.12 ± 0.15 g cm-3
in the containers used to calculate field capacity and for the purpose of selecting slurry
application rate, it was assumed that land applied slurry only interacts with the upper 20
mm of soil. Studies have shown that the STP in the upper 20 mm of grassland soils tends
to be higher than for the equivalent depth in tillage soils receiving the same manure. This
is due to the absence of tilling, which ploughs the nutrients into the soil (Andraski et al.,
2003). Although the peat had a significantly different bulk density, it was decided to
apply the same rate to the peat. The containers were covered with para-film. Throughout
this study, water was added intermittently to ensure that approximately 50% field
capacity was always maintained.
After 1, 3, 6 and 9 mo, the DM and WEP of the wet soil was first determined. The
remaining soil sample was air dried and crushed to pass a 2 mm sieve. Sub-samples were
taken, dried at 40 °C for 72 h, and analysed for soil pH and Morgan‘s P using Morgan‘s
extracting solution.
7.3.4. Statistical analysis
The data (Appendix G) were analysed as a factorial design with soil type, month and
treatment as factors. All interactions were examined. Soil type was a blocking effect in
this structure, but its interactions with the randomised factors were of interest. The
interactions were interpreted in the first instance by testing simple effects and then
making comparisons of means, with adjustment for multiplicity of testing. The
GLIMMIX procedure of SAS 9.2 was used to fit the analysis model. This procedure
allowed the addition of heterogeneous variance structures and a number of options for
examining a large number of means. Residual checks were made to check the
assumptions of the analysis method.
131
7.4.
Results
7.4.1. Water extractable phosphorus
There was a significant interaction between soil type, month and treatment for WEP
(p<0.001). The WEP of incubated soil samples at each sampling time is shown in Figure
7.3. The WEP of the soil-only treatments for the four mineral soils examined was lower
after 1 mo of incubation than the WEP of the soil before the start of the experiment. This
was in agreement with Kalbasi and Karthikeyan (2004) and Penn and Bryant (2006). This
was likely due to the effect of drying and re-wetting, and breaking down of soil as a result
of sieving (Penn and Bryant, 2006). In general, the WEP of the soil-only treatment did
not vary significantly during the study for soils A, B and E. The WEP of soil C was
significantly higher at the 6 mo sampling event than at any other time in the study. The
WEP of soil D increased significantly between mo 1 and 3, and stayed steady for the
remainder of the study. In contrast, the WEP of the peat soil increased initially as a result
of incubation; however, there was no significant variation during the study.
Addition of slurry increased the WEP of soil compared to the soil-only treatment for all
soils. This was in agreement with result of other studies (Kalbasi and Karthikeyan, 2004;
Murphy, 2007). However, in general, these increases were not statistically significant.
The WEP of soil A, when amended with slurry, was significantly different to the soilonly treatment at the 3 mo sampling event. There were also significant differences for soil
B (at the 1 and 3 mo sampling times) and for soil D (mo 1) (p<0.05).
For the four mineral soils, alum-amended slurry reduced the average WEP of soil
compared to the study control (average of 4 sampling events) by between 52 and 73%,
lime by between 50 and 83%, PAC by between 21 and 64%, and FeCl3 by between 0 and
38%. These reductions in WEP were not consistently statistically significant. After 1 mo
of incubation, the WEP of alum-amended slurry was significantly different to the slurrycontrol for soil B (89%), soil C (98%) and soil D (94%). Lime addition was also effective
at reducing WEP compared to the slurry-control and there were significant reductions
132
after 1 mo for soils B (94%), C (98%) and D (97%) and after 3 mo for soils C (88%) and
D (78%). Poly-aluminium chloride was less effective than alum or lime at reducing the
WEP compared to the slurry-control with the only significant reductions occurring for
soils C (81%) and D (54%) at the 1 mo sampling event. Ferric chloride was less effective
than other amendments and much more variable: in soil C, WEP was significantly lower
for soil which was mixed with FeCl3 treated slurry than the slurry-control after 1 mo
(p<0.05). After 3 mo, soils A and D were significantly different to the slurry-control
(p<0.05). There were no significant differences between WEP of the slurry-control and
the soil amended with chemically amended slurry at the 6 and 9 mo sampling event.
7.4.2. Soil test phosphorus
There was a significant interaction between soil type, month and treatment for the STP of
the soil (p<0.001). The STP of incubated soil samples at each sampling time are shown in
Figure 7.4. The STP of the soil only was observed to be much more stable than the WEP,
and did not vary significantly during the course of the experiment. This was consistent
with the results of Kalbasi and Karthikeyan (2004). The STP of soils which received
dairy cattle slurry also remained relatively stable throughout the course of the experiment
and although there were observed differences in STP between the control and soil-only
treatments, these differences were not all statistically significant (p<0.05).
For the four mineral soils, during the first month, alum reduced average STP of soil
amended with alum-treated slurry compared to the slurry-control by between 13 to 58%,
lime by between 0 and 62%, and PAC by between 13 and 46%. Ferric chloride increased
STP by up to 30% at 1 mo; this was in agreement with the findings of Kalbasi and
Karthikeyan (2004). The STP of the soil amended with alum, lime, PAC and FeCl3 was
greater than the STP for each un-amended soil during the study. Chemical amendments
did not have a significant effect on STP of the peat soil. These results indicated that there
was no negative effect on plant available P with the use of a chemical amendment, with
the exception of soil receiving FeCl3 amended slurry, the STP of which was significantly
different to the slurry-control for soil A (mo 9) and soil B (mo 6 and 9).
133
Tunney et al. (2000) found a strong association between STP (measured using Morgan‘s
extracting solution) and DRP concentrations in overland flow in Irish grassland soils.
This relationship can vary between different hydrological conditions (Kurz et al, 2005)
and soil types (Daly et al., 2001). Daly et al (2001) examined 11 soils chosen to best
represent important agricultural grassland soils in Ireland varying in parent material,
drainage, soil type and soil chemical properties. Daly et al (2001) found that, although
STP was an important factor controlling P desorption, soil type also affected levels of
sorption and desorption. Regan et al. (2010) found a similar relationship for tillage soils.
7.4.3. Soil pH
There was a significant interaction between soil type, month and treatment for pH of soil
(p<0.001). The pH of incubated soil samples at each sampling time are shown in Figure
7.5. The pH of the soil-only treatments did not significantly change as a result of the
incubation experiment. Addition of dairy cattle slurry did not significantly alter soil pH
for any of the soils examined. With the exception of FeCl3 (soil A, mo 9) (p<0.05), none
of the amendments examined appeared to significantly affect soil pH.
7.5.
Discussion
7.5.1. WEP
The results of this study show that although there was an interaction with soil type,
treatment and incubation duration, the WEP of soils mixed with chemically amended
slurry was generally lower than the un-amended slurry-control. There were some
instances where the WEP of soil which was incubated with FeCl3 amended slurry was
greater than the control. Although these increases were not statistically significant, this
may indicate that FeCl3 is not as stable as other amendments examined. These results
indicate that chemical amendment may have beneficial impacts on the mitigation of longterm losses of P to surface runoff.
134
Soil
Slurry
Alum
Lime
0
1
3
PAC
FeCl
6
9
25
20
30
25
20
Soil A
35
15
15
10
5
10
0
20
5
0
Soil B
15
10
5
0
Soil C
10
5
Soil D
0
15
10
5
0
120
100
Soil E
80
60
40
20
0
Time (months)
Figure 7.3 Water extractable phosphorus (WEP) of incubated soil samples at each
sampling time (n=3)
135
Soil A
35
30
25
20
15
10
5
0
Soil B
Soil
35
30
25
20
15
10
5
0
35
30
25
20
15
10
5
0
Slurry
Alum
Lime
PAC
FeCl
Soil C
20
15
10
5
0
Soil D
20
15
10
5
0
Soil E
60
40
20
0
0
1
3
6
9
Time (months)
Figure 7.4 Soil test P of incubated soil samples at each sampling time (n=3)
136
Soil
Slurry
Alum
Lime
PAC
FeCl
8
6
30
25
20
Soil A
35
4
2
15
0
8
10
5
0
Soil B
6
4
2
0
8
Soil C
6
4
2
0
8
6
Soil D
4
2
0
8
Soil E
6
4
2
0
0
1
3
6
9
Time (months)
Figure 7.5 pH of incubated soil samples at each sampling time (n=3)
137
In a similar study, Kalbasi and Karthikeyan (2004) found that application of alum and
FeCl3 decreased P solubility in silt loam soil, while lime amendments increased WEP.
This study found that Al-compounds (alum and PAC) reduced WEP in mineral soils.
However, FeCl3 was as effective as the Al compounds, and lime addition resulted in the
greatest reduction in WEP. In this study, lime was applied at a higher rate (16:1 compared
to 10:1 (Ca:TP) in the Kalbasi and Karthikeyan (2004) study) and this may explain the
difference in effectiveness. Anderson et al. (1995) amended soils - with a history of
receiving dairy manure - with calcium carbonate (with the slurry pH adjusted to 7.5),
gypsum (0 to 100 g kg-1 soil), ferrous sulphate (0 to 1 g kg-1 as Fe) and alum (0 to 1 g kg-1
as Al) in an incubation experiment. Calcium carbonate effectiveness was limited to soils
with pH < 7.0 and gypsum was effective over a broad range of manure loading, pH and
redox conditions. Although Al and Fe amendments to soil increased P retention by 400%
relative to an un-amended control, Anderson et al. (1995) acknowledged elevated costs
associated with amendments and the potential for biological toxicity.
Runoff studies have been used to examine the addition of amendments to high STP soils
to reduce P losses (McFarland et al, 2003; Novak and Watts, 2005; Brauer et al., 2005).
Brauer et al. (2005) incorporated alum (127 kg Al ha-1) and gypsum at two rates (349 and
1163 kg Ca ha-1) into the upper 10 cm of a high STP soil on an annual basis for three
years. Only the high gypsum treatment was observed to reduce WEP and STP values
significantly during the study. A limited number of runoff studies have been carried out
with chemical amendment of dairy cattle slurry (Elliot et al, 2005; Torbert et al, 2005)
and swine slurry (Smith et al, 2001b), but little work has focused on the long-term effects
of chemical amendments to slurry on the nutrient content of soil.
Although this study gives a good indication of the stability of these amendments in the
soil used in this study, it did not examine the effect of chemical amendments on the rate
of mineralisation of fixed P to soluble WEP following loss of soluble P in runoff, or in
drainage water.
138
7.5.2. Soil test phosphorus
This study shows that one application of chemically amended slurry does not reduce plant
availability of P in the soils examined in this study. In fact, in the case of FeCl3, STP was
significantly increased for certain soils at the end of the study. This indicates that
chemical amendment of dairy cattle may be a short-term management practice to control
P surplus on a farm, but does not pose a risk to plant availability of P. In addition, it
validates the work of Kalbasi and Karthikeyan (2004) for a range of soils found in Ireland
using commercially available amendments. The amendments were buffered by organics
in the peat soil examined in this study. In a high OM soil with a pH of 5.5, there is no free
Al available, and any metals in the amendments are immediately buffered by organics,
which reduces their effectiveness in reducing P solubility. There is a need to examine the
effect of repeated applications of slurry amended with chemical amendments on STP and
other soil properties.
7.5.3. Soil pH
The pH of the mineral soils receiving FeCl3-amended dairy cattle slurry was consistently
higher than the slurry-control (Figure 7.5), background and all other treatments. The Clin the FeCl3 treatment may have replaced OH- ions on the variable charge exchange sites
in these soils, resulting in an increase in pH. This mechanism has been shown on HCltreated mineral soils with low starting pH and free iron oxides (Wang and Yu, 1998). An
elevated soil pH was not measured in soil E. This was likely due to the high buffering
capacity and lack of free iron sites in this organic soil.
The national average soil pH is 5.5 for grasslands (Fay et al., 2007), which is below the
recommended pH for optimum production of grass (6.3 for mineral soils and 5.5 for peat
soils; Coulter and Lalor, 2008). Therefore, the soils examined in this study are
representative of the pH range found in Ireland. The pH of a soil has a significant
influence on nutrient availability (Tunney et al., 2010), and changes in pH can alter
community composition and activity of microbes in soil (Sylvia et al., 2005). In addition,
139
if the amendments adversely affect the microbes, the microbes could potentially change
the pH by their activity. Therefore, pH was examined as a means of determining if the
amendments had the potential to have a significant effect on soil microbiology.
7.6.
Conclusions
This study found that although there were variations in the reductions in WEP of soil
amended with dairy cattle slurry across soil types, the WEP of soil receiving chemically
treated dairy cattle slurry was consistently, although not significantly, lower than the
slurry-control. Soil test phosphorus and soil pH were not significantly affected by
application of amended slurry, with the exception of FeCl3 amended slurry in some
instances. Therefore, chemical amendment of dairy cattle slurry as a short-term
management practice to control P loss does not pose a risk to plant availability of soil.
There is a need to examine long-term effects of repeated applications of chemically
amended dairy cattle slurry to develop an understanding of how amendments affect soil P
release processes over time.
7.7.
Summary
This study indicates that the use of chemical amendment as a once-off management
practice reduced WEP in soil compared to soil amended with slurry, but did not result in
immobilisation of STP or have any significant effect on soil physical and chemical
properties. Therefore, chemical amendment of dairy cattle slurry as a short-term
management practice to control P loss does not pose an immediate risk to plant
availability of soil.
140
Chapter 8
8.1.
Conclusions and Recommendations
Overview
The objective of this study was to identify possible mitigation methods to prevent P loss
to the environment during the land application of dairy cattle slurry. To address this,
experiments were designed and conducted to evaluate the effectiveness, feasibility and
pollution swapping potential of chemically amended dairy cattle slurry. The main
conclusions of the study are now presented.
8.2.
Conclusions
1. Experiments conducted at laboratory micro- and meso-scale, and micro plot-scale
showed that chemical amendment was very successful in reducing incidental
losses of DRP, TP, PP, TDP, DUP and SS from land-applied slurry. The results of
the study demonstrate that PAC was the most effective amendment for decreasing
DRP losses in runoff following slurry application, while alum was the most
effective for TP and PP reduction. Incidental loss of metals (Al, Ca and Fe) from
chemically amended dairy cattle slurry was below the MAC for receiving waters.
2. Although these treatments are expensive, they may be feasible if used
strategically to mitigate P loss from dairy slurry in critical source areas within a
farm.
3. The results of this study show that even with chemical amendment, P
concentration in runoff was above the MAC. Therefore, amendments may not be
141
the best option for minimising incidental P losses, as timing of applications may
be just as effective at controlling incidental P losses and may be much more cost
effective.
4. This study showed that P mitigating amendments can result in pollution
swapping. The amendments selected for recommendation for further study are,
from best to worst, PAC, alum and lime (Table 8.1). In addition, at the current
cost of treatment, the increase in fertiliser value of the slurry due to some
treatments is not sufficient to offset the cost of treatment. In this study, there was
no significant effect of any amendment, with the exception of charcoal, of slurry
on GWP caused by the land application dairy cattle slurry.
5. Although there were variations in the reductions in WEP of soil amended with
dairy cattle slurry across soil types, the WEP of soil receiving chemically treated
dairy cattle slurry was consistently, although not significantly, lower than the
slurry-control. Soil test phosphorus and soil pH were not significantly affected by
the application of amended slurry, with the exception of FeCl3-amended slurry in
some instances. Therefore, chemical amendment of dairy cattle slurry as a shortterm management practice to control P loss does not pose a risk to plant
availability of soil.
142
Table 8.1 Summary of feasibility of amendments (adapted from Chapter 3). Marks for
feasibility, pollution swapping, incubation study and plot study are from 1 to 5. 1 = best;
5 = worst.
Chemical
Agitator
score P
Pollution
swapping
Incubatio
n study
Plot
Combined
feasibility
score
Notes
Alum
1
4
1
1
8
Risk of effervescence
Risk of release of H2S due to anaerobic
conditions and reduced pH
Cheap and used widely in water treatment
Reduced ammonia emissions
AlCl3
(PAC)
2
1
3
2
7
No risk of effervescence (Smith et al.,
2004)
AlCl3 increased handling difficulty
Expensive
Reduced ammonia emissions
FeCl2
(FeCl3)
3
3
4
4
14
Potential for Fe bonds to break down in
anaerobic conditions
Increased release of N2O
Reduced ammonia emissions
Not examined in plot study
Ca(OH)2
4
2
2
3
11
Increased NH3 loss
Strong odour
Hazardous substance
Not effective in plot study
8.3.
Recommendations for future work
1. This work indicates that if amendments are to be implemented, extensive
catchment-scale experiments, carried out over a number of years, are necessary to
examine how amendments affect N leaching, plant availability of P, soil
microbiology and structure, metal build-up in the soil, long-term release of P to
runoff, gaseous emissions and pollution swapping. Such work should use land
spreading equipment at farm-scale.
2. These results suggest that chemical amendment of dairy cattle slurry with PAC
could be used to control P solubility and thus reduce incidental P losses from soils
143
receiving dairy cattle slurry without adversely affecting metal and N losses.
Future work must examine the long-term stability of metal-to-P bonds formed as a
result of chemical amendment of dairy cattle slurry following land application.
There is a need to examine the use of chemical amendments to slurry under a
wide range of conditions.
3. Results show that a once-off application of any of the chemical amendments
examined will not result in a significant change in chemical and chemical
properties, an increase in GHG emissions, a release of metals to runoff, or
significant pollution swapping. It is, however, critical that the long-term effect of
repeated applications of amendments on STP, soil pH, soil WEP, soil
microbiology and macro-biology be examined.
4. The results of the gas experiment indicated that if a biochar could be engineered
to sequester P as effectively as alum and PAC, it would be the ideal amendment,
as charcoal has the potential to dramatically reduce GHG emissions.
8.4.
Context
Ireland has committed to meeting the requirements of the European Union Water
Framework Directive (EU WFD; 2000/60/EC, OJEC, 2000) to achieve at least ‗good
status‘ of all surface and groundwater by 2015. It is expected that the current programmes
of measures (POM) will not reduce P losses sufficiently within this timeframe and that
that substantial measures will be required to fulfil these obligations. While current
practices are effective, there will be a time-lag before current changes in farming
practices will result in an observable reduction in nutrient losses and reduction in risk to
water quality. This study showed that amendments are effective and that there is no major
risk of pollution swapping associated with alum and PAC. This is a significant finding as
there is now potential to use amendments strategically, in combination with existing
programme of measures (POM), to mitigate P losses. The next step will be to examine the
use of chemical amendments at catchment-scale.
144
In future, farm nutrient management in Ireland must focus on examining all farms within
a catchment and identifying areas which pose the greatest risk. It is hoped that there will
be economic incentives given to farmers to reduce nutrient losses. It is possible that P
mitigating methods, such as chemical amendment of dairy cattle slurry, may be used
strategically within a catchment to bind P in cow and pig slurries.
145
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APPENDIX
171
Appendix A List of publications
JOURNAL PAPERS (Accepted)
Brennan RB, Fenton O, Rodgers M, Healy MG. 2011. Evaluation of chemical
amendments to control phosphorus losses from dairy slurry. Soil Use and Management
27: 238-246.
Brennan RB, Fenton O, Grant J, Healy MG. 2011. Impact of chemical amendment of
dairy cattle slurry on phosphorus, suspended sediment and metal loss to runoff from a
grassland soil. Science of the Total Environment 409(23):5111-8.
MANUCRIPTS IN PREPARATION
Brennan RB, Fenton O, Healy MG, Lanigan G. Effect of chemical amendment of dairy
cattle slurry on greenhouse gas and ammonia emissions (Submitted: Biological
Engineering)
Brennan RB, Fenton O, Grant J, Healy MG. Rainfall simulation study investigating the
effect of chemical amendment of dairy cattle slurry on runoff characteristics and nutrient
loss from grassland plots (Target journal: Science of the Total Environment).
Brennan RB, Fenton O, Grant J, Healy MG. The long term impact of adding chemically
amended dairy slurry to WEP, soil test phosphorus and pH in five grassland soils
(Submitted: Journal of Environmental Quality).
INTERNATIONAL CONFERENCE PAPERS
Brennan RB, Fenton O, Healy MG. 2010. Chemical amendment of dairy cattle slurry for
control of phosphorus in runoff from grasslands. A05 symposium on emerging
172
technologies to remove phosphorus. ASA-CSA-SSSA International Meetings, Long
Beach, CA. 31 October - 4 November, 2010 (Oral presentation).
Brennan RB, Fenton O, Healy MG. 2010. Evaluation of chemical amendments to control
soluble phosphorus losses from dairy cattle slurry. (Eds. Turtola E, Ekholm P, Chardon
W). In: MTT Science 10. Novel methods for reducing agricultural nutrient loading and
eutrophication: Meeting of COST 869, 14-16 June, Jokioinen, Finland. p. 18 (Oral
presentation).
NATIONAL CONFERENCE PAPERS
Brennan RB, Healy MG, Lanigan G, Fenton O. 2011. Chemical amendment of dairy
cattle slurry for control of P in runoff from grasslands. Walsh Fellowship Seminars. 12
July, RDS, Co Dublin (Poster presentation).
Brennan RB, Fenton O, Grant J, Healy MG. 2011. Mitigating incidental DRP losses from
land application of dairy cattle slurry using chemical amendments. Agricultural Research
Forum Conference. 14-15 March, Tullamore, Co. Offaly (Oral presentation).
Brennan RB, Fenton O, Rodgers M, Healy MG. 2010. Chemical amendment of dairy
cattle slurry for control of phosphorus in runoff from grasslands. SEGH 2010. 27 June - 2
July, 2010. National University of Ireland, Galway (Oral presentation).
Brennan RB, Fenton O, Rodgers M, Healy MG. 2010. The addition of chemical
amendments to dairy cattle slurry for the control of phosphorus in runoff from grasslands.
BSAS/WPSA/Agricultural Research Forum Conference. Queen's University, Belfast. 1214 April, 2010 (Oral presentation).
Brennan RB, Fenton O, Rodgers M, Healy MG. 2010. Chemical amendment of dairy
cattle slurry to reduce P loss from grasslands. 19th World Congress of Soil Science.
Brisbane, Australia, 1-6 August, 2010 (Poster presentation).
173
Appendix B Results of agitator test
174
Notation used in Appendix:
DRP, dissolved reactive phosphorus
Soil only – grassed soil sample
Slurry – slurry control
High, low and medium are rates as described in chapter 3
Alum, aluminium sulphate
Wtr dry, sieved and dried Al-WTR
Wtr wet, sludge Al-WTR
Vw; represents volume of sample removed for analysis
Vc, cumulative volume of sample removed during the experiment
P is the concentration of P in overlying water
Padj is the P concentration adjusted to take account of the change in volume of the overlying water during
the experiment
AlCl3, aluminium chloride
FeCl2 ferric chloride
FGD, flue gas desulphurisation by-product
Table B.1 Results of preliminary batch study
WTR
FeCl2
FeSO4
MgCl2
Ca(OH)2
Amendment g/kg slurry
pH
DRP (mg/L)
% reduction soluble P
0
7.3
23.9
20
7.5
17.1
28.5
50
7.6
13.29
44.4
100
7.7
11.6
51.5
150
7.84
5.6
76.6
300
7.95
0.5
97.9
0
7.4
24.4
1.6
7.2
5.6
77
5.5
6.84
0.33
98.6
10
6.6
0.1
99.6
20
6.2
0.05
99.8
0
7.38
20.4
1
7.23
18
11.8
Effective
Effective
Effective
5
6.98
11.6
43.1
10
6.8
0.7
96.6
20
6.56
0.13
99.4
0
7.38
14.943
1
7.4
2.612
82.5
5
7.33
2.171
85.5
10
7.24
3.081
79.4
20
6.96
3.305
77.9
50
6.28
7.673
48.7
0
7.5
31.707
1
8.2
12.221
61.5
5
10.1
10.499
66.9
10
12.5
3.156
90
20
12.6
1.057
96.7
50
12.7
0.707
97.8
175
Comment
Not effective
Effective
CaO
Al2(SO4)3
Fly ash
Al2(SO4)3
Bottom ash
Ferriox
Septiox
0
7.4
22.681
Effective
1
7.66
16.323
28
5
7.93
12.207
46.2
10
8.12
9.926
56.2
20
8.42
2.481
89.1
50
12.63
0.684
97
0
7.48
20.941
1
6.64
17.457
16.6
5
4.37
5.128
75.5
10
3.89
5.13
75.5
20
3.55
2.971
85.8
50
2.97
0.939
95.5
0
7.3
18.412
10
7.43
16.953
7.9
20
7.49
13.387
27.3
50
7.56
15.182
17.5
100
7.62
9.331
49.3
150
7.72
5.385
70.8
300
7.76
2.926
84.1
400
7.92
1.38
92.5
0
7.31
24.512
0.3
7.02
19.115
22
0.5
6.89
11.564
52.8
1
6.63
3.933
84
1.5
6.21
1.357
94.5
2
5.73
0.375
98.5
0
7.33
14.263
10
7.4
14.067
1.4
20
7.44
16.088
-12.8
Effective
Effective
Effective
Not effective
50
7.52
14.185
0.5
100
7.63
15.203
-6.6
150
7.74
14.626
-2.5
300
7.79
13.654
4.3
400
7.92
13.325
6.6
0
7.43
1
7.41
20.921
9.8
5
7.32
18.866
37.6
10
7.17
13.057
82.2
20
6.69
3.729
98
50
5.41
0.415
99.5
0
7.34
1
7.39
22.764
18.7
5
7.4
18.516
16.8
Effective
Effective
176
FGD
Charcoal
Polyaluminium
chloride
10
7.47
18.949
22.5
20
7.48
17.643
27.8
50
7.33
16.432
57.6
0
7.13
10
7.21
22.51
15.9
20
7.27
18.922
19.8
50
7.31
18.05
38.5
100
7.34
13.833
56.2
150
7.37
9.856
71.4
300
7.39
6.436
90.2
400
7.5
2.203
96.1
100
7.32
18.57
8
0
7.37
20.185
0
Effective
2
7.34
16
20.7
10
7.45
18.7
7.4
50
7.5
26
-28.8
0
7.18
20.921
0.3
7.22
18.866
10
0.5
7.3
13.057
38
1
7.36
3.729
82
1.5
3.43
0.415
98
2
7.48
0.103
100
Not effective
Effective
Note: The rates used in this experiment were based on values found in the literature. The
most effective amendments were selected and examined in the agitator test. There are
some exceptions to this rule: Calcium oxide (CaO) was not chosen as it is hazardous.
Ferric sulphate (FeSO4) was not examined as it resulted in very strong smell. In addition
commercial products Ferriox and Septiox were not examined further as they were
expensive for this purpose.
177
Table B.2 Langmuir model applied to amendments which were effective in preliminary experiment
and selected for use in agitator test (Chapter 3).
0.5
1.2
1
0.4
0.8
0.3
0.6
0.2
0.4
a=1
b = 1 mg P/ g Alum
0.2
0
0
0
5
10
0
15
6
6
5
5
4
4
3
2
4
6
3
a =0.35,
b = 9.15 mg P /g Ca(OH)2
2
2
1
a =0.7,
b = 11.2 mg P /g FeCl2
1
0
0
0
5
10
0
2
4
6
0.2
0.12
0.1
0.15
0.08
Cs
Langmuir model (mg L-1)
a =1,
b = 0.52 mg P /g PAC
0.1
0.1
0.06
0.04
0
0
5
10
a =0.2,
b = 0.21 mg P /g FGD
0.05
a =0.13,
b = 0.45 mg P /g flyash
0.02
0
0
15
0.3
0.25
0.2
0.15
0.1
a =0.1,
b = 0.31 mg P /g WTR
0.05
0
0
5
10
15
20
Solution equilibrium concentration (mg L-1)
178
5
10
15
Table B.3 Relationship between percentage reductions in dissolved reactive phosphorus and
% reduction in P in overlying water
percentage reduction in water extractable phosphorus of slurry (Chapter 3).
Alum (aluminum sulphate)
Aluminum chloride
Ferric chloride
Lime
AL WTR (dry sieved)
Al WTR (sludge)
Fly ash
FGD
% reduction in water extractable P in slurry
179
Table B.4 Results of agitator test
Control soil only
Volume of water added ml
Soil only
Slurry
Time (h)
ml
Vw
Vc
P
Padj
Mass P
ml
ml
μg/l
μg/l
mg/m2
0
2
2
0
0
0
24
0.25
2
4
203
0.2
12.8
205
0.5
4
8
240
0.2
15
334
1
4
12
277
0.3
17.2
301
2
4
16
282
0.3
17.4
367
4
4
20
347
0.3
21.2
401
8
4
24
363
0.3
22
448
12
4
28
382
0.4
23
479
24
4
32
379
0.4
22.6
460
0
0
0
0
0
0
0.25
4
4
3100
3.1
195.8
3700
0.5
4
8
4100
4
256.8
4200
1
4
12
5800
5.7
360.4
6400
2
4
16
7600
7.4
468.3
8800
4
4
20
9900
9.5
605
10600
8
4
24
10700
10.2
648.5
13100
12
4
28
10900
10.3
655.1
11000
24
4
32
10900
10.2
649.5
11000
36
4
36
10400
9.7
614.4
10200
36
low alum
Sample 1
500
0
10900
13100
0
0
0
0
0
0.25
4
4
324
0.3
20.5
487
0.5
4
8
563
0.6
35.3
785
1
4
12
709
0.7
44.1
1162
2
4
16
454
0.4
28
856
4
4
20
973
0.9
59.5
2025
8
4
24
1042
1
63.2
2325
12
4
28
1086
1
65.3
2470
4
32
1163
1.1
69.3
2669
24
32
high alum
0
69.3
0
0
0
0
0
4
549
0.5
34.7
500
0.25
4
0.5
4
8
770
0.8
48.2
795
1
4
12
1195
1.2
74.3
1295
2
4
16
1512
1.5
93.2
1812
4
4
20
1781
1.7
108.8
1981
180
8
4
24
1943
1.8
117.8
2143
12
4
28
2222
2.1
133.5
2348
4
32
2721
2.5
162.1
2721
24
32
med alum
0
162.1
0
0
0
0
0
0.25
4
4
199.054
0.2
12.6
269.079
0.5
4
8
236.702
0.2
14.8
335.064
1
4
12
325.291
0.3
20.2
429.671
2
4
16
497.673
0.5
30.7
647.708
4
4
20
592.011
0.6
36.2
760.275
8
4
24
609.977
0.6
37
835
12
4
28
831.11
0.8
49.9
1005.124
24
4
32
901
0.8
53.7
984
32
low lime
0
53.7
0
0
0
0
0
4
2859
2.8
180.6
2329
0.25
4
0.5
4
8
4293
4.2
268.9
3112
1
4
12
5730
5.6
356
4454
2
4
16
7050
6.8
434.5
6194
4
4
20
8485
8.1
518.6
8118
8
4
24
9986
9.5
605.2
9888
12
4
28
9513
9
571.7
8604
24
4
32
12158
11.4
724.5
9960
32
med lime
0
724.5
0
0
0
0
0
0.25
4
4
1438
1.4
90.8
1031
0.5
4
8
1698
1.7
106.4
1500
1
4
12
1739
1.7
108.1
1987
2
4
16
1888
1.8
116.3
2512
4
4
20
2184
2.1
133.5
2360
8
4
24
2268
2.2
137.5
2419
12
4
28
2912
2.7
175
2059
24
4
32
3066
2.9
182.7
2990
32
high lime
0
182.7
0
0
0
0
0
0.25
4
4
304
0.3
19.2
514
0.5
4
8
365
0.4
22.9
670
1
4
12
513
0.5
31.9
1154
2
4
16
746
0.7
46
544
181
4
4
20
674
0.6
41.2
1317
8
4
24
796
0.8
48.2
1443
12
4
28
2245
2.1
134.9
2289
24
4
32
1359
1.3
81
2163
32
low dry wtr
0
134.9
0
0
0
0
0
0.25
4
4
2016
2
127.3
2450
0.5
4
8
2282
2.2
143
2642
1
4
12
2670
2.6
165.9
2771
2
4
16
3015
2.9
185.8
2919
4
4
20
6672
6.4
407.8
5446
8
4
24
6975
6.6
422.7
5570
12
4
28
6920
6.5
415.9
5603
4
32
8353
7.8
497.7
8058
24
32
med dry wtr
0
497.7
0
0
0
0
0
0.25
4
4
626
0.6
39.5
433
0.5
4
8
869
0.9
54.4
456
1
4
12
819
0.8
50.9
673
2
4
16
1701
1.6
104.8
877
4
4
20
1887
1.8
115.3
1024
8
4
24
1885
1.8
114.2
1066
12
4
28
1795
1.7
107.9
1074
24
4
32
4814
4.5
286.9
1760
32
high dry wtr
0
286.9
0
0
0
0
0
4
393
0.4
24.8
224
0.25
4
0.5
4
8
574
0.6
36
333
1
4
12
419
0.4
26
355
2
4
16
411
0.4
25.3
336
4
4
20
361
0.3
22.1
287
8
4
24
281
0.3
17
242
12
4
28
295
0.3
17.7
236
24
4
32
2221
2.1
132.3
3759
32
low wet wtr
0
132.3
0
0
0
0
0
0.25
4
4
4345
4.3
274.4
6256
0.5
4
8
4305
4.2
269.7
6258
1
4
12
5720
5.6
355.4
8423
182
2
4
16
7610
7.4
469
10748
4
4
20
9656
9.3
590.1
11080
8
4
24
11359
10.8
688.4
13012
12
4
28
11722
11.1
704.5
13265
24
4
32
13090
12.3
780
13553
32
med wet wtr
0
780
0
0
0
0
0
0.25
4
4
2655
2.6
167.7
3482
0.5
4
8
1268
1.2
79.4
1584
1
4
12
2361
2.3
146.7
2749
2
4
16
2739
2.7
168.8
1331
4
4
20
2709
2.6
165.6
1924
8
4
24
2313
2.2
140.2
2657
12
4
28
1973
1.9
118.6
2145
4
32
2148
2
128
2577
24
32
high wet wtr
0
168.8
0
0
0
0
0
0.25
4
4
3591
3.6
226.8
3797
0.5
4
8
2604
2.6
163.1
2385
1
4
12
3354
3.3
208.4
3046
2
4
16
3857
3.7
237.7
3409
4
4
20
4027
3.9
246.1
3471
8
4
24
3536
3.4
214.3
3130
12
4
28
3151
3
189.4
2865
24
4
32
2233
2.1
133.1
2063
32
Flyash high
0
246.1
0
0
0
0
0
4
1029
1
65
1411
0.25
4
0.5
4
8
2461
2.4
154.2
780
1
4
12
2102
2.1
130.6
2191
2
4
16
3045
2.9
187.6
3094
4
4
20
2918
2.8
178.3
3108
8
4
24
1825
1.7
110.6
2094
12
4
28
1639
1.5
98.5
1639
24
4
32
1426
1.3
85
1797
32
Flyash
medium
0
187.6
0
0
0
0
0
0.25
4
4
352
0.3
22.2
1391
0.5
4
8
459
0.5
28.8
2277
1
4
12
676
0.7
42
2001
183
2
4
16
898
0.9
55.3
2198
4
4
20
1143
1.1
69.9
2283
8
4
24
1391
1.3
84.3
2563
12
4
28
1399
1.3
84.1
2525
24
4
32
1661
1.6
99
3171
32
Flyash low
0
99
0
0
0
0
0
0.25
4
4
1965
1.9
124.1
2243
0.5
4
8
2790
2.7
174.8
3016
1
4
12
3240
3.2
201.3
3780
2
4
16
4181
4
257.7
4083
4
4
20
4732
4.5
289.2
4343
8
4
24
5122
4.9
310.4
4641
12
4
28
6888
6.5
413.9
5725
24
4
32
7967
7.5
474.7
6640
32
FeCl low
0
474.7
0
0
0
0
0
0.25
4
4
485
0.5
30.7
0
0.5
4
8
610
0.6
38.3
819
1
4
12
759
0.7
47.2
934
2
4
16
1002
1
61.8
1109
4
4
20
1331
1.3
81.4
1289
8
4
24
1750
1.7
106.1
1598
12
4
28
1945
1.8
116.9
1634
4
32
2398
2.2
142.9
1556
24
32
FeCl2 high
0
142.9
0
0
0
0
0
0.25
4
4
428
0.4
27.1
73
0.5
4
8
442
0.4
27.7
96
1
4
12
430
0.4
26.7
107
2
4
16
519
0.5
32
103
4
4
20
367
0.4
22.5
97
8
4
24
123
0.1
7.5
4.152
12
4
28
57
0.1
3.5
14
24
4
32
2
0
1.4
18
32
FeCl2 med
0
32
0
0
0
0
0
0.25
4
4
418
0.4
26.5
601
0.5
4
8
552
0.5
34.6
732
184
1
4
12
797
0.8
49.5
943
2
4
16
1056
1
65.1
1086
4
4
20
1519
1.5
92.8
1090
8
4
24
1680
1.6
101.8
968
12
4
28
1742
1.6
104.7
939
24
4
32
1889
1.8
112.6
821
32
AlCl3 low
0
112.6
0
0
0
0
0
4
645
0.6
40.8
192
0.25
4
0.5
4
8
914
0.9
57.2
360
1
4
12
1124
1.1
69.8
448
2
4
16
1536
1.5
94.7
700
4
4
20
1730
1.7
105.7
860
8
4
24
1809
1.7
109.7
1006
12
4
28
1851
1.7
111.2
998
24
4
32
2454
2.3
146.2
949
32
AlCl3 med
0
146.2
0
0
0
0
0
0.25
4
4
367
0.4
23.1
365
0.5
4
8
553
0.5
34.7
415
1
4
12
735
0.7
45.7
423
2
4
16
932
0.9
57.4
519
4
4
20
1063
1
65
606
8
4
24
1055
1
63.9
713
12
4
28
1085
1
65.2
745
24
4
32
1037
1
61.8
811
32
AlCl3 high
0
65.2
0
0
0
0
0
0.25
4
4
105
0.1
6.7
96
0.5
4
8
126
0.1
7.9
122
1
4
12
142
0.1
8.8
148
2
4
16
123
0.1
7.6
182
4
4
20
100
0.1
6.1
189
8
4
24
13
0
0.8
83
12
4
28
16
0
0.9
30
4
32
15
0
0.9
77
24
32
FGD high
0
0.25
4
8.8
0
0
0
0
0
4
269
0.3
17
185
185
0.5
4
8
348
0.3
21.8
281
1
4
12
395
0.4
24.5
318
2
4
16
482
0.5
29.7
467
4
4
20
624
0.6
38.1
532
8
4
24
809
0.8
49
679
12
4
28
888
0.8
53.4
722
4
32
880
0.8
52.4
744
24
32
FGD med
0
53.4
0
0
0
0
0
0.25
4
4
354
0.4
22.4
287
0.5
4
8
465
0.5
29.1
432
1
4
12
602
0.6
37.4
506
2
4
16
755
0.7
46.5
744
4
4
20
942
0.9
57.6
976
8
4
24
1206
1.1
73.1
1450
12
4
28
1265
1.2
76
1378
24
4
32
1445
1.4
86.1
1459
32
FGD low
0
86.1
0
0
0
0
0
4
379
0.4
23.9
1269
0.25
4
0.5
4
8
420
0.4
26.3
1634
1
4
12
620
0.6
38.5
2018
2
4
16
850
0.8
52.4
2477
4
4
20
1282
1.2
78.4
3272
8
4
24
1662
1.6
100.7
3611
12
4
28
1938
1.8
116.5
4516
24
4
32
2359
2.2
140.6
4815
32
Sample 2
Soil only
140.6
Sample 3
500
ml
Padj
Mass P
μg/l
Mean of adjusted values
500
ml
P
Padj
mg/m2
mg/l
mg/l
Mass
P
mg/m2
0.023904
1.5
0
0.20
13
66
0.07
4.17
0.33
20
79
0.08
4.95
0.29
19
110
0.11
6.83
0.36
23
131
0.13
0.38
25
162
0.43
27
171
Mass P
mg/m2
dev
t^(1/2)
0.88
0
6.17
5.03
0.25
10.98
8.08
0.5
14.99
6.46
1
8.07
14.72
7.37
2
0.16
9.9
17.91
7.66
4
0.16
10.36
18.96
8.6
8
0
186
Slurry
0.45
29
203
0.19
12.2
20.77
8.41
12
0.43
27
174
0.16
10.37
20.58
8.78
24
0
0
0
0
0
0
0
4
234
5200
5.16
328.39
252.61
68.31
0.25
4
263
6500
6.4
407.18
309.04
85.05
0.5
6
398
7700
7.52
478.43
412.16
60.35
1
9
543
9500
9.2
585.44
532.03
59.22
2
10
647
9500
9.12
580.6
611.15
34.03
4
12
794
11800
11.23
715.15
719.19
72.81
8
10
661
13000
12.27
781.26
699.13
71.19
12
10
655
10400
9.73
619.71
641.56
19.15
24
9
603
10500
9.74
620.32
612.45
9.02
36
13000
low alum
719.19
0.00
0
0
0
0
0
0
0.48
30
407
0.4
24.72
25.31
5.17
0.25
0.77
49
563
0.55
33.91
39.45
8.45
0.5
1.13
72
812
0.79
48.49
54.91
15.13
1
0.83
52
1147
1.11
67.91
49.55
20.16
2
1.94
124
1585
1.52
93.03
92.09
32.16
4
2.21
141
1258
1.2
73.2
92.42
42.29
8
2.33
148
1720
1.62
99.21
104.3
41.82
12
2.50
159
2340
2.18
133.77
120.7
46.28
24
133.77
120.7
159
high alum
0.00
0
0
0
0
0.49
22
496
0.49
31.32
0.78
35
877
0.86
1.25
56
1493
1.46
1.72
77
2011
1.86
83
1.99
2.16
2.47
0
0
29.34
6.55
0.25
54.94
45.93
10.35
0.5
92.77
74.25
18.52
1
1.95
123.93
98.05
23.81
2
2371
2.28
144.9
112.33
30.98
4
89
2429
2.31
147.21
117.97
29.13
8
96
2500
2.36
150.24
126.68
27.63
12
110
2524
2.36
150.4
140.9
27.25
24
150.4
140.9
110
med alum
0
0.00
0
0
0
0
0.26
17
169
0.17
10.68
0.32
15
217
0.21
0.41
19
277
0.62
28
385
0.72
33
0.79
0.95
0
0
0
13.41
3.24
0.25
13.6
14.37
0.67
0.5
0.27
17.23
18.71
1.49
1
0.37
23.71
27.44
3.51
2
502
0.48
30.71
33.14
2.79
4
35
675
0.64
40.91
37.77
2.83
8
42
710
0.67
42.68
44.97
4.32
12
187
0.92
41
733
0.69
42
low lime
46.14
0
0
0
2.31
147
3730
3.7
235.56
3.06
194
4761
4.68
4.30
276
5823
5.90
381
7233
7.70
496
9.41
6.67
24
0
0
0
187.73
44.67
0.25
298.25
254.04
53.23
0.5
5.68
361.81
331.53
47.53
1
7
445.73
420.63
34.18
2
8816
8.46
538.79
517.83
21.34
4
599
9139
8.7
553.88
586.12
28.08
8
8.12
517
10465
9.88
628.91
572.56
55.93
12
9.32
593
13972
13.08
832.56
716.84
119.72
24
832.56
716.84
0
0.00
0
0
0
0
0
1.02
65
2996
2.97
189.21
115.04
78.54
0.25
1.48
93
2901
2.85
181.73
127.35
74.56
0.5
1.94
123
2951
2.88
183.36
138.29
76.39
1
2.43
154
3080
2.98
189.8
153.65
82.48
2
2.27
144
3000
2.88
183.35
153.69
79.77
4
2.30
146
2777
2.64
168.3
150.79
76.5
8
1.94
123
2760
2.61
165.87
154.87
80.59
12
2.80
178
3522
3.3
209.87
190.24
96.15
24
209.87
190.24
0.00
0
0
0
0
0.51
32
330
0.33
20.84
0.66
42
407
0.4
25.5
1.13
72
1144
1.12
0.53
34
1148
1.26
80
1.37
87
2.16
2.02
0
0
0
24.17
7.23
0.25
30.11
10.36
0.5
71.08
58.22
22.82
1
1.11
70.75
50.08
18.95
2
789
0.76
48.22
56.63
20.96
4
806
0.77
48.85
61.52
22.47
8
138
2416
2.28
145.19
139.22
5.34
12
129
1448
1.36
86.28
98.72
26.26
24
145.19
139.22
138
low dry wtr
43.68
0
178
high lime
46.14
0.00
599
med lime
43.68
0.00
0
0
0
0
2.43
155
1837
1.82
116.01
2.60
166
2142
2.11
2.70
172
2572
2.51
2.83
180
5090
5.23
333
5.30
338
0
0
0
132.7
19.92
0.25
134.18
147.55
16.16
0.5
159.8
165.97
6.19
1
4.93
313.67
226.45
75.59
2
5378
5.16
328.68
356.43
44.51
4
5639
5.37
341.76
367.35
48
8
188
5.29
337
5528
5.22
332.22
361.6
47.05
12
7.54
480
8478
7.94
505.18
494.36
12.85
24
505.18
494.36
480
med dry wtr
0.00
0
0
0
0
0.43
27
479
0.48
30.25
0.45
29
650
0.64
0.66
42
895
0.87
0.85
54
1277
0.98
63
1.01
1.01
1.65
0
0
32.38
6.37
0.25
40.72
41.24
12.94
0.5
55.61
49.43
7.01
1
1.24
78.69
79.19
25.39
2
1401
1.34
85.62
87.84
26.44
4
65
1300
1.24
78.79
85.88
25.57
8
65
1253
1.18
75.3
82.57
22.56
12
105
1496
1.4
89.14
160.29
109.89
24
89.14
160.29
105
high dry wtr
0.00
0
0
0
0
0.22
14
3984
3.95
251.6
0.33
21
1964
1.93
123.03
0.35
22
3084
3.01
0.33
21
2307
2.23
0.28
18
1507
0.23
15
0
96.86
134.12
0.25
59.95
55.15
0.5
191.62
79.9
96.77
1
142.17
62.73
68.83
2
1.45
92.1
43.9
41.8
4
888
0.85
53.82
28.51
21.95
8
0.22
14
984
0.93
59.14
30.35
24.99
12
3.52
224
3302
3.09
196.76
184.36
47.06
24
251.6
184.36
0
0.00
0
0
0
0
0
0
6.21
395
1681
1.67
106.16
258.55
145.11
0.25
6.16
392
2577
2.54
161.43
274.38
115.37
0.5
8.22
523
3963
3.87
246.24
375
139.59
1
10.40
662
5813
5.63
358.22
496.51
153.92
2
10.64
677
8452
8.11
516.55
594.61
80.4
4
12.39
789
9595
9.13
581.52
686.18
103.56
8
12.52
797
9749
9.2
585.88
695.84
105.91
12
12.69
808
9216
8.63
549.16
712.25
141.91
24
585.88
712.25
808
med wet wtr
0
0
224
low wet wtr
0
0.00
0
0
0
0
3.45
220
3764
3.73
237.71
1.56
99
1878
1.85
2.68
171
3097
3.02
1.29
82
1634
1.85
118
2.53
161
0
0
0
208.42
36.4
0.25
117.64
98.77
19.11
0.5
192.43
169.98
22.88
1
1.58
100.69
117.17
45.67
2
1336
1.28
81.65
121.6
42.1
4
1602
1.53
97.09
132.77
32.61
8
189
2.02
129
2528
2.39
151.92
133.13
17.07
12
2.41
154
2673
2.5
159.28
146.94
16.66
24
237.71
208.42
220
high wet wtr
0.00
0
0
0
0
3.77
240
1541
1.53
97.32
2.35
149
2111
2.08
2.97
189
2828
2.76
3.30
210
3650
3.33
212
2.98
2.70
1.93
0
0
187.96
78.77
0.25
132.24
148.26
15.47
0.5
175.72
191.12
16.42
1
3.53
224.93
224.23
13.82
2
3895
3.74
238.04
232.1
17.75
4
190
3628
3.45
219.88
207.96
16.06
8
172
3223
3.04
193.69
185.08
11.38
12
123
2455
2.3
146.29
134.09
11.71
24
238.04
232.1
240
Flyash high
0.00
0
0
0
0
1.40
89
1994
1.98
125.93
0.77
49
1007
0.99
2.14
136
2020
2.99
191
3531
2.98
190
1.99
0
93.34
30.69
0.25
63.08
88.7
57.14
0.5
1.97
125.51
130.75
5.31
1
3.42
217.6
198.64
16.49
2
3036
2.91
185.55
184.61
5.86
4
127
2318
2.21
140.49
126
14.96
8
1.55
98
2254
2.13
135.46
110.82
21.34
12
1.68
107
2026
1.9
120.72
104.26
18.04
24
217.6
198.64
0.00
0
0
0
0
1.38
88
551
0.55
34.8
2.24
143
692
0.68
1.95
124
861
0.84
2.13
135
1101
2.19
140
2.44
2.38
2.97
0
0
0
48.29
34.83
0.25
43.35
71.58
61.97
0.5
53.5
73.28
44.59
1
1.07
67.85
86.21
43.1
2
1335
1.28
81.59
96.99
37.3
4
155
1623
1.55
98.36
112.67
37.61
8
152
1619
1.53
97.3
111.04
35.87
12
189
1965
1.84
117.09
135.01
47.59
24
117.09
135.01
189
Fly ash low
0
0
191
Fly ash
medium
0
0.00
0
0
0
0
2.23
142
2204
2.19
139.19
2.97
189
2197
2.16
3.69
235
3113
3.95
252
3286
4.17
265
3860
0
0
0
134.98
9.51
0.25
137.63
167.11
26.5
0.5
3.04
193.42
209.87
22.01
1
3.18
202.5
237.26
30.25
2
3.71
235.91
263.51
26.7
4
190
4.42
281
4463
4.25
270.49
287.39
20.66
8
5.40
344
5248
4.95
315.39
357.8
50.7
12
6.22
396
6007
5.62
357.94
409.45
59.6
24
357.94
409.45
396
FeCl low
0.00
0
0
0
0
0.00
0
332
0.33
20.97
0.81
51
410
0.4
25.71
0.91
58
437
0.43
1.07
68
554
1.24
79
1.52
97
1.54
1.46
0
0
17.21
15.67
0.25
38.42
12.8
0.5
27.18
44.14
15.66
1
0.54
34.15
54.76
18.15
2
539
0.52
32.97
64.38
27.23
4
501
0.48
30.37
77.79
41.32
8
98
458
0.43
27.55
80.88
47.12
12
93
583
0.55
34.74
90.13
54.12
24
34.74
90.13
98
FeCl high
0.00
0
0
0
0
0.07
5
49
0.05
3.07
0.09
6
58
0.06
0.10
7
76
0.07
0.10
6
77
0.09
6
0.00
0.01
0.02
0
11.59
13.41
0.25
3.64
12.46
13.25
0.5
4.75
12.72
12.18
1
0.07
4.77
14.39
15.27
2
65
0.06
3.95
10.8
10.16
4
0
7
0.01
0.4
2.7
4.12
8
1
3
0
0.18
1.5
1.73
12
1
19
0.02
1.13
1.22
0.2
24
4.77
14.39
0.00
0
0
0
0
0.60
38
289
0.29
18.23
0.72
46
383
0.38
23.98
0.92
59
539
0.53
1.05
67
673
0.65
1.05
67
734
0.92
59
0.89
0.77
0
0
0
27.55
9.92
0.25
34.82
10.94
0.5
33.46
47.2
12.73
1
41.47
57.85
14.21
2
0.7
44.86
68.11
24.03
4
723
0.69
43.82
68.12
30.13
8
56
750
0.71
45.07
68.75
31.68
12
49
781
0.73
46.52
69.35
37.44
24
46.52
69.35
67
AlCl3 low
0
0
7
FeCl med
0
0
0.00
0
0
0
0
0
0
0.19
12
512
0.51
32.34
28.41
14.71
0.25
0.35
23
625
0.61
39.13
39.64
17.35
0.5
0.44
28
786
0.77
48.84
48.82
21
1
0.68
43
1019
0.99
62.8
66.87
26.01
2
191
0.83
53
1253
1.2
76.57
78.28
26.63
4
0.96
61
1404
1.34
85.08
85.23
24.35
8
0.94
60
1454
1.37
87.38
86.2
25.66
12
0.89
57
1503
1.41
89.53
97.43
45.36
24
89.53
97.43
61
AlCl3 med
0.00
0
0
0
0
0
0
0.36
23
302
0.3
19.04
21.75
2.34
0.25
0.41
26
455
0.45
28.52
29.73
4.46
0.5
0.41
26
622
0.61
38.62
36.87
9.81
1
0.50
32
820
0.79
50.55
46.64
13.18
2
0.58
37
1034
0.99
63.19
55.07
15.63
4
0.68
43
1080
1.03
65.46
57.54
12.43
8
0.70
45
999
0.94
60.01
56.67
10.62
12
0.76
48
857
0.8
51.07
53.72
7.12
24
65.46
57.54
48
AlCl3 high
0.00
0
0
0
0
0.10
0.12
6
94
0.09
5.94
8
120
0.12
7.52
0.14
9
145
0.14
0.18
11
150
0.18
12
0.08
5
0.03
0.07
0
6.23
0.38
0.25
7.68
0.19
0.5
9.01
9.01
0.19
1
0.15
9.24
9.36
1.81
2
145
0.14
8.86
8.85
2.73
4
50
0.05
3.03
2.95
2.14
8
2
25
0.02
1.5
1.41
0.44
12
5
40
0.04
2.38
2.61
1.85
24
9.24
9.36
0.00
0
0
0
0
0.18
12
527
0.52
33.25
0.28
18
591
0.58
0.31
20
683
0.67
0.45
29
810
0.51
33
0.65
0.68
0.70
0
0
0
20.64
11.24
0.25
37.02
25.47
10.22
0.5
42.43
28.91
11.95
1
0.78
49.92
36.13
11.95
2
929
0.89
56.76
42.47
12.69
4
41
901
0.86
54.62
48.27
6.77
8
43
1020
0.96
61.3
52.68
8.97
12
44
1315
1.23
78.36
58.38
17.77
24
78.36
58.38
44
FGD med
0
0
12
FGD high
0
0.00
0
0
0
0
0.28
18
431
0.43
27.22
0.43
27
436
0.43
0.49
31
481
0.47
192
0
0
0
22.57
4.55
0.25
27.31
27.83
1.13
0.5
29.89
32.91
3.97
1
0.72
46
643
0.62
39.62
44
3.8
2
0.94
60
846
0.81
51.7
56.31
4.12
4
1.38
88
998
0.95
60.48
73.82
13.71
8
1.30
83
1120
1.06
67.31
75.38
7.77
12
1.37
87
1160
1.09
69.12
80.72
10.05
24
69.12
80.72
88
FGD low
0.00
0
0
0
0
1.26
80
361
0.36
22.8
1.61
102
496
0.49
1.97
125
658
2.40
153
928
3.14
200
3.44
0
0
0
42.29
32.78
0.25
31.07
53.25
42.6
0.5
0.64
40.88
68.26
49.48
1
0.9
57.19
87.4
56.55
2
1416
1.36
86.54
121.62
67.98
4
219
2071
1.97
125.52
148.36
62.29
8
4.26
271
3084
2.91
185.34
191.07
77.62
12
4.51
287
3071
2.87
182.99
203.49
75.3
24
185.34
203.49
287
193
0
Appendix C Runoff box study results
194
Notation used in Appendix C
Treatment: treatments as described in chapter 4
Event: This number corresponds to the number of the rainfall simulation event
Volume runoff: total volume of runoff collected during 1 hr runoff event
SS FWMC: flow-weighted mean concentration of suspended solids
DRP FWMC: flow-weighted mean concentration of dissolved reactive phosphorus
TP FWMC: flow-weighted mean concentration of total phosphorus
PP FWMC: flow-weighted mean concentration of particulate phosphorus
Cd: flow-weighted mean concentration of cadmium
Cr: flow-weighted mean concentration of chromium
Cu: flow-weighted mean concentration of copper
K: flow-weighted mean concentration of potassium
Ni: flow-weighted mean concentration of nickel
Pb: flow-weighted mean concentration of lead
Zn: flow-weighted mean concentration of zinc
Al: flow-weighted mean concentration of aluminium
Ca: flow-weighted mean concentration of calcium
Fe: flow-weighted mean concentration of iron
Time to runoff, time from start of rainfall simulator to start of event and thus start of 1 hr
collection period
WEP: Slurry WEP at time of application
DM: slurry DM at time of application
pH runoff water: pH of runoff collected
RS rainfall simulation event as described in Chapter 4
Tank: source mains water in NUI Galway
Table C.1. Runoff box study flow weighted mean concentrations
Treatment
Event
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
alum
alum
alum
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
Volume runoff
ml
4610.7
4764.36
4688.3
4697.4
4752.2
4770.2
5198
4495
5576
4647
4975.7
4849.3
3982
4685
4648
4476
4696
4784
4519
4516
4560
Intensity
mm/hr
10
11
10
10
11
11
12
12
10
10
11
11
9
10
10
10
10
11
10
10
10
SSFWMC
mg/l
296
93
82
235
139
202
192
138
84
4552
4573
1763
3217
3409
1999
2362
3673
1720
406
231
330
195
DRPFWMC
μg/l
87.66
100.80
85.15
169.39
171.49
188.61
238.44
271.73
222.78
896.26
952.73
342.29
358.98
821.19
1114.64
477.02
459.10
478.21
66.34
104.55
61.13
PPFWMC
μg/l
124.74
76.03
50.73
42.59
36.10
24.43
122.95
438.16
93.82
7847.17
9362.10
4183.47
7527.58
8242.42
3931.55
6622.45
7108.90
3291.73
397.81
218.33
204.44
TPFWMC
mg/l
0.32
0.23
0.18
0.23
0.24
0.25
0.59
0.88
0.45
9.17
11.15
5.02
9.45
10.35
5.52
7.79
11.57
5.60
0.64
0.36
0.33
Cd
µg/l
1.89
1.25
1.41
1.52
1.27
1.72
0.15
0.05
0.38
0.92
0.12
1.45
0.05
0.21
1.51
0.29
0.24
0.63
0.47
0.50
1.69
alum
alum
alum
alum
alum
alum
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
lime
lime
lime
lime
lime
lime
lime
lime
lime
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
Treatment
Event
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
alum
alum
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
4916
4871
4609
4226
4403
4565.8
4712
4766
4474
4181
4029
4213
4524
4559
4352
5399.6
4251
4689
5930
5119
5061.8
4343
4650
4769
4533
4679
4638
4226
4315
4278
4210
4243
4342
Cr
µg/l
5.34
2.11
2.17
1.09
1.00
1.29
0.12
0.82
2.19
5.84
4.01
4.54
3.38
2.16
3.46
3.43
2.28
3.83
2.47
2.53
Cu
µg/l
22.26
11.91
15.07
14.33
9.88
15.09
23.14
9.69
12.32
29.17
32.78
66.03
33.38
28.52
73.17
20.67
18.56
59.41
14.22
20.39
K
mg/l
38.99
31.06
26.17
21.21
16.69
16.31
14.02
11.24
11.74
21.27
35.02
74.17
51.49
60.51
81.82
56.12
53.13
78.69
129.86
149.74
11
11
10
9
10
10
10
11
10
9
9
9
10
10
10
12
9
10
13
11
11
10
10
11
10
10
10
9
10
10
9
9
10
Ni
µg/l
0
0
0.7857
0
0.4031
1.1919
2.0594
8.065
2.2605
4.5977
3.0928
38.751
6.416
1.3506
15.89
0.1083
1.1696
9.9897
1.3875
3.9019
357
249
293
536
520
392
772
478
450
683
638
497
465
316
416
753
582
462
641
652
496
572
462
410
1758
1406
1023
852
731
711
808
1275
913
Pb
µg/l
6.4
11.0
5.8
4.2
2.0
13.9
1.2
7.2
8.4
3.5
1.7
3.0
3.0
4.4
17.4
0.1
4.3
10.3
6.5
12.3
196
176.48
185.55
200.02
52.15
86.92
90.55
83.49
50.13
73.06
138.13
97.66
166.55
67.99
68.17
55.16
277.47
283.89
114.31
264.65
195.07
84.67
216.34
183.95
174.58
152.26
246.03
254.56
171.94
149.38
190.67
236.03
275.97
291.02
Zn
µg/l
407.9
460.8
718.9
279.2
419.6
752.5
419.2
413.8
520.4
258.9
349.2
216.4
333.1
332.3
345.3
446.7
440.1
263.3
666.8
1413.1
Al
µg/l
176.3
67.5
79.4
83.5
81.5
51.2
54.3
56.8
45.3
63.4
52.0
116.2
59.3
59.1
210.9
59.7
81.9
112.9
65.6
65.6
555.08
136.40
247.20
385.32
293.28
123.70
1269.21
935.78
899.53
439.34
639.87
309.39
1110.15
896.58
621.26
936.10
620.63
205.23
838.61
1125.78
601.92
312.81
16.85
298.41
2971.16
2488.45
1910.10
1420.25
1002.18
1020.95
1898.58
1878.18
1268.48
Ca
mg/l
91.3
83.2
87.8
85.4
80.5
84.2
83.9
81.3
80.8
106.3
110.7
103.3
117.4
110.5
102.6
114.7
107.5
97.3
141.8
150.3
0.84
0.36
0.51
0.58
0.54
0.39
1.59
1.13
1.08
1.12
1.44
0.69
1.35
1.16
0.80
1.77
1.53
0.70
1.78
1.88
1.08
1.03
0.67
0.94
3.31
3.25
2.69
1.97
1.56
1.45
2.70
2.67
1.94
Fe
µg/l
128.7
74.6
67.5
61.2
70.6
65.5
73.1
53.0
44.8
128.0
190.6
103.6
194.0
227.7
137.1
127.2
116.9
131.1
110.8
148.3
1.33
1.02
0.85
0.96
0.04
0.88
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Time to
runoff
min
pH tank
water
10
7
11
10
7
11
10.45
8
9
17
9
26
20
12
20
18
10
23
21
13
8
8
8
8
8
7.9
8
8.1
8
8
7.6
7.8
8
8
4
8
8
8
8
8
alum
alum
alum
alum
alum
alum
alum
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
lime
lime
lime
lime
lime
lime
lime
lime
lime
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
Treatment
Event
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
slurryonly
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
3.14
2.70
2.92
1.92
1.96
3.61
3.90
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
27.12
23.89
12.58
12.48
20.24
14.20
16.55
8.29
1.21
4.58
3.00
3.00
6.26
9.10
1.32
11.64
3.29
0.00
1.72
1.80
8.41
0.10
1.44
0.00
13.62
1.58
0.18
87.78
112.96
131.18
119.57
88.42
83.54
74.85
33.95
50.13
59.73
54.47
61.21
75.61
60.01
58.22
53.86
37.16
53.27
57.34
68.34
69.40
61.94
79.36
83.94
48.56
71.88
79.16
6.2817
8.6688
0.4569
1.7282
4.5567
0.2449
0.9945
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
6.2
1.9
0.5
2.4
0.9
15.4
11.6
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1737.1
1762.9
618.9
1349.5
1742.3
749.2
1237.2
1317.7
1312.7
1064.8
1476.4
1471.2
1114.0
1801.5
1967.8
1323.8
467.1
595.2
961.9
633.1
690.2
949.4
628.3
591.1
567.7
367.9
371.3
65.6
54.4
54.4
54.4
50.6
50.6
50.6
25.6
23.3
43.6
23.7
25.8
17.8
22.0
18.7
12.8
2.1
2.1
21.6
4.7
5.4
14.2
5.4
2.9
6.0
4.9
6.0
129.3
140.7
146.4
142.3
127.0
126.4
122.8
165.8
194.3
203.0
207.6
193.1
238.9
203.3
192.3
187.4
156.3
216.6
218.2
234.3
203.1
217.1
225.1
194.2
206.0
242.5
254.7
313.7
240.6
131.5
178.9
353.8
123.4
161.2
18.8
9.1
28.1
13.6
0.0
7.5
0.0
1.1
34.4
54.7
113.5
21.3
85.1
122.5
47.2
93.4
193.7
30.7
50.8
77.9
0.00
0.00
32.79
0.00
72.28
75.76
0
0
0
0
645.8
445.4
40.7
4.4
177.2
213.0
54.3
81.5
0.00
0.00
0.00
28.83
23.84
17.83
85.67
64.64
75.64
0
0
0
0
0
0
978.0
879.6
1010.5
89.0
78.0
98.0
207.0
215.5
213.2
19.6
21.6
17.5
Water extractable P of
slurry at time of application
mg/kg
Slurry DM at time of application
%
1.9364
1.9364
1.9364
1.7387
1.7387
1.7387
1.8468
1.8468
1.8468
10.56
10.49
10.4
197
19
21
13
19
14
10
12
17
10
20
29
8
15
17
10
20
29
12
17
27
12
14
29
8
16
19
6
16
20
5
12
17
6
16
pH runoff water
7.5
7.6
7.6
7.6
7.7
7.6
7.5
7.6
7.9
7.6
7.6
7.5
7.8
7.8
7.7
7.8
7.7
7.8
8
8
8
8
8
8
8
7.9
8
8
8
8
8
7.98
8
8.3
8
8
7.8
8
8
8
8
8
8
8.1
8
8
8
8
8
8
8.1
8.1
alum
alum
alum
alum
alum
alum
alum
alum
alum
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
lime
lime
lime
lime
lime
lime
lime
lime
lime
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
ferrous
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1
2
3
1.8468
1.8468
1.8468
1.8468
1.8468
1.8468
0.0074
0.0074
0.0074
0.012
0.012
0.012
0.013
0.013
0.013
0.0094
0.0094
0.0094
0.0153
0.0153
0.0153
0.0124
0.0124
0.0124
0.0134
0.0134
0.0134
0.0171
0.0171
0.0171
0.0187
0.0187
0.0187
0.0159
0.0159
0.0159
9.4
9.6
9.3
9.3
9.63
9.86
8
8.6
9.8
10.25
10.16
198
7.5
7.4
7.5
7.44
7.4
7.6
7.47
7.5
7.5
7.9
7.9
7.9
7.8
7.8
7.8
7.9
7.9
7.9
7.4
7.5
7.45
7.4
7.5
7.6
7.6
7.6
7.6
7.7
7.8
7.8
7.5
7.5
7.5
7.8
7.8
7.8
Table C.2. Runoff box study flow weighted mean metal concentrations
Fe
Lime
PAC
alum
Slurry
RS
Cd
Cr
Cu
K
Ni
Pb
Zn
µg/l
µg/l
µg/l
mg/l
µg/l
µg/l
1
0.8 (0.7)
4.8 (0.9)
42.7 (20.3)
43.5 (27.5)
µg/l
15.5
(20)
2.7 (1)
274 (67)
2
0.6 (0.8)
3 (0.7)
45 (24.5)
64.6 (15.6)
7.9 (7.4)
8.3 (7.9)
337 (7)
3
0.4 (0.2)
3.2 (0.8)
32.9 (23)
62.6 (14)
3.8 (5.4)
4.9 (5.5)
383 (104)
1
0.9 (0.7)
2.7 (0.4)
20.6 (6.5)
122.5 (31.6)
3.9 (2.5)
8.3 (3.4)
1272 (549)
2
1.1 (0.2)
2.5 (0.5)
16.3 (6.6)
121.2 (9.2)
3.6 (4.2)
1.6 (1)
1244 (579)
3
0.6 (0.5)
3.2 (1)
17 (3.1)
82.3 (6.9)
1.9 (2.2)
9.3 (7.5)
1243 (497)
1
< limit
< limit
4.7 (3.5)
47.9 (13)
< limit
< limit
1232 (145)
2
< limit
< limit
2.2 (3.5)
63.7 (10.8)
< limit
< limit
1354 (208)
3
< limit
< limit
7.4 (5.4)
57.4 (3.2)
< limit
< limit
1698 (344)
1
< limit
< limit
1.7 (1.7)
49.3 (10.7)
< limit
< limit
674 (257)
2
< limit
< limit
3.4 (4.4)
66.6 (4)
< limit
< limit
758 (169)
3
< limit
< limit
5 (7.5)
70.6 (19.2)
< limit
< limit
596 (31)
1
< limit
< limit
0.9 (1)
75.5 (5.5)
< limit
< limit
370 (23)
2
< limit
< limit
< limit
< limit
16.4 (23.2)
24.8 (5.5)
74 (2.5)
75.6 (10.5)
< limit
< limit
< limit
< limit
546 (142)
978 (68)
1
1.2 (0.9)
2.2 (2.8)
19.9 (4.9)
24.7 (12.9)
0.7 (1.2)
4 (2.6)
369 (78)
2
0.9 (0.7)
1.3 (0.7)
10.5 (1.2)
19.7 (10.2)
2.8 (4.5)
6.8 (4.5)
431 (26)
3
1.2 (0.7)
1.9 (0.5)
14.2 (1.6)
18.1 (7.4)
1.4 (0.8)
9.4 (4.2)
664 (125)
< limit
0.7 (0.1)
22.1 (1.5)
1.8 (0.1)
6.3 (3.2)
< limit
613 (136)
Grass
3
Tank
199
Table C.3 Runoff box study box nutrient concentrations (Chapter 4)
Date
10-May
Treatment
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
RS
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
Time
after 0
min
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
pH
runoff
7.44
7.39
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.6
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.7
7.6
7.6
Vol
runoff
mg
438
374
377
402
428
389
416
410
449
389
454
390
345
390
436
399
410
426
415
411
410
474
370
385
356
315
374
374
382
425
359
408
375
391
395
455
255
357
352
413
412
411
420
420
430
410
407
411
267
316
386
200
SS
mg/l
393
419
459
430
404
383
228
427
325
340
138
372
276
288
308
280
253
261
224
255
199
218
224
202
410
476
365
302
218
326
251
357
226
237
211
189
288
305
102
357
184
204
227
327
350
150
200
125
131
206
84
DRP
μg/l
189
188
174
224
152
177
157
174
171
181
171
162
149
161
149
165
187
198
199
210
177
207
196
221
153
168
194
198
192
206
215
188
192
224
231
225
177
174
175
168
164
187
147
145
166
172
203
159
198
175
158
PP
μg/l
374
504
482
572
447
700
626
278
600
678
688
721
164
196
149
137
139
100
107
103
122
157
165
105
414
417
63
206
284
203
231
51
249
250
332
306
44
57
111
96
56
15
31
10
14
21
24
47
24
75
72
TP
μg/l
DUP
μg/l
615
773
780
871
745
989
926
599
893
949
958
993
404
431
362
356
364
327
334
327
318
375
368
360
620
590
317
463
510
491
533
341
496
547
607
599
264
231
296
282
235
204
219
191
195
220
233
212
273
269
273
TDP
μg/l
53
81
124
76
146
112
143
146
122
89
99
110
90
74
65
54
38
28
28
13
19
11
7
34
54
4
60
60
34
82
86
101
56
73
44
67
44
0
9
19
14
1
41
36
14
26
6
7
51
19
43
242
269
298
299
298
289
300
320
293
271
270
271
239
235
214
219
225
227
227
224
196
218
203
255
207
173
254
257
226
288
302
289
248
297
275
292
221
174
185
187
178
189
188
181
181
199
210
166
249
194
201
17-May10
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.6
7.6
7.7
7.7
7.7
7.7
7.7
7.7
7.7
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
395
418
438
442
420
417
412
422
420
298
368
386
438
440
372
437
410
399
411
396
415
46
179
88
25
313
268
235
52
57
536
159
175
129
72
190
247
167
290
132
200
229
147
163
138
153
157
238
198
167
177
121
202
260
290
182
185
204
186
174
177
187
182
95
15
27
48
46
20
18
56
22
129
43
31
30
31
29
29
20
66
47
89
32
283
228
222
236
242
272
267
246
211
278
267
312
387
253
263
316
315
357
235
278
221
40
50
57
34
39
14
51
22
12
28
22
21
67
40
49
83
109
117
11
2
7
188
213
195
188
196
251
249
189
189
149
224
281
357
222
234
287
295
291
188
189
189
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
353
345
374
363
384
384
398
398
383
383
380
380
307
391
381
390
335
335
386
386
444
444
382
382
347
340
321
374
369
369
367
367
374
374
377
377
197
225
367
392
219
390
570
570
550
550
750
750
290
450
320
240
220
440
290
290
280
280
350
350
180
410
940
390
280
280
320
320
530
530
430
430
23
89
86
85
75
75
82
82
26
26
82
82
90
33
86
26
87
87
30
30
86
86
91
91
69
73
24
82
28
28
84
84
58
58
37
37
1725
1850
1828
1915
1981
772
652
652
555
557
520
520
862
973
895
979
1126
1090
1156
1156
969
946
616
616
1183
1113
1035
1021
153
247
335
335
489
489
495
495
1981
2017
2100
2182
2245
1000
844
844
789
789
783
783
1107
1225
1251
1277
1367
1345
1424
1424
1234
1234
907
907
1384
1291
1256
1221
332
450
562
562
689
689
668
668
233
78
185
183
189
153
110
110
208
205
181
181
155
219
270
272
154
168
239
239
179
202
200
200
133
105
197
119
152
175
143
143
142
142
136
136
256
167
271
268
264
228
193
192
234
232
263
263
245
252
356
298
241
255
268
268
265
288
291
291
201
178
221
200
179
203
227
227
200
200
174
174
201
24-May10
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.6
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
366
363
376
376
388
393
388
405
392
395
405
400
356
404
444
507
358
367
417
408
433
427
433
422
347
395
400
401
406
419
419
391
426
425
391
429
1933
4200
3267
5000
3333
4000
4133
4867
5533
5933
6600
5467
7300
5933
3509
5404
4759
3950
3600
5250
2500
4600
4000
4467
1640
1353
2238
1793
1231
1792
1950
750
2235
2467
1563
2000
701
636
766
837
874
992
944
1054
1055
1047
881
922
705
783
891
812
941
1050
1142
995
1003
1109
1193
799
176
128
305
346
305
389
341
376
441
431
403
423
947
1623
2982
4553
6157
7461
8867
10672
11213
11834
13760
12427
9595
9198
9996
10352
9902
11742
9206
9890
9154
6763
4697
12212
4286
4105
4465
4603
4950
5246
4108
4404
3703
3026
1760
5460
1791
2372
3861
5402
7050
8536
10230
12131
12751
13559
15754
14814
11196
10904
11668
12160
11707
13617
10919
11721
11003
8628
6606
13980
5038
4907
5251
5472
5798
6128
4913
5275
4572
3883
2658
6291
144
113
113
11
18
82
420
405
483
678
1113
1465
896
923
781
996
863
825
571
837
846
756
717
969
576
674
481
522
544
493
464
494
428
425
494
408
845
750
879
848
892
1074
1364
1459
1538
1725
1994
2387
1601
1706
1673
1808
1805
1875
1713
1831
1849
1865
1910
1768
752
802
786
869
848
881
805
871
869
856
898
831
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
7.7
7.7
7.7
7.7
7.7
7.8
7.8
7.7
7.7
7.7
7.7
7.7
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
394
337
371
359
398
398
371
371
385
385
383
383
395
371
371
371
390
390
403
403
413
1600
1960
1280
1460
1580
1580
1740
1740
1560
1560
1620
1620
1500
1300
940
1400
1440
1440
1560
1560
1500
110
110
102
145
169
194
152
152
106
106
322
322
156
196
171
174
248
214
236
236
325
1647
2226
2513
2471
2643
2621
2612
2679
2699
2712
2733
2702
2349
2696
2788
2774
2376
2377
2400
2427
2562
2241
2925
3313
3313
3488
3488
3488
3488
3501
3501
3501
3501
3086
3395
3545
3545
3165
3165
3165
3165
3218
484
590
699
697
676
673
724
657
696
683
446
476
581
503
586
597
541
574
529
502
332
594
699
801
842
845
867
876
809
802
789
768
798
737
699
756
771
789
788
765
738
656
202
31-May10
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.8
7.8
7.8
7.8
7.8
7.9
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
413
381
381
370
372
439
342
398
398
411
411
389
389
360
360
315
293
324
349
326
333
367
360
378
380
456
345
284
384
347
360
370
365
375
369
371
370
360
360
280
342
380
334
431
431
299
299
361
361
381
381
1500
1340
1340
760
460
1660
920
1000
1000
1120
1120
880
880
1180
1180
550
600
680
530
850
850
940
940
940
940
1110
1110
470
690
660
650
830
830
640
640
840
840
810
810
720
670
620
700
690
690
720
720
680
680
820
820
325
330
330
162
95
299
298
312
349
355
355
194
194
184
224
218
202
198
183
184
184
161
161
149
149
150
150
154
155
150
155
149
149
151
151
148
148
141
141
188
180
187
183
190
190
185
185
194
194
203
203
2450
2353
2345
1419
1661
1939
1924
1996
2015
1967
1941
1977
2022
2034
1997
1283
1153
1165
1158
1151
1461
1771
1771
1588
1569
1414
1414
1302
1241
946
886
827
935
1043
1043
1042
913
949
949
1029
984
918
1030
1142
1077
1012
1012
1111
1000
910
1003
3218
3218
3218
2062
2415
2711
2711
2796
2796
2756
2756
2823
2823
2823
2823
1616
1616
1703
1730
1758
2057
2355
2355
2134
2136
2000
2000
1857
1857
1539
1473
1406
1498
1591
1591
1498
1468
1500
1500
1441
1441
1345
1401
1456
1448
1440
1440
1567
1456
1456
1456
444
535
544
480
658
473
490
488
432
434
461
652
607
605
602
115
261
340
390
423
412
423
423
397
418
436
436
401
461
444
431
430
414
396
396
308
407
410
410
224
277
240
188
124
181
243
243
262
262
343
250
768
865
873
642
754
772
788
800
781
789
816
846
801
789
825
333
464
538
572
607
596
584
584
546
567
586
586
555
616
594
587
579
563
547
547
456
555
551
551
412
457
427
371
314
371
428
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456
456
546
453
PAC
PAC
PAC
PAC
PAC
PAC
1
1
1
1
1
1
2.5
7.5
12.5
17.5
22.5
27.5
7.9
7.9
7.9
7.9
7.9
7.9
352
356
386
383
431
431
360
250
467
404
923
900
101
106
103
65
130
130
886
825
1236
1589
1595
1688
1141
1133
1504
1876
1899
2000
154
202
165
222
174
182
256
307
269
287
305
312
203
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.9
378
378
410
410
399
399
372
442
343
432
352
352
414
414
422
422
402
402
283
303
351
401
386
386
397
397
395
395
392
392
339
290
377
310
384
384
324
324
363
363
362
362
181
245
323
333
359
359
356
356
383
383
377
377
222
295
351
204
925
925
1000
1000
981
981
580
390
100
30
596
741
702
702
444
444
520
520
440
360
460
440
460
460
410
410
480
480
490
490
617
783
783
967
667
667
500
500
700
700
667
667
717
850
783
600
633
633
650
650
783
783
350
350
450
217
400
36
36
59
59
85
85
38
30
38
25
97
97
50
50
42
42
54
54
33
91
82
52
116
116
116
116
32
32
44
44
258
125
245
59
237
237
61
61
110
110
58
58
62
49
54
61
45
45
100
100
95
95
207
207
139
142
146
1618
1618
1155
1156
884
884
742
918
954
911
1044
972
818
818
849
896
1027
1027
762
1043
926
865
312
411
545
545
967
976
1637
1637
1410
1261
915
310
178
20
46
46
89
89
210
210
134
338
673
876
966
926
833
833
311
311
411
411
431
43
47
1938
1938
1500
1500
1268
1268
1043
1252
1213
1174
1312
1200
1006
1006
1050
1050
1133
1133
873
1154
1099
1043
497
600
739
739
1200
1200
1865
1865
2087
2046
1586
1127
943
760
760
760
823
823
956
956
926
1058
1295
1532
1586
1640
1640
1640
1300
1300
1479
1479
752
429
440
284
284
286
285
299
299
263
304
222
239
171
131
139
139
159
112
52
52
78
19
90
127
69
74
78
78
201
192
184
184
419
659
426
757
528
502
653
653
624
624
688
688
730
671
567
595
575
669
706
706
894
894
860
860
182
245
247
320
320
345
344
384
384
301
334
259
264
268
228
189
189
201
154
106
106
111
110
173
179
185
189
194
194
233
224
228
228
677
785
671
817
765
739
714
714
734
734
746
746
792
720
622
656
620
713
807
807
989
989
1068
1068
321
386
393
14-Jun10
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
PAC
3
3
3
3
3
3
3
3
3
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.8
7.7
7.8
7.8
7.8
7.8
7.8
7.8
7.8
332
366
366
368
368
395
395
379
379
617
617
433
433
517
583
583
517
517
171
176
176
157
157
177
177
181
181
113
189
246
228
228
477
477
504
504
502
576
650
650
650
900
900
909
909
218
212
229
265
265
246
246
225
225
389
387
405
422
422
423
423
405
405
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.5
7.4
7.4
7.3
7.3
7.3
7.3
7.3
7.3
7.3
7.3
7.3
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.6
7.6
7.6
7.6
7.6
7.6
7.6
412
346
343
347
392
361
385
387
415
372
392
367
337
358
380
367
374
400
370
387
386
448
343
366
343
285
366
373
393
428
356
402
380
387
391
456
402
406
401
449
412
451
446
422
464
449
462
434
345
376
396
385
313
754
386
359
327
426
460
368
215
270
251
261
232
244
226
242
248
183
200
209
256
337
301
306
357
453
325
255
354
219
514
277
318
237
160
133
200
197
92
204
188
168
145
280
97
71
68
65
77
48
63
57
58
52
70
67
46
54
50
148
47
48
73
47
60
112
39
42
60
72
69
69
62
61
56
66
51
47
55
66
195
231
206
236
220
227
221
215
238
326
262
273
623
582
520
701
504
319
204
477
229
229
220
208
142
243
177
127
225
179
142
179
266
313
269
217
271
154
189
353
297
149
70
491
33
212
139
254
133
107
132
91
145
81
61
37
45
93
70
23
832
805
761
926
768
755
449
694
442
444
416
406
359
410
333
314
410
315
286
312
388
434
381
333
374
328
341
483
433
235
191
645
152
328
296
374
643
623
643
654
643
590
567
543
547
564
523
543
112
152
173
160
187
388
182
160
155
163
126
132
170
112
105
39
138
87
71
86
62
9
73
74
44
101
83
61
73
25
66
87
67
69
102
53
314
285
305
327
278
283
285
291
265
145
191
246
209
223
241
225
264
436
245
216
213
216
196
199
216
166
156
187
185
136
144
133
122
121
112
116
104
174
152
130
136
86
122
153
118
116
157
120
510
516
511
563
498
509
506
506
502
471
453
520
205
28-Jun10
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.6
7.5
7.5
7.5
7.5
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.9
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
477
376
427
436
480
550
398
421
545
407
520
539
434
566
413
267
367
340
368
343
383
315
343
356
191
183
183
174
182
61
112
110
78
166
154
103
125
99
116
74
69
84
88
48
37
108
67
71
280
267
272
256
265
261
258
267
283
289
278
279
102
166
156
261
255
266
280
237
234
236
281
281
593
502
530
476
445
411
356
421
444
389
321
394
198
109
20
96
118
138
107
89
79
35
62
49
958
931
987
955
943
888
819
841
853
796
757
812
345
322
457
567
523
546
521
476
453
432
456
432
85
161
185
223
234
216
205
153
126
118
158
139
45
47
280
210
150
142
134
150
140
161
113
102
365
429
457
479
499
477
463
420
409
408
436
418
147
213
437
471
405
408
414
387
374
397
394
383
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.45
7.4
7.44
7.45
7.5
7.5
7.5
7.6
7.4
374
418
460
456
532
385
478
453
466
476
463
439
287
396
349
358
370
360
414
392
323
362
376
265
348
380
390
390
386
403
404
384
415
691
698
696
1000
794
739
713
826
747
716
778
611
654
632
674
558
711
293
429
667
607
767
485
520
386
394
425
491
316
341
200
885
755
190
259
270
286
334
244
173
293
326
309
360
255
207
223
224
286
287
328
278
241
295
324
345
388
118
78
95
107
108
111
131
135
117
932
1080
1240
1159
965
1037
1171
1050
909
843
602
237
18
73
191
126
1215
1290
1383
1082
1220
183
267
80
136
333
87
118
114
58
152
128
484
1964
2112
2255
2081
1890
1994
2177
1922
1753
1524
1079
543
871
911
1040
974
1891
1957
2023
1862
1666
1835
1634
1564
529
493
566
620
729
639
663
662
1081
842
773
745
637
591
713
834
578
518
373
117
51
645
614
625
562
389
338
363
539
151
1328
1021
1096
275
83
384
395
507
470
380
399
480
1033
1032
1015
922
925
957
1007
871
844
681
477
306
853
837
849
848
676
666
640
780
446
1652
1367
1484
393
160
479
502
616
581
511
534
597
206
05-Jul-10
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
7.4
7.4
7.4
7.4
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.6
7.5
7.53
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.47
7.46
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.4
7.5
7.5
7.5
7.5
7.5
7.5
414
388
387
456
402
520
520
612
443
538
327
533
540
529
510
341
462
409
420
436
419
477
455
389
442
442
427
352
411
425
423
420
423
443
423
458
445
422
417
248
272
258
347
373
397
388
435
362
382
396
368
331
359
320
365
379
392
207
586
303
448
347
410
571
711
771
464
690
852
694
628
1044
439
500
517
619
581
736
733
732
699
787
674
543
684
786
633
435
263
468
383
588
431
404
229
735
667
478
485
580
554
625
531
553
523
575
543
500
476
333
556
722
505
427
727
133
139
98
210
231
242
200
278
202
304
285
253
368
297
282
216
177
192
193
122
173
206
162
173
219
248
263
62
66
81
76
80
81
80
75
83
89
95
145
58
46
79
48
46
43
58
47
43
52
56
59
126
66
74
69
84
80
680
39
86
157
863
751
1014
1080
518
1025
1101
837
688
1050
905
1041
1216
1200
1224
1072
1180
1149
1080
1103
1075
1042
1112
123
602
683
768
719
625
670
643
488
655
529
641
453
443
413
451
349
350
372
371
342
379
344
415
400
643
323
256
217
202
1232
575
531
968
1425
1507
1733
1886
1930
2156
2068
1995
1959
1930
1724
1845
1950
1991
1999
1900
1938
1910
1776
1848
1793
1722
1849
864
1022
1080
1220
1219
1074
1110
1163
870
1076
1066
1146
643
646
648
654
548
574
602
567
543
563
531
520
628
875
526
553
496
488
419
396
347
601
331
514
520
528
1210
828
683
905
902
583
537
588
557
599
582
706
586
555
534
572
499
432
474
679
354
316
376
420
368
359
445
299
331
443
359
133
156
156
155
153
181
172
149
158
133
131
46
102
167
128
228
194
206
551
535
445
811
562
756
720
806
1412
1131
967
1158
1271
880
819
804
734
791
775
828
759
761
696
744
718
680
736
741
420
397
451
500
449
439
520
382
421
538
505
191
202
235
202
199
224
231
196
201
185
187
105
228
233
202
297
278
286
07-Jul-10
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
alum
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
Grass
lime
lime
lime
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.5
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
361
387
404
336
384
385
392
250
338
387
386
413
404
380
447
375
389
405
326
384
351
390
394
392
397
400
408
364
416
389
295
433
381
382
397
412
427
398
408
404
417
411
335
393
356
409
416
362
414
394
403
408
389
409
366
295
381
208
529
500
660
254
551
446
309
371
624
467
378
544
167
212
143
486
638
420
286
213
370
240
253
267
301
302
300
433
344
256
158
88
138
45
25
76
23
42
170
100
216
48
63
85
134
50
33
95
95
115
68
85
130
43
550
367
850
81
85
89
91
94
105
73
89
84
83
84
86
115
99
97
90
97
87
67
71
69
75
82
77
74
76
194
102
77
81
79
72
75
77
83
84
106
100
65
109
122
130
48
44
68
75
79
113
81
96
89
82
95
145
280
105
132
216
204
248
253
291
301
85
31
147
145
160
78
101
146
37
107
182
248
166
187
206
228
172
144
74
59
74
56
58
93
90
91
101
85
83
86
66
63
74
60
73
45
138
88
89
46
22
11
34
31
40
54
66
8
405
304
461
480
484
453
476
526
525
391
393
388
383
436
378
400
402
367
377
394
425
352
372
401
424
375
347
293
281
288
223
256
265
278
271
269
246
244
227
198
206
206
192
209
177
233
176
186
168
145
156
179
187
167
165
198
166
1095
1030
1084
183
195
117
132
141
119
234
273
157
155
192
215
184
157
232
180
115
90
119
114
125
121
121
126
146
146
20
65
121
91
109
108
93
83
78
57
26
44
66
24
14
2
47
44
29
47
44
32
64
60
38
29
37
13
410
621
491
264
280
205
223
235
224
306
362
241
237
276
300
299
256
330
270
212
177
186
185
194
196
203
203
220
222
214
167
197
172
188
180
168
161
161
141
132
144
131
133
135
132
95
88
97
122
123
145
145
156
127
111
132
158
690
726
624
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
lime
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.5
7.6
7.7
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.6
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.7
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
7.9
327
395
395
354
354
373
373
366
366
392
295
389
377
391
391
395
395
434
434
379
379
340
380
405
382
399
399
403
403
429
429
401
401
153
216
274
304
326
339
358
373
378
411
393
457
276
268
348
390
357
395
406
435
439
449
436
486
209
533
650
650
650
650
450
450
500
500
567
467
517
400
450
450
567
567
400
400
383
383
567
500
433
450
450
500
500
450
167
167
400
400
1067
1667
3000
2880
2900
3933
4200
2400
3733
3600
3267
3800
1950
3400
3300
3350
3050
3333
3533
3600
3267
4067
2600
4667
129
100
100
286
286
291
291
295
295
122
86
133
98
269
269
132
132
169
169
306
306
150
145
158
186
193
193
167
167
188
188
177
177
150
169
177
225
351
363
472
384
375
512
460
373
918
826
700
541
735
709
691
714
1166
867
1134
800
335
257
260
306
306
200
200
18
18
32
28
14
38
8
50
9
9
143
177
253
253
46
402
176
501
292
306
265
265
277
277
459
459
663
47
672
306
3892
5735
10434
11737
12089
10821
11021
10748
10786
4776
5785
8786
10025
9238
9341
9244
9054
6303
9224
6279
1139
1097
1055
1055
1055
1000
1000
863
863
410
790
628
566
629
713
713
713
800
834
926
926
211
929
901
873
928
983
983
983
1000
1000
1186
1186
1219
798
1686
1974
5565
7519
12419
13855
14089
12982
13890
13330
12350
6317
8099
11029
12592
11764
11279
11031
10603
8857
11022
8878
674
740
694
463
463
509
509
550
550
256
676
481
430
351
393
572
572
488
488
367
367
15
382
566
186
442
484
551
551
535
535
550
550
406
582
837
1443
1322
1421
1514
1735
1625
1649
2410
2209
646
715
1614
1702
1832
1817
1248
1073
383
1687
665
1799
803
840
794
749
749
800
800
845
845
378
762
613
528
621
662
704
704
657
657
673
673
165
526
725
372
635
677
718
718
723
723
727
727
556
751
1014
1668
1673
1784
1986
2119
2000
2161
2870
2582
1564
1541
2314
2243
2567
2526
1939
1787
1549
2554
1799
2599
12-Jul-10
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
slurry
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
1
1
1
1
1
1
1
1
1
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
7.7
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.7
7.7
7.7
7.7
7.7
7.7
7.7
7.7
7.9
7.9
7.9
7.9
7.9
7.7
7.7
7.7
7.7
7.9
7.7
7.8
7.6
7.7
7.7
7.7
7.7
7.7
7.7
7.7
7.7
7.7
7.7
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
235
334
335
400
312
384
399
426
409
480
446
488
320
334
357
364
380
379
385
390
384
438
347
398
342
298
384
412
376
401
413
415
411
421
403
420
330
381
405
434
345
405
411
413
415
429
409
407
360
323
348
345
371
371
342
342
356
210
3000
1575
1000
880
5480
2040
2200
2600
1250
1367
1833
1867
3050
3200
960
1080
1360
1233
1950
3550
2800
3150
2600
3300
1550
1257
4200
7333
1550
3150
3700
4867
4867
3800
3200
3400
1525
1200
2367
1800
2650
1667
1933
1467
1500
1833
1367
1400
670
670
620
660
700
700
860
860
960
868
984
1138
1077
1093
1057
1050
1134
1125
1130
1224
1309
574
529
72
40
166
430
517
557
538
649
758
850
256
340
271
280
491
368
390
448
517
609
777
682
410
364
369
495
482
556
514
466
619
558
543
334
256
95
272
272
277
280
274
274
256
4973
4168
3806
2338
2957
3191
4536
5369
3377
4483
4416
3596
11485
8524
796
1380
2470
3460
5202
6553
7400
10152
10881
11207
7439
8363
4052
5659
7138
7785
8233
7800
7690
6985
6176
8159
307
448
677
1992
1344
4779
4282
5711
4982
4619
4558
4682
1154
1333
1336
1314
1827
1847
1834
1851
2563
6049
5191
4994
4060
4692
5098
6247
6896
5324
6061
5858
5469
12084
9125
1528
2141
3287
4588
6520
7995
8951
11741
12506
12850
10819
12188
11596
11883
11550
11701
12245
11784
11642
10977
10100
12347
2589
2566
3225
4971
4930
6867
6902
7053
7209
6699
7076
6206
1745
1993
2150
2150
2668
2668
2668
2668
3417
208
39
50
645
642
850
661
393
822
448
218
564
25
72
660
721
651
698
800
885
1013
939
867
793
3124
3485
7273
5944
3921
3548
3622
3536
3435
3383
3147
3506
1872
1754
2179
2484
3104
1533
2106
876
1608
1522
1975
1190
336
564
541
563
564
541
560
543
598
1076
1023
1188
1722
1735
1907
1711
1527
1947
1578
1442
1873
599
601
732
761
817
1128
1317
1442
1551
1588
1625
1643
3380
3825
7544
6224
4412
3916
4012
3984
3952
3992
3924
4188
2282
2118
2548
2979
3586
2089
2620
1342
2227
2080
2518
1524
591
659
813
836
841
821
834
817
854
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
Fe
1
1
1
2
2
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
3
3
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
57.5
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
7.8
356
349
349
362
334
334
352
355
355
361
361
373
373
342
342
324
330
396
311
365
365
370
370
377
377
380
380
211
960
1020
1020
1100
1760
980
1320
1240
1240
1280
1280
1280
1280
1280
1280
960
1420
1540
1080
540
540
900
900
560
560
1000
1000
256
152
152
312
292
273
271
292
300
289
289
315
315
176
176
319
333
332
342
350
290
369
369
224
224
182
182
2553
2585
2541
1575
1879
2266
2231
1835
1751
1785
1655
1838
1857
1968
1942
586
912
570
650
1241
1261
1582
1552
1594
1704
1655
1710
3417
3417
3417
2452
2615
2993
2993
2536
2536
2536
2536
2718
2718
2718
2718
1160
1445
1321
1321
1942
1942
2332
2332
2305
2305
2305
2305
608
680
724
565
444
455
491
409
485
462
592
565
546
574
601
255
199
419
329
351
391
381
411
487
377
468
412
864
832
877
877
736
728
762
701
785
751
882
880
861
750
777
574
533
751
671
701
681
750
780
711
601
650
594
Appendix D Results from Chapter 5
212
Table D.1 Ammonia emissions data
mass
N
Cumulative runtime
Run
time
Period
mins
hours
mg/l
mgN m2
mgN
NH3-N loss kg/ha
hourly KG HAmeasurement
1
period
(mins)
Slurry
Slurry
Slurry
Alum
Alum
Alum
Ferrous
1
120
120
2
45.56
29
3699
18
18
2
240
360
4
22.97
13
1703
4
4
3
1080
1440
18
44.83
26
3325
2
2
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
16.76
9
1215
0
0
6
4320
10080
72
0.00
0
0
0
0
1
120
120
2
31.99
20
2570
13
13
2
240
360
4
31.90
17
2234
6
6
3
1080
1440
18
52.33
30
3881
2
2
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
22.00
12
1577
0
0
6
4320
10080
72
0.00
0
0
0
0
1
120
120
2
33.49
21
2732
14
14
2
240
360
4
35.55
21
2637
7
7
3
1080
1440
18
45.97
27
3429
2
2
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
15.34
9
1112
0
0
6
4320
10080
72
0.00
0
0
0
0
1
120
120
2
0.41
0
33
0
0
2
240
360
4
1.14
1
83
0
0
3
1080
1440
18
3.22
2
236
0
0
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
7.40
4
549
0
0
6
4320
10080
72
0.00
0
0
0
0
1
120
120
2
0.67
0
54
0
0
2
240
360
4
2.42
1
156
0
0
3
1080
1440
18
4.04
2
250
0
0
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
5.33
3
389
0
0
6
4320
10080
72
0.00
0
0
0
0
1
120
120
2
0.39
0
32
0
0
2
240
360
4
13.77
8
1021
3
3
3
1080
1440
18
15.63
9
1159
1
1
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
6.59
4
473
0
0
6
4320
10080
72
0.26
0
14
0
0
1
120
120
2
9.39
6
774
4
4
2
240
360
4
16.64
11
1358
3
3
3
1080
1440
18
26.66
17
2175
1
1
213
Ferrous
Ferrous
Lime
Lime
Lime
PAC
PAC
4
1440
2880
24
35.60
21
2641
1
1
5
2880
5760
48
24.40
13
1639
0
0
6
4320
10080
72
3.55
2
226
0
0
1
120
120
2
7.00
4
574
3
3
2
240
360
4
18.86
12
1531
4
4
3
1080
1440
18
24.60
15
1895
1
1
4
1440
2880
24
39.62
22
2775
1
1
5
2880
5760
48
21.87
13
1649
0
0
6
4320
10080
72
2.88
1
154
0
0
1
120
120
2
9.92
6
817
4
4
2
240
360
4
23.51
15
1918
5
5
3
1080
1440
18
25.98
16
1991
1
1
4
1440
2880
24
36.88
22
2765
1
1
5
2880
5760
48
15.60
10
1285
0
0
6
4320
10080
72
2.51
1
149
0
0
1
120
120
2
115.47
73
9421
47
47
2
240
360
4
30.75
19
2496
6
6
3
1080
1440
18
18.58
11
1371
1
1
4
1440
2880
24
4.47
2
313
0
0
5
2880
5760
48
0.63
0
34
0
0
6
4320
10080
72
0.66
0
42
0
0
1
120
120
2
112.20
71
9108
46
46
2
240
360
4
33.94
22
2769
7
7
3
1080
1440
18
11.84
7
927
1
1
4
1440
2880
24
4.80
3
334
0
0
5
2880
5760
48
0.47
0
33
0
0
6
4320
10080
72
0.01
0
0
0
0
1
120
120
2
79.14
50
6457
32
32
2
240
360
4
25.26
15
1977
5
5
3
1080
1440
18
15.10
9
1182
1
1
4
1440
2880
24
4.92
3
345
0
0
5
2880
5760
48
0.17
0
12
0
0
6
4320
10080
72
4.14
2
278
0
0
1
120
120
2
4.50
3
365
2
2
2
240
360
4
9.07
6
732
2
2
3
1080
1440
18
25.48
15
1963
1
1
4
1440
2880
24
35.97
20
2609
1
1
5
2880
5760
48
22.52
12
1596
0
0
6
4320
10080
72
7.18
3
361
0
0
1
120
120
2
8.42
5
694
3
3
2
240
360
4
14.97
10
1221
3
3
3
1080
1440
18
27.44
16
2103
1
1
4
1440
2880
24
41.35
24
3067
1
1
214
Char
Char
Charcoal
Soil Only
Soil Only
Soil Only
5
2880
5760
48
25.71
16
2013
0
0
6
4320
10080
72
7.29
4
453
0
0
1
120
120
2
9.46
6
780
4
4
2
240
360
4
13.55
9
1116
3
3
3
1080
1440
18
14.69
9
1186
1
1
4
1440
2880
24
11.07
7
894
0
0
5
2880
5760
48
0.00
0
0
0
0
6
4320
10080
72
3.89
2
288
0
0
1
120
120
2
1.74
1
143
1
1
2
240
360
4
10.05
6
820
2
2
3
1080
1440
18
10.01
6
825
0
0
4
1440
2880
24
5.44
3
440
0
0
5
2880
5760
48
1.12
1
91
0
0
6
4320
10080
72
4.23
3
342
0
0
1
120
120
2
2.93
2
241
1
1
2
240
360
4
9.98
6
822
2
2
3
1080
1440
18
19.55
12
1563
1
1
4
1440
2880
24
11.74
6
813
0
0
5
2880
5760
48
5.61
3
448
0
0
6
4320
10080
72
0.76
0
52
0
0
1
120
120
2
0.00
0
0
0
0
2
240
360
4
0.09
0
7
0
0
3
1080
1440
18
0.00
0
0
0
0
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
0.00
0
0
0
0
6
4320
10080
72
0.00
0
0
0
0
1
120
120
2
0.00
0
0
0
0
2
240
360
4
0.01
0
1
0
0
3
1080
1440
18
0.00
0
0
0
0
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
0.00
0
0
0
0
6
4320
10080
72
0.00
0
0
0
0
1
120
120
2
0.92
1
76
0
0
2
240
360
4
0.00
0
0
0
0
3
1080
1440
18
0.06
0
5
0
0
4
1440
2880
24
0.00
0
0
0
0
5
2880
5760
48
0.00
0
0
0
0
6
4320
10080
72
0.00
0
0
0
0
215
Table D.2 Nitrous oxide flux
Nitrous oxide
Atmospheric pressure
ppb
g N2O
1014.4
-1
-
g ha hr
28
Slurry
26
Slurry
27
Slurry
Time
Temp
RH
DewPt
(hr)
°C
23.1
24.4
22.3
20.8
22.3
18.1
22.7
22.5
17.7
22
20.9
21.1
24
23.1
23.8
23.9
24.1
23.3
0
23.1
24.4
22.3
20.8
22.3
18.1
22.7
22.5
17.7
22
20.9
21.1
24
23.1
23.8
23.9
24.1
23.3
0
23.1
24.4
22.3
20.8
22.3
18.1
22.7
22.5
17.7
22
20.9
21.1
%
32
31
35
35
42
44
38
38
41
32
32
35
37
39
34
32
33
31
°C
-1
0
6
24
48
72
96
144
168
192
216
240
264
312
336
360
384
408
-1
0
6
24
48
72
96
144
168
192
216
240
264
312
336
360
384
408
-1
0
6
24
48
72
96
144
168
192
216
240
0
1
2
3
4
ppm
0.25
1.25
3.14
6.56
1.84
1.18
0.45
1.23
0.8
1.15
0.77
2.08
0.57
1.03
4.64
1.22
1.87
1.18
0.03
0.73
0.84
0.99
0.83
0.75
0.06
0.57
0.65
0.77
0.54
0.98
0.75
0.51
1
0.88
0.69
0.61
N2O
-2 -1
μg m h
22.8
113.1
285.1
599.6
167.4
109
40.8
111.7
74.2
104.8
70.1
190
51.5
93.5
419.9
110.1
168.5
106.5
0.55
0.58
0.56
0.11
0.89
2.69
9.95
-0.52
3.65
4.28
1
2.93
3.58
2.66
1.69
1.21
1.15
1.89
0.95
1.34
1.3
0.02
0.41
0.98
0.98
0.33
0.77
0.97
0.53
0.97
0.87
0.84
0.84
0.91
0.34
0.6
0.62
0.69
0.9
10.3
80.7
244.3
908.6
-46.9
336.3
388.3
90.5
270.8
325.3
242.7
154.4
109.5
103.9
170.9
85.7
121.4
117.9
0.1
0.81
2.44
9.09
-0.47
3.36
3.88
0.9
2.71
3.25
2.43
1.54
1.1
1.04
1.71
0.86
1.21
1.18
0.53
0.41
0.65
1.66
0.98
0.61
0.6
0.46
0.51
0.51
0.51
0.55
0.89
-0.35
1.6
10.86
5.74
0.35
0.29
0.02
0.4
0.23
0.4
-0.25
0.72
0.07
0.93
1
0.97
0.02
0.04
0
0.55
0.08
0.21
0.44
80.5
-31.4
145
991.9
521.3
32.1
26.7
1.6
37.1
20.7
36.7
-23
0.8
-0.31
1.45
9.92
5.21
0.32
0.27
0.02
0.37
0.21
0.37
-0.23
h
5.7
6.6
6.5
5
8.9
5.9
8.1
7.7
4.4
5
3.8
5.5
8.9
8.8
7.3
6.5
7.1
5.7
0.53
0.47
0.58
0.81
0.54
0.53
0.58
0.55
0.53
0.5
0.53
0.52
0.5
0.53
0.59
0.52
0.49
0.48
0.56
0.45
0.7
0.88
0.58
0.54
0.51
0.52
0.54
0.56
0.58
0.55
0.51
0.54
0.66
0.54
0.51
0.54
0.55
0.48
0.74
1.01
0.56
0.53
0.53
0.57
0.59
0.55
0.55
0.6
0.53
0.59
0.75
0.57
0.55
0.51
0.62
0.5
0.81
1.14
0.65
0.59
0.59
0.56
0.56
0.56
0.6
0.63
0.52
0.54
0.82
0.56
0.64
0.55
0.52
0.55
0.79
1.23
0.66
0.61
32
31
35
35
42
44
38
38
41
32
32
35
37
39
34
32
33
31
5.7
6.6
6.5
5
8.9
5.9
8.1
7.7
4.4
5
3.8
5.5
8.9
8.8
7.3
6.5
7.1
5.7
0.54
0.51
0.58
0.89
0.46
0.46
0.59
0.48
0.52
0.6
0.48
0.49
0.54
0.5
0.38
0.5
0.51
0.48
0.49
0.47
0.62
1.08
0.46
0.58
0.61
0.44
0.54
0.58
0.58
0.49
0.56
0.53
0.46
0.51
0.52
0.48
0.55
0.56
0.66
1.26
0.49
0.58
0.72
0.5
0.59
0.67
0.61
0.51
0.56
0.61
0.51
0.56
0.58
0.5
0.53
0.54
0.73
1.45
0.44
0.75
0.78
0.53
0.64
0.79
0.62
0.59
0.6
0.62
0.47
0.56
0.61
0.54
0.53
0.55
0.75
1.53
0.43
0.68
0.86
0.51
0.71
0.79
32
31
35
35
42
44
38
38
41
32
32
35
5.7
6.6
6.5
5
8.9
5.9
8.1
7.7
4.4
5
3.8
5.5
0.49
0.44
0.54
0.93
0.62
0.52
0.54
0.48
0.48
0.51
0.48
0.57
0.47
0.45
0.56
1.11
0.66
0.57
0.58
0.45
0.5
0.46
0.52
0.55
0.52
0.5
0.57
1.3
0.82
0.56
0.62
0.49
0.51
0.5
0.49
0.56
0.53
0.46
0.6
1.46
0.9
0.44
0.52
0.5
0.5
0.49
0.54
0.54
216
0.63
0.59
0.6
0.58
0.65
0.54
0.61
0.61
0.58
0.58
0.62
0.55
R²
1
-1
0.23
1.13
2.85
6
1.67
1.09
0.41
1.12
0.74
1.05
0.7
1.9
0.52
0.94
4.2
1.1
1.69
1.07
264
312
336
360
384
408
31
Alum
-1
0
6
24
48
72
96
144
168
192
216
240
264
312
336
360
384
408
30
Alum
-1
0
6
24
48
72
96
144
168
192
216
240
264
312
336
360
384
408
32
Alum
-1
0
6
24
48
72
96
144
168
192
216
240
24
23.1
23.8
23.9
24.1
23.3
0
23.1
24.4
22.3
20.8
22.3
18.1
22.7
22.5
17.7
22
20.9
21.1
24
23.1
23.8
23.9
24.1
23.3
0
23.1
24.4
22.3
20.8
22.3
18.1
22.7
22.5
17.7
22
20.9
21.1
24
23.1
23.8
23.9
24.1
23.3
0
23.1
24.4
22.3
20.8
22.3
18.1
22.7
22.5
17.7
22
20.9
21.1
37
39
34
32
33
31
8.9
8.8
7.3
6.5
7.1
5.7
0.58
0.47
0.52
0.53
0.47
0.57
0.54
0.49
0.51
0.5
0.46
0.5
0.53
0.51
0.5
0.56
0.48
0.55
0.51
0.56
0.54
0.54
0.49
0.54
0.52
0.51
0.57
0.51
0.55
-0.85
0.94
0.39
0.68
0.66
0.04
0.7
0.55
0.18
0.49
0.87
0
-76.5
85.4
35.3
61.8
59.6
3.8
-0.76
0.85
0.35
0.62
0.6
0.04
32
31
35
35
42
44
38
38
41
32
32
35
37
39
34
32
33
31
5.7
6.6
6.5
5
8.9
5.9
8.1
7.7
4.4
5
3.8
5.5
8.9
8.8
7.3
6.5
7.1
5.7
0.51
0.44
0.66
1.1
0.87
0.63
0.66
0.79
0.56
0.68
0.52
0.58
0.49
0.49
0.47
0.58
0.68
0.69
0.58
0.51
0.69
1.4
1.11
0.86
0.93
1.02
0.72
0.8
0.53
0.62
0.61
0.55
0.52
0.54
0.7
0.81
0.58
0.49
0.83
1.69
1.32
1.19
1.18
1.71
0.89
0.9
0.61
0.64
0.63
0.58
0.51
0.53
0.74
0.83
0.52
0.55
0.85
1.97
1.56
1.46
1.41
2.07
1.05
1.04
0.65
0.7
0.61
0.61
0.54
0.6
0.79
0.9
0.51
0.66
0.93
2.25
1.74
1.76
1.62
2.52
1.18
1.08
0.71
0.71
0.67
0.69
0.55
0.61
0.83
0.71
-0.38
2.84
4.26
17.22
13.1
17.17
14.39
27.02
9.37
6.23
2.95
2.11
2.11
2.77
1.09
0.66
2.29
0.75
0.07
0.81
0.96
1
1
1
1
0.98
1
0.98
0.97
0.96
0.73
0.97
0.86
0.25
0.98
0.05
-34.3
256
387.1
1572.9
1191
1582.7
1306.5
2454.4
865.1
567.1
269
192.7
190.3
251.2
98.2
59.6
206.5
67.9
-0.34
2.56
3.87
15.73
11.91
15.83
13.06
24.54
8.65
5.67
2.69
1.93
1.9
2.51
0.98
0.6
2.06
0.68
32
31
35
35
42
44
38
38
41
32
32
35
37
39
34
32
33
31
5.7
6.6
6.5
5
8.9
5.9
8.1
7.7
4.4
5
3.8
5.5
8.9
8.8
7.3
6.5
7.1
5.7
0.58
0.49
0.73
0.68
0.65
0.74
0.61
0.6
0.51
0.41
0.55
0.55
0.51
0.61
0.71
0.49
0.57
0.57
0.62
0.42
0.82
0.91
0.72
0.8
0.74
0.89
0.6
0.49
0.6
0.6
0.62
0.76
0.99
0.68
0.64
0.63
0.67
0.66
0.83
0.91
0.77
0.84
0.81
0.9
0.59
0.61
0.6
0.68
0.62
0.87
1.28
0.71
0.74
0.69
0.64
0.79
0.91
1.03
0.81
0.91
0.87
0.9
0.69
0.66
0.62
0.73
0.7
0.9
1.42
0.86
0.82
0.74
0.63
0.91
0.92
1.11
0.88
0.99
0.9
0.77
7.29
2.84
5.85
3.29
3.7
4.18
5.37
2.96
4.92
0.7
3.84
3.65
5.89
3.67
6.19
3.98
3.79
0.36
0.89
0.93
0.91
0.99
0.99
0.94
0.61
0.91
0.99
0.6
0.99
0.95
0.96
0.1
0.96
0.91
0.99
69.6
657.7
257.9
534.3
299.4
340.8
379
487.7
273.1
447.6
64.1
350.3
330.2
534
332
559.1
359.3
342.9
0.7
6.58
2.58
5.34
2.99
3.41
3.79
4.88
2.73
4.48
0.64
3.5
3.3
5.34
3.32
5.59
3.59
3.43
32
31
35
35
42
44
38
38
41
32
32
35
5.7
6.6
6.5
5
8.9
5.9
8.1
7.7
4.4
5
3.8
5.5
0.72
0.72
0.8
0.73
0.49
0.59
0.57
0.53
0.56
0.61
0.51
0.44
0.85
0.8
0.93
0.77
0.58
0.64
0.58
0.52
0.54
0.64
0.52
0.47
0.95
0.99
1.01
0.93
0.61
0.67
0.61
0.65
0.56
0.64
0.53
0.5
0.97
0.99
1.17
0.9
0.64
0.7
0.7
0.64
0.57
0.65
0.54
0.51
1.01
1.14
1.27
0.94
0.69
0.69
0.68
0.69
0.6
0.65
0.56
4.24
6.15
7.12
3.31
2.77
1.59
1.96
2.62
0.62
0.51
0.65
1.4
0.91
0.95
0.99
0.8
0.96
0.83
0.82
0.83
0.55
0.78
0.96
0.99
383.9
554.9
647.2
302.5
251.9
146.6
178.1
237.6
57.6
46.4
59.2
127.5
3.84
5.55
6.47
3.03
2.52
1.47
1.78
2.38
0.58
0.46
0.59
1.28
217
0.71
0.74
0.6
0.8
0.77
1.03
0.8
0.92
0.81
0.83
264
312
336
360
384
408
23
FeCl
24
FeCl
18
FeCl
-1
0
2
8
24
48
96
192
216
240
312
336
360
384
408
504
528
552
576
-1
0
2
8
24
48
96
192
216
240
312
336
360
384
408
504
528
552
576
-1
0
2
8
24
48
96
192
216
240
24
23.1
23.8
23.9
24.1
23.3
0
21.1
19.7
19.7
24
24.3
23.8
23.8
22.7
21.6
22.4
23.2
22.9
23.4
22.5
22.5
22.3
22.1
21.9
22.9
0
21.1
19.7
19.7
24
24.3
23.8
23.8
22.7
21.6
22.4
23.2
22.9
23.4
22.5
22.5
22.3
22.1
21.9
22.9
0
21.1
19.7
19.7
24
24.3
23.8
23.8
22.7
21.6
22.4
37
39
34
32
33
31
8.9
8.8
7.3
6.5
7.1
5.7
0.58
0.55
0.66
0.48
0.47
0.5
0.54
0.65
0.86
0.5
0.52
0.53
0.53
0.68
0.89
0.57
0.62
0.56
0.6
0.72
0.99
0.52
0.54
0.54
0.61
0.75
35
40
42
37
38
34
29
27
27
29
33
32
30
30
30
29
28
31
27
5.5
6
6.8
8.9
9.3
7.3
4.8
3
2
4
6.5
5.4
5
4.4
4.5
4.3
4.4
5.1
3.9
0.56
0.57
0.54
0.47
0.63
0.64
0.87
0.59
0.47
0.51
0.53
0.53
0.47
0.47
0.47
0.62
0.46
0.44
0.48
0.52
0.6
0.53
0.52
0.71
0.78
1.15
0.65
0.51
0.55
0.58
0.59
0.54
0.51
0.47
0.6
0.49
0.46
0.46
0.54
0.64
0.54
0.52
0.76
0.88
1.38
0.65
0.57
0.52
0.56
0.59
0.51
0.48
0.51
0.63
0.49
0.49
0.54
0.55
0.71
0.54
0.5
0.86
1.01
1.71
0.73
0.58
0.6
0.57
0.63
0.52
0.49
0.53
0.62
0.5
0.51
0.5
0.56
35
40
42
37
38
34
29
27
27
29
33
32
30
30
30
29
28
31
27
5.5
6
6.8
8.9
9.3
7.3
4.8
3
2
4
6.5
5.4
5
4.4
4.5
4.3
4.4
5.1
3.9
0.52
0.62
0.56
0.5
0.68
0.79
0.73
0.59
0.46
0.48
0.45
0.49
0.46
0.48
0.45
0.58
0.51
0.46
0.44
0.47
0.59
0.57
0.53
0.78
0.97
0.97
0.55
0.47
0.54
0.53
0.53
0.51
0.5
0.52
0.56
0.46
0.43
0.47
0.52
0.58
0.62
0.56
0.87
1.06
1.15
0.57
0.43
0.5
0.48
0.5
0.46
0.49
0.5
0.55
0.52
0.48
0.49
0.53
0.69
0.58
0.53
0.93
1.26
1.39
0.5
0.47
0.48
0.51
0.53
0.47
0.5
0.45
0.57
0.52
0.53
0.49
0.56
0.77
0.63
0.56
1.04
1.38
1.58
35
40
42
37
38
34
29
27
27
29
5.5
6
6.8
8.9
9.3
7.3
4.8
3
2
4
0.48
0.6
0.56
0.52
0.77
0.63
0.42
0.54
0.49
0.45
0.47
0.64
0.57
0.56
0.87
0.85
0.62
0.55
0.52
0.47
0.51
0.6
0.57
0.57
1.01
1.12
0.8
0.59
0.52
0.5
0.54
0.63
0.62
0.57
1.07
1.29
0.95
0.58
0.49
0.51
0.56
0.65
218
0.6
0.57
0.56
0.55
0.9
1.14
1.99
1.14
0.61
1.14
0.57
0.49
0.49
0.49
0.5
0.49
1.38
0.55
1.38
0.52
0.47
0.49
0.53
0.51
0.43
0.61
1.24
1.52
1.18
0.68
1.52
0.53
0.66
2.74
6.08
1.55
1.31
0.75
0.25
0.91
0.89
0.71
0.4
0.46
59.6
248.5
550.2
139.9
118.1
67.9
0.6
2.48
5.5
1.4
1.18
0.68
0.13
2.7
0.35
0.97
4.19
7.37
16.79
2.45
8.43
1.51
0.7
7.6
1.1
0.08
0.59
0.19
0.43
0.98
0.29
0.04
0.95
0.44
0.62
0.98
1
1
0.87
0.66
0.73
0.39
0.64
0.62
0.02
0.42
0.14
0.57
0.87
0.07
11.5
247.6
32.5
87.8
378
666.3
1517.7
222.1
768
136.8
63.1
688.9
99.9
7.1
53.4
17.4
39.3
89.6
26.1
0.11
2.48
0.32
0.88
3.78
6.66
15.18
2.22
7.68
1.37
0.63
6.89
1
0.07
0.53
0.17
0.39
0.9
0.26
0.78
2.35
0.83
0.72
5.19
8.76
12.79
-1.45
11.09
0.39
0.94
10.67
0.46
-0.12
0.11
-0.25
0.65
1.22
0.04
0.4
0.61
0.51
0.53
0.99
0.99
1
0.67
0.5
0.1
0.28
0.52
0.21
0.07
0.01
0.2
0.4
0.65
0
71.2
215.7
76.5
65.1
468.5
792.1
1156.5
-131.8
1010.7
35.4
85.3
967.5
41.8
-10.9
10.4
-22.9
58.9
110.9
3.8
0.71
2.16
0.76
0.65
4.68
7.92
11.56
-1.32
10.11
0.35
0.85
9.67
0.42
-0.11
0.1
-0.23
0.59
1.11
0.04
1.4
0.52
0.95
1.24
6.82
13.36
11.14
1.9
12.14
1.24
0.9
0.43
0.76
0.85
0.98
1
1
0.79
0.5
0.97
128.1
47.9
87.5
111.7
615.2
1207.7
1006.7
172.6
1106.3
112.8
1.28
0.48
0.87
1.12
6.15
12.08
10.07
1.73
11.06
1.13
312
336
360
384
408
504
528
552
576
17
Lime
21
Lime
19
Lime
-1
0
2
8
24
48
96
192
216
240
264
336
360
384
432
528
552
576
600
-1
0
2
8
24
48
96
192
216
240
264
336
360
384
432
528
552
576
600
-1
0
2
8
24
48
96
23.2
22.9
23.4
22.5
22.5
22.3
22.1
21.9
22.9
0
21.1
19.7
19.7
24
24.3
23.8
23.8
22.7
21.6
22.4
23.2
22.9
23.4
22.5
22.5
22.3
22.1
21.9
22.9
0
21.1
19.7
19.7
24
24.3
23.8
23.8
22.7
21.6
22.4
23.2
22.9
23.4
22.5
22.5
22.3
22.1
21.9
22.9
0
21.1
19.7
19.7
24
24.3
23.8
23.8
33
32
30
30
30
29
28
31
27
6.5
5.4
5
4.4
4.5
4.3
4.4
5.1
3.9
0.44
0.54
0.48
0.5
0.45
0.5
0.44
0.87
0.46
0.48
0.51
0.51
0.47
0.49
0.52
0.49
0.46
0.47
0.48
0.57
0.47
0.5
0.48
0.52
0.48
0.46
0.5
0.55
0.55
0.51
0.51
0.49
0.51
0.51
0.47
0.48
35
40
42
37
38
34
29
27
27
29
33
32
30
30
30
29
28
31
27
5.5
6
6.8
8.9
9.3
7.3
4.8
3
2
4
6.5
5.4
5
4.4
4.5
4.3
4.4
5.1
3.9
0.48
0.63
0.58
0.56
0.87
0.55
0.42
0.44
0.46
0.52
0.48
0.51
0.54
0.47
0.49
0.49
0.47
0.48
0.47
0.47
0.7
0.58
0.59
0.95
0.63
0.49
0.53
0.56
0.51
0.46
0.47
0.5
0.49
0.46
0.52
0.51
0.49
0.46
0.51
0.7
0.59
0.63
1.07
0.66
0.54
0.53
0.49
0.47
0.48
0.47
0.48
0.41
0.53
0.54
0.53
0.45
0.51
0.54
0.74
0.64
0.64
1.24
0.74
0.51
0.51
0.54
0.5
0.47
0.51
0.47
0.53
0.5
0.52
0.47
0.48
0.46
0.56
35
40
42
37
38
34
29
27
27
29
33
32
30
30
30
29
28
31
27
5.5
6
6.8
8.9
9.3
7.3
4.8
3
2
4
6.5
5.4
5
4.4
4.5
4.3
4.4
5.1
3.9
0.49
0.58
0.54
0.53
0.75
0.53
0.42
0.47
0.43
0.44
0.45
0.51
0.5
0.43
0.45
0.58
0.46
0.53
0.44
0.5
0.6
0.52
0.53
0.77
0.55
0.51
0.51
0.47
0.51
0.5
0.52
0.49
0.49
0.46
0.56
0.54
0.5
0.52
0.5
0.69
0.57
0.59
0.86
0.64
0.5
0.47
0.45
0.46
0.49
0.54
0.54
0.5
0.47
0.55
0.57
0.5
0.44
0.49
0.68
0.59
0.57
0.98
0.68
0.51
0.49
0.48
0.52
0.55
0.55
0.54
0.49
0.52
0.57
0.55
0.51
0.48
0.55
0.71
0.64
0.63
1.03
0.77
0.47
0.59
0.48
0.49
0.48
0.58
0.53
0.5
0.53
35
40
42
37
38
34
29
5.5
6
6.8
8.9
9.3
7.3
4.8
0.52
0.52
0.53
0.55
0.68
0.45
0.37
0.52
0.57
0.57
0.56
0.66
0.45
0.49
0.48
0.61
0.6
0.57
0.74
0.52
0.5
0.51
0.65
0.63
0.59
0.75
0.5
0.47
219
2.09
11.95
0.78
0.11
0.52
0.19
0.91
-4.4
-0.15
0.89
0.52
0.45
0.03
0.74
0.2
0.75
0.42
0.04
189.7
1083.9
70.6
9.8
47.4
16.9
82.9
-400.8
-13.6
1.9
10.84
0.71
0.1
0.47
0.17
0.83
-4.01
-0.14
1.4
1.97
1.18
3.38
7.34
3.26
1.24
0.73
0.71
0.38
-0.05
0.25
-0.34
0.65
0.54
0.67
0.79
0.46
0.2
0.9
0.89
0.85
0.8
0.99
0.98
0.53
0.27
0.22
0.1
0.01
0.1
0.09
0.15
0.23
0.52
0.31
0.21
0.06
128.1
180.5
108.4
305.3
662.4
295.2
112.3
66.4
64.5
34.3
-4.3
22.9
-30.4
58.9
49
60.5
72
41.5
18.5
1.28
1.8
1.08
3.05
6.62
2.95
1.12
0.66
0.65
0.34
-0.04
0.23
-0.3
0.59
0.49
0.61
0.72
0.42
0.19
0.57
0.53
0.46
0.66
2.02
1.53
1.48
4.57
3.65
0.62
1.33
0.71
0.67
0.64
0.97
0.65
0.85
1.37
-0.25
1.38
-0.01
-0.13
0.45
0.85
0.81
0.82
0.95
0.96
0.19
0.53
0.65
0.28
0.24
0.93
0.52
0.54
0.92
0.2
0.64
0
0.01
60.2
184.9
140.3
133.9
412.7
329.9
56.4
120.9
64.5
61
57.6
88.2
58.7
77.4
124.2
-22.9
125.5
-1.1
-11.4
0.6
1.85
1.4
1.34
4.13
3.3
0.56
1.21
0.65
0.61
0.58
0.88
0.59
0.77
1.24
-0.23
1.26
-0.01
-0.11
0.48
0.63
0.64
0.58
0.79
0.6
0.52
-0.55
1.74
1.67
0.47
1.86
2.14
1.75
0.51
0.86
0.98
0.74
0.8
0.79
0.58
-49.8
159.6
152.9
42.3
167.9
193.2
158.4
-0.5
1.6
1.53
0.42
1.68
1.93
1.58
1.52
0.55
0.48
0.5
0.51
0.49
0.45
0.65
0.81
1.33
0.77
0.52
0.52
0.54
0.56
0.47
0.51
0.53
0.51
0.52
0.56
0.52
0.48
192
216
240
264
336
360
384
432
528
552
576
600
PAC
PAC
Char
27
27
29
33
32
30
30
30
29
28
31
27
3
2
4
6.5
5.4
5
4.4
4.5
4.3
4.4
5.1
3.9
0.59
0.44
0.48
0.49
0.55
0.49
0.51
0.46
0.48
0.43
0.46
0.47
0.57
0.49
0.53
0.54
0.49
0.47
0.49
0.47
0.56
0.49
0.48
0.46
0.47
0.47
0.52
0.54
0.53
0.5
0.47
0.5
0.54
0.54
0.48
0.49
0.52
0.53
0.48
0.47
0.53
0.52
0.48
0.46
0.55
0.52
0.45
0.46
0.54
0.52
0.49
0.51
0.57
0.5
0.47
0.48
32
31
35
35
42
44
38
38
41
32
32
35
37
39
34
32
33
31
5.7
6.6
6.5
5
8.9
5.9
8.1
7.7
4.4
5
3.8
5.5
8.9
8.8
7.3
6.5
7.1
5.7
0.6
0.54
0.53
0.78
0.43
0.36
0.52
0.42
0.52
0.45
0.52
0.49
0.49
0.49
0.49
0.52
0.53
0.48
0.73
0.54
0.54
0.9
0.55
0.5
0.52
0.52
0.51
0.48
0.48
0.46
0.49
0.54
0.52
0.51
0.5
0.48
0.78
0.58
0.54
1.01
0.65
0.54
0.51
0.53
0.47
0.5
0.53
0.53
0.5
0.52
0.54
0.49
0.5
0.48
0.87
0.58
0.56
1.2
0.76
0.63
0.54
0.49
0.5
0.51
0.54
0.56
0.51
0.51
0.52
0.53
0.51
0.44
0.93
0.58
0.6
1.3
0.84
0.73
0.49
0.58
0.56
0.55
0.58
0.54
0.51
0.54
-1
0
6
24
48
72
96
144
168
192
216
240
264
312
336
360
384
408
22.7
21.6
22.4
23.2
22.9
23.4
22.5
22.5
22.3
22.1
21.9
22.9
0
23.1
24.4
22.3
20.8
22.3
18.1
22.7
22.5
17.7
22
20.9
21.1
24
23.1
23.8
23.9
24.1
23.3
0
23.1
24.4
22.3
20.8
22.3
18.1
22.7
22.5
17.7
22
20.9
21.1
24
23.1
23.8
23.9
24.1
23.3
32
31
35
35
42
44
38
38
41
32
32
35
37
39
34
32
33
31
5.7
6.6
6.5
5
8.9
5.9
8.1
7.7
4.4
5
3.8
5.5
8.9
8.8
7.3
6.5
7.1
5.7
0.57
0.5
0.5
0.7
0.46
0.39
0.51
0.53
0.5
0.49
0.46
0.49
0.46
0.46
0.5
0.51
0.4
0.5
0.63
0.54
0.56
0.77
0.52
0.59
0.54
0.53
0.49
0.45
0.5
0.52
0.49
0.47
0.52
0.5
0.45
0.45
0.67
0.53
0.57
0.84
0.54
0.57
0.61
0.53
0.53
0.52
0.46
0.55
0.48
0.52
0.52
0.49
0.48
0.44
0.74
0.54
0.56
0.94
0.63
0.61
0.61
0.51
0.6
0.49
0.51
0.54
0.49
0.48
0.51
0.53
0.49
0.51
0.77
0.58
0.59
0.97
0.73
0.67
0.63
0.52
0.62
0.49
0.53
0.5
0.48
0.51
-1
0
6
24
48
72
21.1
19.7
19.7
24
24.3
23.8
35
40
42
37
38
34
5.5
6
6.8
8.9
9.3
7.3
0.49
0.48
0.5
0.49
0.51
0.48
0.49
0.48
0.51
0.5
0.51
0.49
0.5
0.49
0.51
0.5
0.51
0.49
0.5
0.49
0.5
0.5
0.51
0.49
-1
0
6
24
48
72
96
144
168
192
216
240
264
312
336
360
384
408
220
-0.86
1.22
-0.16
-0.18
0.5
0.55
-0.59
0.25
1.12
0.78
0.17
0.05
0.23
0.81
0.03
0.03
0.19
0.49
0.83
0.16
0.42
0.29
0.09
0.01
-77.9
111.5
-14.2
-16.3
45.7
50
-53.9
22.9
101.4
70.9
15.8
4.4
-0.78
1.12
-0.14
-0.16
0.46
0.5
-0.54
0.23
1.01
0.71
0.16
0.04
4.73
0.74
0.95
8.05
6.22
5.2
-0.25
1.69
0.34
1.31
1.12
1.21
0.34
0.47
0.67
0.23
-0.01
0.1
0.98
0.68
0.79
0.99
1
0.98
0.16
0.58
0.08
0.97
0.66
0.62
0.86
0.34
0.52
0.12
0
0.01
429.1
66.6
86.1
735.5
565
479.6
-22.9
153.1
31.6
119
102.4
110
30.4
43
60.2
20.6
-1.1
9.2
4.29
0.67
0.86
7.35
5.65
4.8
-0.23
1.53
0.32
1.19
1.02
1.1
0.3
0.43
0.6
0.21
-0.01
0.09
0.52
0.45
0.51
3.04
0.95
1.04
4.37
3.95
3.43
1.86
-0.23
2.13
0.32
0.88
0.26
0.29
0.7
0.19
0.29
0.86
0.4
0.99
0.74
0.68
0.98
0.95
0.76
0.9
0.47
0.9
0.11
0.57
0.06
0.43
0.51
0.2
0.28
0.44
0.11
275.7
86.1
94.9
399.5
358.8
316.4
168.8
-20.7
196.6
29.5
80
24.1
26.6
63.6
16.8
26.6
77.5
36.4
2.76
0.86
0.95
4
3.59
3.16
1.69
-0.21
1.97
0.29
0.8
0.24
0.27
0.64
0.17
0.27
0.77
0.36
0.5
0.49
0.5
0.5
0.51
0.5
0.24
0.17
0.02
0.06
0.11
0.23
0.94
0.57
0.1
0.93
0.95
1
21.9
16
1.7
5.4
9.7
21.2
0.22
0.16
0.02
0.05
0.1
0.21
0.49
0.49
0.47
0.53
0.53
0.51
Char
Soil
96
144
168
192
216
240
264
312
336
360
384
408
23.8
22.7
21.6
22.4
23.2
22.9
23.4
22.5
22.5
22.3
22.1
21.9
29
27
27
29
33
32
30
30
30
29
28
31
4.8
3
2
4
6.5
5.4
5
4.4
4.5
4.3
4.4
5.1
0.49
0.48
0.5
0.49
0.49
0.48
0.5
0.49
0.49
0.5
0.49
0.48
0.5
0.5
0.51
0.49
0.5
0.48
0.52
0.51
0.5
0.51
0.49
0.49
0.51
0.51
0.52
0.49
0.51
0.49
0.53
0.52
0.51
0.51
0.5
0.49
0.52
0.53
0.53
0.5
0.52
0.49
0.55
0.54
0.52
0.52
0.5
0.5
0.53
0.55
0.53
0.5
0.52
0.49
0.57
0.55
0.53
0.53
0.51
0.5
0.58
1.04
0.47
0.16
0.5
0.13
1.09
0.86
0.66
0.37
0.26
0.36
1
0.99
0.98
0.93
0.97
0.98
1
0.99
1
0.98
0.96
0.97
52.1
94.2
42.6
14.2
45.7
11.4
98.9
78.5
59.9
33.8
23.5
32.8
0.52
0.94
0.43
0.14
0.46
0.11
0.99
0.78
0.6
0.34
0.23
0.33
-1
0
6
24
48
72
96
144
168
192
216
240
264
312
336
360
384
408
21.1
19.7
19.7
24
24.3
23.8
23.8
22.7
21.6
22.4
23.2
22.9
23.4
22.5
22.5
22.3
22.1
21.9
35
40
42
37
38
34
29
27
27
29
33
32
30
30
30
29
28
31
5.5
6
6.8
8.9
9.3
7.3
4.8
3
2
4
6.5
5.4
5
4.4
4.5
4.3
4.4
5.1
0.42
0.4
0.38
0.4
0.43
0.47
0.5
0.43
0.4
0.38
0.4
0.46
0.5
0.5
0.47
0.51
0.41
0.5
0.42
0.4
0.39
0.41
0.44
0.48
0.5
0.44
0.4
0.43
0.44
0.46
0.5
0.52
0.49
0.52
0.42
0.5
0.43
0.41
0.4
0.41
0.45
0.48
0.51
0.46
0.41
0.44
0.46
0.46
0.51
0.54
0.53
0.52
0.44
0.5
0.43
0.41
0.4
0.41
0.45
0.48
0.51
0.46
0.42
0.48
0.46
0.47
0.52
0.56
0.56
0.52
0.44
0.51
0.44
0.41
0.41
0.28
0.2
0.43
0.14
0.41
0.25
0.2
0.58
0.25
1.79
0.98
0.21
0.61
1.02
1.46
0.08
0.45
0.13
0.99
0.99
0.99
0.96
0.98
0.98
0.96
0.99
0.61
0.98
0.82
0.88
0.96
0.98
0.96
0.72
0.9
0.76
25.7
18.2
39.6
13
36.8
22.8
17.9
52.3
23
163
89.1
19
54.9
92.6
132.4
7.6
40.9
11.5
0.26
0.18
0.4
0.13
0.37
0.23
0.18
0.52
0.23
1.63
0.89
0.19
0.55
0.93
1.32
0.08
0.41
0.11
-1
0
6
24
48
72
96
144
168
192
216
240
264
312
336
360
384
21.1
19.7
19.7
24
24.3
23.8
23.8
22.7
21.6
22.4
23.2
22.9
23.4
22.5
22.5
22.3
22.1
35
40
42
37
38
34
29
27
27
29
33
32
30
30
30
29
28
5.5
6
6.8
8.9
9.3
7.3
4.8
3
2
4
6.5
5.4
5
4.4
4.5
4.3
4.4
0.48
0.5
0.42
0.48
0.5
0.48
0.48
0.51
0.42
0.39
0.43
0.51
0.49
0.43
0.47
0.44
0.46
0.48
0.5
0.43
0.48
0.51
0.49
0.52
0.53
0.43
0.44
0.44
0.52
0.49
0.44
0.48
0.47
0.46
0.48
0.5
0.43
0.49
0.52
0.5
0.56
0.54
0.46
0.46
0.46
0.53
0.5
0.45
0.48
0.47
0.46
0.48
0.5
0.43
0.49
0.53
0.53
0.59
0.56
0.46
0.48
0.46
0.54
0.5
0.45
0.49
0.48
0.46
0.49
0.48
0.47
0.04
0.02
0.17
0.31
0.53
0.97
2.01
1.22
0.76
1.6
0.53
0.52
0.21
0.46
0.26
0.46
0.1
0.3
0.17
0.81
0.88
0.99
0.97
0.99
0.98
0.94
0.97
0.81
0.95
0.95
0.97
0.92
0.73
0.63
3.3
1.7
15.4
27.7
48.2
87.9
181.7
110.5
68.9
145.5
48.4
46.8
19
41.4
24
42
9.3
0.03
0.02
0.15
0.28
0.48
0.88
1.82
1.11
0.69
1.46
0.48
0.47
0.19
0.41
0.24
0.42
0.09
408
21.9
31
5.1
0.45
0.46
0.47
0.48
0.48
0.4
0.89
36.6
0.37
221
0.46
0.49
0.51
0.47
0.41
0.5
0.48
0.47
0.54
0.57
0.56
0.52
0.44
0.51
0.5
0.43
0.49
0.54
0.54
0.62
0.59
0.47
0.5
0.46
Table D 3 Methane flux
ug ch4 m
-1
h
Time
0
1
2
3
4
ppm
-1
h
-2
R²
CH4
-1
g ha
-1
hr
CH4-C
-1
g ha
-1
hr
(hr)
28
-1
2.8
2.6
2.4
2.8
3.1
4.8
0.2
158.2
1.6
1.2
Slurry
0
27.4
38.1
48.5
57.5
66.1
580.8
1.0
19050.4
190.5
142.9
6
0.4
0.8
0.9
1.0
2.8
29.6
0.7
976.8
9.8
7.3
24
2.4
2.2
2.2
1.7
2.9
2.5
0.0
82.1
0.8
0.6
48
1.1
1.2
1.6
1.3
1.3
3.0
0.2
99.1
1.0
0.7
72
2.7
1.9
2.6
2.1
2.6
0.0
0.0
0.0
0.0
0.0
96
1.7
1.6
1.6
1.2
-9.0
0.8
-297.0
-3.0
-2.2
144
2.9
2.7
1.9
2.4
-13.8
0.5
-455.7
-4.6
-3.4
168
2.0
3.2
3.0
3.9
5.0
39.5
0.9
1327.0
13.3
10.0
192
2.1
2.5
1.6
2.2
2.0
-3.0
0.1
-99.2
-1.0
-0.7
216
2.4
2.0
1.9
1.9
1.9
-6.6
0.6
-219.1
-2.2
-1.6
240
2.4
2.0
1.8
2.3
2.6
4.2
0.1
139.3
1.4
1.0
264
2.1
1.5
1.1
1.5
1.2
-10.8
0.5
-354.8
-3.5
-2.7
312
2.2
1.6
0.7
1.2
1.2
-14.7
0.5
-485.9
-4.9
-3.6
336
1.9
2.1
2.0
1.1
-15.0
0.5
-493.1
-4.9
-3.7
360
3.3
2.8
2.6
3.0
3.1
-1.2
0.0
-39.4
-0.4
-0.3
384
2.3
2.9
3.5
2.5
2.7
2.4
0.0
78.8
0.8
0.6
408
1.9
1.7
2.1
2.5
13.2
0.7
434.7
4.3
3.3
26
-1
2.1
2.1
2.8
2.3
1.6
-4.8
0.1
-158.2
-1.6
-1.2
Slurry
0
29.3
37.8
45.7
52.6
59.1
446.4
1.0
14642.0
146.4
109.8
6
2.0
3.1
2.8
4.4
3.7
28.7
0.7
949.4
9.5
7.1
24
2.7
2.0
2.5
1.9
1.8
-11.8
0.6
-390.7
-3.9
-2.9
48
2.1
1.9
2.8
4.6
4.8
48.4
0.9
1598.6
16.0
12.0
72
1.5
2.8
2.2
1.9
6.0
48.0
0.5
1610.5
16.1
12.1
96
0.7
2.4
2.4
5.5
8.3
109.6
0.9
3617.8
36.2
27.1
144
1.8
2.7
2.4
5.1
7.2
79.4
0.8
2620.4
26.2
19.7
168
0.7
2.4
3.2
4.3
5.5
68.5
1.0
2299.7
23.0
17.2
192
2.3
5.0
6.5
7.0
7.8
77.7
0.9
2569.7
25.7
19.3
216
1.8
2.9
3.2
4.0
40.4
1.0
1339.9
13.4
10.0
240
2.8
3.3
3.3
4.1
5.4
36.0
0.9
1194.1
11.9
9.0
264
2.4
3.5
3.8
4.1
4.3
26.4
0.9
867.3
8.7
6.5
312
1.6
6.5
9.0
12.7
15.3
201.6
1.0
6642.1
66.4
49.8
336
0.9
8.7
17.4
23.3
455.0
1.0
14959.3
149.6
112.2
360
0.6
3.5
9.4
12.8
16.4
245.5
1.0
8065.2
80.7
60.5
384
2.6
5.8
14.3
15.2
19.8
263.7
0.9
8659.3
86.6
64.9
408
2.5
4.6
5.3
7.5
8.4
88.6
1.0
2916.9
29.2
21.9
222
27
-1
2.3
2.5
3.2
2.7
2.0
-2.4
0.0
-79.1
-0.8
-0.6
Slurry
0
27.0
36.8
44.5
52.6
60.4
495.6
1.0
16255.8
162.6
121.9
6
1.2
1.9
2.9
4.2
4.4
52.6
1.0
1736.3
17.4
13.0
24
2.6
3.3
3.6
4.4
4.1
24.0
0.9
798.0
8.0
6.0
48
1.5
1.4
1.8
2.0
2.7
17.9
0.8
592.4
5.9
4.4
72
1.6
1.6
2.5
2.7
2.9
23.0
0.9
770.9
7.7
5.8
96
2.4
3.0
3.6
3.8
4.7
31.0
1.0
1021.8
10.2
7.7
144
1.5
1.2
3.0
4.5
6.8
84.5
0.9
2791.0
27.9
20.9
168
2.0
2.7
2.4
3.5
4.4
34.3
0.9
1152.2
11.5
8.6
192
1.7
3.3
3.9
5.5
5.7
60.1
1.0
1987.3
19.9
14.9
216
1.9
1.7
3.2
3.8
4.4
42.6
0.9
1414.1
14.1
10.6
240
2.1
3.9
4.3
5.3
4.8
41.3
0.8
1369.6
13.7
10.3
264
0.8
1.7
1.9
2.2
3.0
29.4
0.9
965.9
9.7
7.2
312
1.1
2.4
2.6
2.2
4.5
40.4
0.7
1332.4
13.3
10.0
336
1.5
1.2
0.6
0.6
4.2
-19.8
0.9
-650.9
-6.5
-4.9
360
1.9
3.5
4.9
6.5
8.2
93.6
1.0
3073.8
30.7
23.1
384
0.6
2.6
7.4
10.8
12.0
185.7
1.0
6099.1
61.0
45.7
408
6.3
13.7
18.6
23.5
26.4
300.6
1.0
9899.0
99.0
74.2
-1
2.4
1.7
1.0
1.9
2.6
3.6
0.0
118.6
1.2
0.9
0
1.7
3.1
4.8
5.0
7.6
81.2
1.0
2662.7
26.6
20.0
31
Alum
30
Alum
6
1.5
1.7
0.7
3.5
3.2
31.9
0.5
1052.5
10.5
7.9
24
2.5
1.3
2.9
2.9
3.1
16.3
0.4
539.9
5.4
4.0
48
2.6
3.1
3.6
3.7
4.5
26.8
1.0
886.8
8.9
6.7
72
2.7
2.0
3.0
3.8
3.9
24.7
0.7
826.6
8.3
6.2
96
0.6
1.1
0.6
1.2
1.8
15.0
0.6
495.0
4.9
3.7
144
1.9
2.3
2.5
4.7
5.1
52.9
0.9
1745.6
17.5
13.1
168
1.7
2.8
2.6
4.4
5.2
51.2
0.9
1717.8
17.2
12.9
192
1.5
0.9
0.9
0.5
1.0
-8.4
0.4
-277.8
-2.8
-2.1
216
2.3
2.6
4.4
7.3
9.5
115.4
0.9
3830.1
38.3
28.7
240
2.3
2.8
3.1
3.3
3.9
22.2
1.0
736.4
7.4
5.5
264
0.9
1.2
4.2
6.0
7.1
102.8
1.0
3378.6
33.8
25.3
312
1.5
5.3
11.5
14.1
15.7
223.6
1.0
7367.6
73.7
55.3
336
1.5
6.3
10.3
13.1
15.2
205.4
1.0
6751.8
67.5
50.6
360
1.3
2.3
2.6
3.6
3.0
27.9
0.8
917.7
9.2
6.9
384
1.5
2.7
4.1
5.5
6.7
78.5
1.0
2577.1
25.8
19.3
408
1.7
0.5
1.2
1.9
2.3
15.6
0.4
513.7
5.1
3.9
-1
1.3
2.7
3.2
5.1
6.3
74.9
1.0
2468.4
24.7
18.5
0
7.8
11.0
13.6
19.6
22.6
228.7
1.0
7502.1
75.0
56.3
6
0.3
0.8
2.4
2.8
3.3
47.3
0.9
1562.5
15.6
11.7
24
2.2
2.6
3.7
3.5
5.0
39.0
0.9
1295.1
13.0
9.7
48
1.3
2.0
2.6
3.1
3.7
35.3
1.0
1167.1
11.7
8.8
223
32
Alum
72
1.9
2.3
3.1
3.3
4.1
32.3
1.0
23
10.8
8.1
4.3
22.8
0.6
752.7
7.5
5.6
-4.8
0.1
-158.5
-1.6
-1.2
96
2.5
2.7
2.3
3.0
144
1.7
1.2
1.0
1.5
168
2.4
3.0
4.1
4.2
4.9
37.5
1.0
1257.7
12.6
9.4
192
2.0
2.2
2.4
2.5
2.8
11.4
1.0
377.0
3.8
2.8
216
1.8
1.9
1.8
2.0
1.5
-3.0
0.2
-99.6
-1.0
-0.7
240
1.3
5.4
6.6
6.9
7.4
82.7
0.8
2742.4
27.4
20.6
264
1.8
4.5
5.9
7.4
8.6
99.7
1.0
3275.7
32.8
24.6
312
1.6
2.0
3.3
3.9
4.3
43.8
1.0
1443.1
14.4
10.8
336
2.0
1.5
1.2
0.3
7.9
63.7
0.3
2094.8
20.9
15.7
360
1.1
3.5
6.3
8.4
10.5
141.6
1.0
4653.6
46.5
34.9
384
1.8
1.9
1.6
1.7
2.2
3.1
0.1
102.8
1.0
0.8
408
1.1
5.2
8.0
10.1
12.7
169.1
1.0
5567.9
55.7
41.8
-1
3.2
3.3
3.6
4.3
4.4
20.4
0.9
672.2
6.7
5.0
0
4.0
5.5
5.6
7.3
8.6
65.2
1.0
2139.2
21.4
16.0
0.3
3.3
3.9
3.5
62.3
0.6
2057.4
20.6
15.4
6
FeCl
1082.6
24
2.4
4.3
4.5
4.5
4.8
30.3
0.7
1006.2
10.1
7.5
48
2.1
3.0
3.1
3.2
3.8
21.0
0.9
694.7
6.9
5.2
72
2.7
4.3
5.2
5.3
6.5
51.1
0.9
1711.9
17.1
12.8
96
1.9
2.7
4.0
2.7
7.9
71.5
0.6
2358.0
23.6
17.7
144
1.3
1.7
2.2
2.5
3.1
26.4
1.0
873.3
8.7
6.5
168
0.5
1.1
2.4
3.4
4.2
58.4
1.0
1960.8
19.6
14.7
192
0.9
0.9
0.8
0.7
1.0
0.0
0.0
0.0
0.0
0.0
216
1.3
1.3
1.5
2.1
2.3
16.8
0.9
557.7
5.6
4.2
240
1.9
2.7
4.4
5.1
4.9
68.2
1.0
2261.6
22.6
17.0
264
1.8
2.3
2.0
1.9
2.7
8.4
0.4
276.0
2.8
2.1
312
1.7
2.2
3.3
4.3
4.5
47.1
1.0
1551.8
15.5
11.6
336
1.8
2.4
3.9
5.0
66.8
1.0
2197.2
22.0
16.5
360
1.1
1.8
4.5
6.1
7.2
100.0
1.0
3285.3
32.9
24.6
384
1.4
3.2
4.2
6.8
8.2
102.9
1.0
3378.0
33.8
25.3
408
2.3
2.9
3.9
4.8
7.0
51.0
1.0
1679.5
16.8
12.6
-1
1.1
1.5
1.7
1.0
-0.6
0.0
-19.9
-0.2
-0.1
0
5.1
7.8
11.2
13.9
179.1
1.0
5970.5
59.7
44.8
2
1.7
2.3
3.2
3.9
5.0
50.1
1.0
1668.7
16.7
12.5
8
2.1
6.2
2.6
2.8
3.1
-8.4
0.0
-276.0
-2.8
-2.1
24
2.0
2.7
2.3
3.2
2.8
12.6
0.5
413.5
4.1
3.1
48
2.3
2.6
1.9
2.1
3.0
5.0
0.1
163.7
1.6
1.2
96
2.0
1.3
1.0
1.1
0.5
-19.2
0.9
-631.0
-6.3
-4.7
192
1.7
2.3
2.6
1.8
3.0
0.0
100.0
1.0
0.7
216
4.4
3.8
3.0
3.6
-18.5
0.5
-612.1
-6.1
-4.6
240
1.8
2.2
2.3
1.5
-5.4
0.2
-178.3
-1.8
-1.3
1.7
224
24
FeCl
18
FeCl
312
1.9
2.0
2.3
2.4
6.6
10.8
1.0
355.7
3.6
2.7
336
1.6
0.9
0.7
0.5
360
1.8
1.8
1.6
0.8
5.6
46.4
0.3
1529.2
15.3
11.5
0.2
-25.2
0.9
-829.4
-8.3
-6.2
384
1.7
1.8
1.4
0.7
1.1
-13.8
0.7
-455.7
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-3.4
408
1.9
3.2
2.4
2.3
2.0
-4.2
0.0
-138.7
-1.4
-1.0
504
1.1
528
2.5
2.9
2.3
1.8
5.7
9.0
0.1
297.4
3.0
2.2
2.2
2.0
2.4
1.6
-9.6
0.5
-317.4
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552
1.2
0.9
0.9
0.8
1.6
4.2
0.1
139.0
1.4
1.0
576
1.5
1.5
1.6
1.3
1.6
0.0
0.0
0.0
0.0
0.0
-1
2.5
2.4
1.5
2.4
2.1
-4.8
0.1
-159.2
-1.6
-1.2
0
3.4
6.7
9.1
11.6
14.9
167.4
1.0
5580.5
55.8
41.9
2
1.5
2.2
3.2
4.7
5.3
61.2
1.0
2039.7
20.4
15.3
8
1.3
1.2
1.9
2.4
2.3
19.2
0.8
630.8
6.3
4.7
24
1.8
1.7
2.4
2.4
2.1
7.8
0.4
256.0
2.6
1.9
48
1.3
1.5
1.4
1.3
1.8
4.8
0.4
157.8
1.6
1.2
96
1.9
0.1
0.2
0.0
0.3
-19.8
0.4
-650.8
-6.5
-4.9
192
1.5
1.1
1.7
1.8
10.4
0.5
343.0
3.4
2.6
216
3.7
3.8
3.1
3.1
1.4
-31.9
0.8
-1055.4
-10.6
-7.9
240
4.0
1.1
1.2
0.4
0.4
-46.3
0.7
-1527.7
-15.3
-11.5
312
1.1
0.4
0.4
0.6
-9.0
0.3
-296.4
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336
1.8
1.9
2.5
2.2
5.7
48.6
0.6
1602.4
16.0
12.0
360
1.5
1.4
1.4
1.0
1.3
-4.8
0.4
-158.0
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-1.2
384
2.0
1.0
0.8
0.2
0.2
-26.4
0.9
-871.7
-8.7
-6.5
408
1.4
1.1
1.1
1.1
1.5
1.2
0.0
39.6
0.4
0.3
504
1.9
1.7
1.7
2.3
7.2
0.3
237.9
2.4
1.8
528
1.9
3.1
2.4
3.6
3.0
16.2
0.4
535.6
5.4
4.0
552
2.5
3.0
3.1
3.0
2.7
2.4
0.1
79.4
0.8
0.6
576
2.2
2.1
1.6
1.9
2.5
2.4
0.0
79.1
0.8
0.6
-1
1.6
1.6
1.0
1.0
0.7
-14.4
0.9
-477.6
-4.8
-3.6
0
3.2
5.8
8.0
10.6
12.2
136.4
1.0
4548.4
45.5
34.1
2
2.5
1.8
4.7
5.0
62.5
0.7
2083.3
20.8
15.6
8
1.7
2.3
1.6
2.1
2.0
2.4
0.0
78.8
0.8
0.6
24
1.8
2.2
1.4
1.5
1.6
-6.6
0.3
-216.6
-2.2
-1.6
48
2.2
1.6
2.0
2.1
2.2
3.0
0.1
98.6
1.0
0.7
96
2.8
1.4
0.7
-62.7
1.0
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192
2.5
2.7
1.3
2.3
-10.5
0.3
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216
2.3
1.1
1.4
1.3
-17.3
0.5
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-5.7
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240
2.9
2.5
1.5
1.4
-30.9
0.9
-1020.5
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-7.7
312
1.4
0.9
1.3
1.7
7.8
0.3
256.9
2.6
1.9
336
1.8
2.4
2.0
1.6
-6.0
0.1
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360
1.5
0.4
0.3
0.0
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0.8
-908.4
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-6.8
1.9
0.9
225
17
Lime
21
Lime
384
2.0
2.3
1.9
1.7
1.2
-13.2
0.7
-435.8
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408
3.1
2.8
2.9
2.5
2.7
-6.6
0.6
-217.9
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504
1.2
1.6
1.4
0.8
-8.4
0.3
-277.5
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528
1.5
1.3
1.3
0.8
1.3
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0.3
-178.5
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552
2.3
1.8
1.7
2.4
2.0
0.0
0.0
0.0
0.0
0.0
576
1.1
0.7
1.4
1.3
1.1
3.6
0.1
118.7
1.2
0.9
-1
2.6
2.6
2.0
2.0
1.7
-14.4
0.9
-477.6
-4.8
-3.6
0
43.4
47.7
51.6
55.3
237.6
1.0
7920.7
79.2
59.4
2
1.4
1.6
2.1
2.6
2.8
22.6
1.0
753.3
7.5
5.6
8
2.2
2.1
2.0
1.8
1.9
-5.4
0.8
-177.4
-1.8
-1.3
24
1.9
2.1
1.8
1.8
1.7
-4.2
0.5
-137.8
-1.4
-1.0
48
1.9
1.4
1.6
1.6
1.5
-3.6
0.3
-118.3
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96
2.7
0.9
0.2
0.0
1.1
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0.4
-806.6
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192
1.5
2.1
1.1
0.9
0.5
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0.7
-631.0
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-4.7
216
3.5
1.8
2.5
0.9
0.7
-38.6
0.8
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240
2.2
1.8
1.9
1.3
0.7
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0.9
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-7.0
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264
3.0
3.2
0.9
1.6
1.1
-31.2
0.6
-1028.4
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-7.7
336
1.7
2.1
1.5
1.8
1.5
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0.2
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360
3.0
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2.3
1.5
2.2
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0.5
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384
1.7
1.2
1.5
0.3
1.3
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0.2
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432
1.9
0.6
0.8
0.0
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0.6
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528
1.6
1.8
1.5
0.9
1.6
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0.2
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552
2.6
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1.6
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0.5
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576
1.7
1.6
2.1
2.0
2.3
9.6
0.8
317.6
3.2
2.4
600
2.4
1.8
2.2
2.2
2.7
6.0
0.2
197.8
2.0
1.5
-1
1.5
1.6
1.6
1.6
1.4
-1.2
0.1
-39.8
-0.4
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0
14.8
18.1
22.7
25.5
27.8
200.4
1.0
6680.6
66.8
50.1
2
2.3
2.2
3.2
3.3
3.2
17.4
0.7
579.9
5.8
4.3
8
1.6
0.8
1.3
1.5
1.6
4.2
0.1
138.0
1.4
1.0
24
2.1
2.4
2.5
2.3
2.3
1.8
0.1
59.1
0.6
0.4
48
1.7
0.9
1.0
1.3
0.7
-9.6
0.4
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96
2.8
2.2
1.7
1.4
1.8
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0.7
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192
2.7
1.7
1.6
1.5
1.8
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216
2.7
2.5
2.2
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1.3
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240
2.5
1.7
0.6
0.7
1.2
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0.5
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264
2.5
1.7
0.6
0.7
1.2
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0.5
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336
3.5
3.6
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360
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0.9
0.3
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384
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1.7
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528
1.8
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226
19
Lime
PAC
552
1.9
1.7
1.7
2.3
7.2
7.2
0.3
238.1
2.4
1.8
576
1.9
1.7
3.4
2.2
600
2.4
2.7
2.7
2.4
1.1
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3.1
3.0
2.6
3.4
2.9
0.0
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0.0
0
13.9
16.1
2
2.0
1.8
18.4
20.5
22.6
130.8
1.0
4360.4
43.6
32.7
2.5
3.1
2.9
19.0
0.7
632.1
6.3
4.7
8
1.7
1.2
1.9
1.3
1.7
0.6
0.0
19.7
0.2
0.1
24
1.9
2.5
1.6
1.7
1.7
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0.3
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48
1.7
1.2
0.5
0.5
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0.9
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96
2.7
1.1
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192
2.8
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0.6
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216
2.1
0.7
1.0
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0.7
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240
2.5
1.8
1.1
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1.0
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264
2.4
1.7
1.0
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0.8
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0.8
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336
1.5
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360
2.0
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0.8
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0.9
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384
2.8
2.3
1.0
0.7
-45.6
0.9
-1505.7
-15.1
-11.3
432
2.0
1.0
0.7
0.9
1.2
-10.2
0.3
-336.8
-3.4
-2.5
528
1.8
1.3
0.4
0.2
0.2
-25.8
0.9
-852.4
-8.5
-6.4
552
1.9
1.2
0.6
0.5
-28.8
0.9
-952.2
-9.5
-7.1
576
2.0
0.8
0.9
1.4
0.3
-16.8
0.5
-555.9
-5.6
-4.2
600
2.2
1.0
1.7
1.5
1.6
-4.2
0.1
-138.5
-1.4
-1.0
-1
1.6
3.4
5.1
6.6
8.2
98.8
1.0
3256.1
32.6
24.4
0
1.9
1.7
2.0
2.3
2.2
7.2
0.6
236.2
2.4
1.8
6
1.9
1.9
1.9
1.7
1.7
-3.6
0.8
-118.9
-1.2
-0.9
24
1.3
1.0
1.6
1.0
1.3
0.0
0.0
0.0
0.0
0.0
48
2.8
2.4
1.2
2.0
1.8
-13.0
0.4
-430.6
-4.3
-3.2
72
2.5
0.8
0.1
-70.9
0.9
-2376.1
-23.8
-17.8
96
3.2
2.5
2.6
3.0
1.8
-13.3
0.4
-440.3
-4.4
-3.3
144
1.1
1.1
0.8
1.1
1.3
1.9
0.1
61.4
0.6
0.5
168
2.2
1.8
1.9
1.3
0.7
-21.1
0.9
-707.6
-7.1
-5.3
192
1.9
0.9
0.0
0.0
0.8
-18.7
0.4
-619.1
-6.2
-4.6
216
2.0
1.4
0.9
1.1
1.1
-12.6
0.6
-418.3
-4.2
-3.1
240
1.2
0.0
1.0
0.8
0.7
-1.2
0.0
-39.8
-0.4
-0.3
264
1.7
2.0
1.3
1.9
1.8
0.6
0.0
19.7
0.2
0.1
312
1.4
0.6
1.0
1.1
0.7
336
2.2
1.2
0.5
1.2
360
1.5
1.2
1.4
1.4
384
1.2
1.6
1.6
408
1.9
1.8
1.2
1.9
-5.4
0.2
-177.9
-1.8
-1.3
-22.2
0.5
-729.8
-7.3
-5.5
1.3
-1.2
0.1
-39.4
-0.4
-0.3
1.3
0.3
-12.9
0.4
-425.2
-4.3
-3.2
1.5
1.3
-9.0
0.6
-296.4
-3.0
-2.2
227
PAC
Char
Char
-1
0.6
3.3
4.9
5.6
6.6
86.2
0.9
2838.9
28.4
21.3
0
1.4
1.7
1.8
1.7
2.3
10.8
0.8
354.2
3.5
2.7
6
1.8
1.5
1.4
1.8
1.6
-0.6
0.0
-19.8
-0.2
-0.1
24
1.6
1.5
2.2
1.9
2.1
8.4
0.5
278.9
2.8
2.1
48
4.3
2.8
1.6
2.4
2.2
-26.3
0.5
-868.2
-8.7
-6.5
72
4.9
0.0
0.6
-127.5
0.6
-4273.6
-42.7
-32.1
96
4.3
2.4
2.6
1.8
2.2
-28.3
0.6
-932.9
-9.3
-7.0
144
0.9
1.0
0.5
0.5
0.3
-10.1
0.8
-335.0
-3.4
-2.5
168
1.8
1.1
0.9
0.5
0.9
-14.4
0.6
-483.9
-4.8
-3.6
192
1.7
1.5
1.8
0.9
1.4
216
2.1
1.5
0.4
0.8
240
1.6
0.8
0.6
0.9
264
1.8
0.2
0.4
312
1.9
2.3
336
1.9
2.3
360
1.1
384
-7.2
0.3
-238.1
-2.4
-1.8
-30.0
0.7
-995.9
-10.0
-7.5
0.6
-11.4
0.5
-378.1
-3.8
-2.8
0.0
0.3
-19.2
0.5
-630.8
-6.3
-4.7
1.7
1.8
1.8
-4.2
0.2
-138.4
-1.4
-1.0
2.1
1.5
-8.4
0.3
-276.1
-2.8
-2.1
1.6
2.5
1.6
2.2
13.2
0.4
433.7
4.3
3.3
2.2
1.4
1.4
1.5
2.1
-0.6
0.0
-19.7
-0.2
-0.1
408
1.3
1.0
1.6
1.4
1.2
1.2
0.0
39.5
0.4
0.3
-1
1.6
1.7
1.7
1.7
1.7
1.2
0.5
39.8
0.4
0.3
0
8.4
10.2
13.0
16.0
16.9
136.8
1.0
4560.4
45.6
34.2
6
2.9
3.3
4.0
5.1
5.8
45.6
1.0
1519.8
15.2
11.4
24
2.0
2.0
2.1
2.2
2.1
2.4
0.6
78.8
0.8
0.6
48
1.7
1.6
1.6
1.6
1.7
0.0
0.0
0.0
0.0
0.0
72
2.8
2.6
2.5
2.5
2.5
-9.0
0.7
-295.9
-3.0
-2.2
96
2.1
2.0
1.9
1.9
1.9
-3.0
0.8
-98.6
-1.0
-0.7
144
3.3
2.8
1.6
2.4
2.2
-14.3
0.4
-470.9
-4.7
-3.5
168
1.7
2.0
2.1
2.2
2.2
7.2
0.8
238.5
2.4
1.8
192
2.0
2.1
2.2
2.3
2.5
7.2
1.0
237.8
2.4
1.8
216
2.5
3.0
3.5
3.6
3.6
23.0
0.8
756.9
7.6
5.7
240
1.6
1.7
1.7
1.8
1.9
4.2
0.9
138.5
1.4
1.0
264
2.0
1.6
1.8
1.9
2.1
3.0
0.2
98.7
1.0
0.7
312
1.9
2.0
2.1
2.2
2.2
4.4
0.9
146.6
1.5
1.1
336
1.9
1.9
2.0
2.1
2.1
3.8
0.9
124.8
1.2
0.9
360
1.9
1.9
1.7
1.6
1.5
-6.6
0.9
-218.1
-2.2
-1.6
384
2.0
2.1
2.1
2.2
2.2
3.0
0.9
99.2
1.0
0.7
408
1.9
2.1
1.9
1.8
1.8
-3.0
0.4
-99.3
-1.0
-0.7
-1
1.6
1.8
2.2
2.0
1.9
4.8
0.3
159.2
1.6
1.2
0
4.9
5.9
8.1
9.3
11.2
96.2
1.0
3208.3
32.1
24.1
6
2.1
3.1
4.5
5.2
5.7
55.8
1.0
1859.7
18.6
13.9
24
2.1
1.1
1.6
1.7
1.9
1.2
0.0
39.4
0.4
0.3
48
1.7
1.7
1.8
1.8
1.9
3.0
0.9
98.4
1.0
0.7
228
Soil
72
1.3
1.3
1.3
1.3
1.4
1.2
0.5
39.4
0.4
0.3
96
2.0
2.1
2.2
2.2
2.3
4.2
0.9
138.0
1.4
1.0
144
2.0
2.0
2.0
2.1
2.1
1.8
0.8
59.4
0.6
0.4
168
1.8
1.7
1.6
1.6
1.5
-4.2
0.9
-139.1
-1.4
-1.0
192
1.3
1.0
0.6
1.1
0.9
-4.2
0.2
-138.7
-1.4
-1.0
216
2.2
1.2
1.4
1.2
0.9
-15.6
0.7
-513.8
-5.1
-3.9
240
2.3
2.4
2.4
2.2
2.1
-3.6
0.5
-118.7
-1.2
-0.9
264
2.0
2.0
1.7
1.6
1.5
-8.4
0.9
-276.5
-2.8
-2.1
312
2.1
2.1
2.2
2.2
2.3
3.0
0.9
99.1
1.0
0.7
336
2.4
2.5
2.2
1.8
1.7
-12.6
0.9
-416.0
-4.2
-3.1
360
2.6
2.6
2.5
2.6
2.4
-2.4
0.5
-79.3
-0.8
-0.6
384
2.1
2.1
2.0
2.1
2.2
1.2
0.2
39.7
0.4
0.3
408
1.8
1.8
1.7
1.8
1.6
-2.4
0.5
-79.4
-0.8
-0.6
-1
2.4
2.4
2.5
2.6
2.6
3.6
0.9
119.4
1.2
0.9
0
1.8
3.2
4.1
7.2
8.4
103.2
1.0
3440.3
34.4
25.8
6
2.1
2.3
2.6
2.9
3.1
15.6
1.0
519.9
5.2
3.9
24
2.2
2.3
2.3
2.1
1.9
-4.8
0.6
-157.7
-1.6
-1.2
48
2.2
2.3
2.3
2.2
2.2
-0.6
0.1
-19.7
-0.2
-0.1
72
1.2
1.2
1.2
1.3
1.2
0.6
0.1
19.7
0.2
0.1
96
1.8
1.7
1.6
1.4
1.5
-5.4
0.8
-177.5
-1.8
-1.3
144
2.0
2.1
2.1
2.2
2.0
0.6
0.0
19.8
0.2
0.1
168
2.0
2.2
2.3
2.3
2.4
5.4
0.9
178.9
1.8
1.3
192
1.6
1.3
1.2
1.4
1.7
1.8
0.1
59.4
0.6
0.4
216
1.3
1.3
1.1
1.1
1.1
-3.6
0.8
-118.6
-1.2
-0.9
240
1.9
2.0
2.3
2.1
1.8
-0.6
0.0
-19.8
-0.2
-0.1
264
2.0
2.0
2.1
2.1
2.3
4.2
0.8
138.2
1.4
1.0
312
2.1
2.2
2.4
2.4
2.5
6.0
0.9
198.1
2.0
1.5
336
2.4
2.4
2.1
2.2
2.3
-2.4
0.2
-79.2
-0.8
-0.6
360
2.0
2.0
2.0
1.9
1.8
-3.0
0.8
-99.1
-1.0
-0.7
384
2.1
2.2
2.2
2.3
2.5
5.4
0.9
178.5
1.8
1.3
408
1.8
1.8
1.9
2.1
2.1
5.4
0.9
178.7
1.8
1.3
229
Table D 4 Carbon dioxide flux
ug CO2 m
-1
h
ppm
0
1
2
3
4
ppm
h-1
-2
kg CO2-C ha
-1
hr
-1
R²
28
-1
889
1010
1120
1190
1280
5772
0.99
523126
1.4
Slurry
0
2950
3840
4580
5250
5840
43140
0.99
3892138
10.6
6
1330
1630
1900
2140
2360
15420
1.00
1401168
3.8
24
882
1010
1120
1230
1320
6576
1.00
600647
1.6
48
654
728
797
858
912
3876
1.00
352285
1.0
72
669
734
792
846
901
3456
1.00
318634
0.9
96
575
642
698
748
841
3828
0.99
347443
0.9
144
668
734
791
846
897
3420
1.00
310613
0.8
168
819
871
916
962
1010
2838
1.00
261977
0.7
192
756
851
913
972
1100
4854
0.98
441567
1.2
216
672
738
771
858
849
2844
0.92
259684
0.7
240
775
946
1010
1060
1120
4824
0.92
440120
1.2
264
606
678
732
780
819
3168
0.99
286284
0.8
312
795
896
986
1050
1110
4704
0.99
426297
1.2
336
942
1060
1160
1240
5964
0.99
539302
1.5
360
792
869
926
973
1010
3240
0.98
292814
0.8
384
760
867
931
993
1050
4236
0.98
382611
1.0
408
637
729
749
791
2892
0.92
261958
0.7
0
0.0
26
-1
833
956
1060
1140
1230
5868
0.99
531826
1.5
Slurry
0
2750
3490
4110
4670
5100
35280
0.99
3183000
8.7
6
1210
1460
1690
1900
2100
13320
1.00
1210347
3.3
24
846
972
1080
1180
1270
6336
1.00
578726
1.6
48
636
711
786
861
933
4464
1.00
405727
1.1
72
614
739
830
914
999
5670
0.99
522759
1.4
96
625
725
804
887
963
5028
1.00
456360
1.2
144
614
705
778
846
913
4434
1.00
402708
1.1
168
686
808
895
978
1060
5508
0.99
508445
1.4
192
850
955
1050
1120
1190
5070
0.99
461217
1.3
216
832
855
928
969
2904
0.97
265163
0.7
240
635
749
835
907
969
4956
0.99
452164
1.2
264
704
777
831
882
928
3318
0.99
299839
0.8
312
767
887
937
999
1070
4308
0.98
390409
1.1
336
1480
1380
1420
1450
-300
0.02
-27128
-0.1
360
786
896
977
1040
1100
4632
0.98
418616
1.1
384
798
895
969
1040
1090
4374
0.99
395076
1.1
408
665
731
787
835
880
3204
0.99
290219
0.8
230
0
0.0
27
-1
627
773
849
923
987
5220
0.97
473097
1.3
Slurry
0
2900
3730
4410
5010
5560
39600
0.99
3572755
9.7
6
1300
1580
1820
2040
2250
14160
1.00
1286675
3.5
24
868
987
1090
1180
1280
6102
1.00
557352
1.5
48
700
790
864
939
1000
4494
1.00
408454
1.1
72
657
771
850
927
996
5004
0.99
461356
1.3
96
579
694
779
858
932
5220
0.99
473786
1.3
144
591
732
812
893
967
5478
0.98
497526
1.4
168
654
792
866
934
998
4980
0.97
459705
1.3
192
766
852
919
978
1030
3924
0.99
356965
1.0
216
674
750
806
848
889
3168
0.98
289268
0.8
240
709
790
843
887
929
3222
0.98
293961
0.8
264
653
712
759
798
833
2676
0.99
241823
0.7
312
731
803
866
907
952
3276
0.99
296885
0.8
336
872
970
1030
1120
4824
0.99
436216
1.2
360
875
939
990
1030
1070
2886
0.99
260822
0.7
384
734
803
855
898
930
2922
0.98
263926
0.7
408
752
801
836
865
881
1932
0.97
175001
0.5
0
0.0
31
Alum
30
Alum
-1
735
877
963
1050
1120
5658
0.98
512794
1.4
0
1480
2920
3920
4670
5380
57300
0.98
5169669
14.1
6
845
1000
1160
1310
1460
9240
1.00
839610
2.3
24
877
1030
1180
1320
1460
8736
1.00
797940
2.2
48
739
856
970
1070
1180
6576
1.00
597684
1.6
72
545
678
809
937
1060
7734
1.00
713055
1.9
96
569
678
791
898
1000
6492
1.00
589238
1.6
144
637
778
882
976
1070
6384
0.99
579812
1.6
168
637
750
856
966
1060
6372
1.00
588201
1.6
192
882
946
1000
1060
1120
3540
1.00
322033
0.9
216
596
669
726
785
832
3528
0.99
322140
0.9
240
770
845
912
976
1040
4026
1.00
367314
1.0
264
937
982
1030
1080
1130
2904
1.00
262427
0.7
312
727
789
913
969
1030
4716
0.98
427384
1.2
336
978
986
1010
1040
1060
1308
0.97
118277
0.3
360
716
791
845
899
948
3432
0.99
310166
0.8
384
782
867
946
1020
1090
4614
1.00
416753
1.1
408
807
876
953
1020
1040
3660
0.97
331524
0.9
0
0.0
-1
1040
1220
1370
1500
1610
8520
0.99
772182
2.1
0
2900
3890
4770
5590
6210
49920
0.99
4503837
12.3
6
960
1130
1290
1440
1580
9300
1.00
845062
2.3
24
851
991
1110
1230
1340
7302
1.00
666959
1.8
231
32
Alum
23
FeCl
48
781
874
953
1030
1110
4884
1.00
443901
1.2
72
794
906
1020
1110
1210
6216
1.00
573099
1.6
96
623
737
842
927
1000
5664
0.99
514086
1.4
144
640
881
917
1020
7056
0.89
640845
1.7
168
758
891
980
1060
1140
5598
0.99
516753
1.4
192
678
801
890
981
1050
5544
0.99
504336
1.4
216
773
739
805
859
879
1992
0.81
181888
0.5
240
725
831
904
973
1030
4512
0.99
411655
1.1
264
722
822
880
958
1020
4392
0.99
396894
1.1
312
859
952
1030
1100
1150
4380
0.99
396934
1.1
336
843
977
1088
1140
1030
3222
0.55
291353
0.8
360
741
872
965
1040
1110
5436
0.98
491277
1.3
384
779
867
928
980
1020
3570
0.98
322456
0.9
408
706
780
844
897
946
3582
0.99
324459
0.9
0
0.0
-1
843
970
1070
1150
1220
5604
0.99
507900
1.4
0
2000
2530
2990
3410
3780
26640
1.00
2403490
6.6
6
870
1010
1140
1260
1380
7620
1.00
692406
1.9
24
934
1050
1150
1260
1360
6372
1.00
582014
1.6
48
719
813
901
984
1060
5118
1.00
465169
1.3
72
804
911
1010
1110
1200
5946
1.00
548206
1.5
96
624
740
838
928
1010
5760
1.00
522799
1.4
144
651
722
864
948
1030
5904
0.99
536217
1.5
168
896
991
1080
1150
1230
4962
1.00
458044
1.2
192
841
949
1030
1100
1170
4854
0.99
441567
1.2
216
709
777
828
872
911
2994
0.99
273380
0.7
240
642
764
838
909
5250
0.98
478987
1.3
264
703
786
851
908
961
3828
0.99
345927
0.9
312
803
944
1050
1140
1210
6060
0.98
549183
1.5
336
944
1090
1190
1280
6648
0.99
601153
1.6
360
708
795
871
930
982
4098
0.99
370356
1.0
384
669
795
860
939
1000
4836
0.98
436805
1.2
408
671
763
806
846
3408
0.95
308698
0.8
0
0.0
-1
846
992
1060
1120
1160
4536
0.94
413845
1.1
0
2870
3650
4350
4970
5530
39840
1.00
3653149
10.0
2
1110
1280
1440
1590
1730
9300
1.00
852561
2.3
8
620
700
767
833
894
4086
1.00
369241
1.0
24
954
1090
1210
1330
1440
7272
1.00
656408
1.8
48
746
845
927
1000
1080
4938
1.00
446525
1.2
96
697
800
872
949
1020
4770
0.99
431228
1.2
192
960
1030
1090
1130
3420
0.99
310336
0.8
216
747
861
918
1000
4830
0.99
440025
1.2
1080
232
24
FeCl
18
FeCl
240
740
836
909
971
1020
4170
0.98
378792
1.0
312
966
1020
1070
1110
336
955
1020
1070
1120
1080
2892
1.00
262001
0.7
2100
0.76
190450
0.5
360
714
805
877
940
985
4062
0.98
367729
1.0
384
699
742
779
811
839
2094
0.99
190183
0.5
408
841
887
504
823
930
945
971
997
2376
0.97
215771
0.6
993
1050
4464
0.98
405684
1.1
528
873
909
949
985
1020
2220
1.00
201899
0.6
552
738
805
851
889
924
2736
0.98
249008
0.7
576
682
762
799
836
867
2664
0.96
241623
0.7
0
0.0
-1
647
807
862
903
965
4392
0.92
400707
1.1
0
2810
3245
4250
4870
5450
41430
0.99
3798945
10.4
2
1600
1780
1950
2100
2220
9360
0.99
858062
2.3
8
658
747
832
908
982
4854
1.00
438644
1.2
24
1290
1470
1630
1780
1930
9540
1.00
861129
2.3
48
825
941
1040
1140
1230
6054
1.00
547440
1.5
1190
7914
1.00
715459
2.0
4560
1.00
413782
1.1
96
666
809
949
1080
192
1070
1150
1220
1300
216
895
976
1040
1110
1230
4824
0.99
439478
1.2
240
776
861
955
1050
1130
5382
1.00
488887
1.3
312
902
969
1020
1070
3330
0.99
301681
0.8
336
964
1030
1090
1150
1230
3912
1.00
354781
1.0
360
822
903
974
1040
1100
4158
1.00
376419
1.0
384
588
681
749
801
837
3708
0.97
336770
0.9
408
769
817
872
915
951
2772
0.99
251733
0.7
504
866
974
1050
1130
5208
0.99
473298
1.3
528
740
819
883
954
998
3906
0.99
355232
1.0
552
713
779
827
865
897
2724
0.98
247916
0.7
576
701
746
790
827
865
2454
1.00
222576
0.6
0
0.0
-1
605
732
798
856
907
4368
0.96
398517
1.1
0
2130
2670
3160
3620
4030
28500
1.00
2613322
7.1
2
1270
1420
1560
1700
8580
1.00
786557
2.1
8
629
698
766
829
889
3906
1.00
352975
1.0
24
1060
1220
1360
1490
1620
8340
1.00
752811
2.1
48
769
864
950
1030
1010
3888
0.89
351577
1.0
96
573
694
790
886
971
5928
1.00
535917
1.5
192
961
1070
1170
1260
1340
5688
1.00
516138
1.4
216
860
953
1040
1120
1010
2802
0.58
255269
0.7
240
701
885
992
1100
1190
7158
0.98
650214
1.8
312
814
972
1040
1100
5556
0.94
503345
1.4
336
991
1060
1120
1180
3348
0.98
303632
0.8
1210
233
17
Lime
21
Lime
360
760
825
893
951
1010
3756
1.00
340027
0.9
384
904
937
962
990
1020
1710
1.00
155307
0.4
408
719
778
873
916
954
3648
0.97
331285
0.9
504
829
927
997
1060
4578
0.99
416044
1.1
528
702
792
848
903
954
3690
0.99
335588
0.9
552
705
760
816
864
909
3072
1.00
279588
0.8
576
790
816
847
876
898
1656
1.00
150198
0.4
0
0.0
-1
638
701
760
806
847
3138
0.99
286297
0.8
0
350
311
287
273
2
483
479
477
473
469
-1530
0.95
-140294
-0.4
-204
0.99
-18701
-0.1
8
419
416
413
410
407
-180
1.00
-16266
0.0
24
778
831
875
918
959
2694
1.00
243174
0.7
48
758
872
96
713
845
950
1020
1096
4944
0.99
447067
1.2
952
1050
1150
6474
1.00
585277
1.6
192
818
907
982
1050
1110
4362
0.99
395815
1.1
216
813
948
1040
1120
1190
5556
0.98
506165
1.4
240
794
843
893
941
980
2820
1.00
256161
0.7
264
807
856
897
950
1030
3240
0.98
293528
0.8
336
698
801
860
910
953
3714
0.97
336824
0.9
360
770
824
875
918
954
2772
0.99
250946
0.7
384
666
709
751
774
805
2058
0.99
186913
0.5
432
700
782
787
819
872
2286
0.92
207598
0.6
528
811
920
979
1030
4296
0.97
390416
1.1
552
786
839
880
918
944
2370
0.99
215540
0.6
576
720
781
823
863
893
2568
0.98
233718
0.6
600
709
731
752
791
807
1536
0.98
139314
0.4
0
0.0
-1
644
803
861
918
964
4530
0.92
413297
1.1
0
379
324
261
241
228
-2310
0.92
-211817
-0.6
2
437
435
425
419
410
-420
0.97
-38503
-0.1
8
392
382
374
380
361
-384
0.79
-34701
-0.1
24
767
826
892
937
976
3174
0.99
286501
0.8
48
717
826
1010
1090
1070
5820
0.88
526281
1.4
96
711
869
996
1110
1220
7554
0.99
682914
1.9
192
761
905
1010
1090
1160
5898
0.98
535194
1.5
216
848
937
989
1060
1120
4002
0.99
364592
1.0
240
790
921
1010
1090
1160
5454
0.98
495427
1.4
264
739
827
880
939
985
3624
0.99
328316
0.9
336
776
891
940
1060
1130
5262
0.99
477213
1.3
360
751
829
899
956
1010
3870
0.99
350347
1.0
384
688
757
810
852
882
2898
0.98
263204
0.7
432
794
835
878
911
944
2256
1.00
204873
0.6
234
19
Lime
PAC
528
866
974
1050
1130
552
856
955
981
1030
576
821
870
915
955
600
639
675
710
742
5208
0.99
473298
1.3
1070
3018
0.95
274473
0.7
980
2418
0.99
220066
0.6
771
1986
1.00
180129
0.5
0
0.0
-1
872
953
1020
1070
1110
3558
0.98
324616
0.9
0
480
455
432
417
406
-1116
0.97
-102332
-0.3
2
443
435
424
421
414
-432
0.97
-39603
-0.1
8
374
361
351
343
337
-552
0.98
-49883
-0.1
24
713
751
787
820
847
2022
1.00
182516
0.5
48
646
700
789
862
927
4344
1.00
392811
1.1
96
525
688
793
898
995
6900
0.99
623790
1.7
192
820
931
1030
1120
1200
5694
1.00
516683
1.4
216
751
892
1060
1130
1190
6696
0.96
610022
1.7
240
860
1000
1100
1180
1260
5880
0.98
534124
1.5
264
937
1020
1090
1160
1200
3996
0.99
362017
1.0
336
798
915
1000
1080
1150
5214
0.99
472860
1.3
360
711
865
944
1020
1060
5118
0.95
463327
1.3
384
792
849
893
932
968
2610
0.99
237047
0.6
432
611
790
848
899
941
4614
0.89
419010
1.1
528
773
903
997
1070
5910
0.98
537095
1.5
552
754
860
931
987
1040
4194
0.98
381425
1.0
576
687
789
847
899
947
3780
0.97
344024
0.9
600
675
716
764
784
802
1932
0.96
175231
0.5
0
0.0
-1
3310
4150
4840
5500
6070
41220
0.99
3735836
10.2
0
833
1050
1200
1330
1460
9204
0.99
830395
2.3
6
681
765
845
917
987
4584
1.00
416534
1.1
24
1140
1310
1470
1620
1760
9300
1.00
849455
2.3
48
627
735
860
973
1080
6864
1.00
623860
1.7
72
464
586
737
868
993
8040
1.00
741267
2.0
96
781
889
982
1060
1130
5214
0.99
473242
1.3
144
760
882
982
1070
1150
5808
0.99
527498
1.4
168
802
948
1060
1160
1250
6648
0.99
613679
1.7
192
693
795
881
955
1020
4884
0.99
444296
1.2
216
767
863
937
981
1050
4104
0.98
374734
1.0
240
835
930
997
1060
1110
4080
0.99
372241
1.0
264
734
798
844
888
925
2832
0.99
255921
0.7
312
736
813
882
928
975
3558
0.99
322441
0.9
336
811
920
979
1030
4296
0.97
388471
1.1
360
836
910
961
1010
1050
3168
0.99
286307
0.8
384
821
870
915
955
980
2418
0.99
218403
0.6
408
678
738
792
839
887
3114
1.00
282067
0.8
235
0.0
PAC
-1
2010
2234
3430
3820
4200
35796
0.94
3244250
8.8
0
836
962
1080
1190
1300
6936
1.00
625774
1.7
6
612
676
734
842
4488
0.98
407811
1.1
24
886
1010
1120
1220
1320
6468
1.00
590782
1.6
48
617
716
806
889
967
5238
1.00
476075
1.3
72
561
622
697
765
831
4098
1.00
377825
1.0
96
898
1100
1230
1330
1430
7764
0.97
704689
1.9
144
742
858
937
1010
1070
4848
0.98
440308
1.2
168
1150
1240
1280
1320
1360
3000
0.96
276931
0.8
192
960
1040
1060
1090
1120
2220
0.93
201953
0.6
216
758
896
974
1040
1100
4968
0.97
453625
1.2
240
942
994
1040
1080
1110
2532
0.99
231009
0.6
264
663
779
849
907
959
4320
0.97
390387
1.1
312
885
954
1000
1040
1080
2856
0.98
258823
0.7
336
829
827
997
1022
1060
3942
0.84
356460
1.0
360
982
1050
1100
1150
1190
3096
0.99
279800
0.8
384
836
874
914
953
999
2430
1.00
219487
0.6
408
708
744
783
815
851
2142
1.00
194023
0.5
0.0
Char
-1
1012
1022
1038
1044
1052
612
0.97
55836
0.2
0
678
681
688
693
698
312
0.99
28609
0.1
6
552
555
562
568
573
330
0.99
30252
0.1
24
704
706
708
709
710
102
0.98
9217
0.0
48
783
789
793
803
812
432
0.97
38995
0.1
72
722
717
724
731
729
204
0.57
18447
0.1
96
691
702
704
707
708
300
0.86
27121
0.1
144
829
832
844
847
851
354
0.94
32123
0.1
168
449
452
467
473
488
594
0.96
54115
0.1
192
594
596
598
604
609
228
0.95
20711
0.1
216
560
652
655
656
661
1236
0.57
111975
0.3
240
723
726
732
738
741
288
0.98
26119
0.1
264
890
902
917
926
943
780
0.99
70613
0.2
312
882
886
892
899
903
330
0.99
29971
0.1
336
1001
1004
1012
1014
1019
276
0.97
25064
0.1
360
702
708
714
723
736
498
0.97
45258
0.1
384
722
723
723
725
729
96
0.82
8731
0.0
408
511
524
555
571
579
1098
0.96
99931
0.3
0.0
Char
-1
736
754
777
823
896
2334
0.92
212944
0.6
0
1003
1021
1134
1146
1204
3162
0.93
289941
0.8
6
823
879
933
972
1011
2814
0.99
257969
0.7
24
742
890
1023
1085
6972
0.97
630042
1.7
236
48
825
922
1057
1108
1239
6084
0.99
549173
1.5
72
552
627
645
674
681
2304
0.91
208342
0.6
96
716
724
748
776
779
1224
0.95
110655
0.3
144
713
735
746
772
783
1062
0.98
96368
0.3
168
924
926
931
937
946
330
0.95
30064
0.1
192
801
810
814
823
834
474
0.98
43057
0.1
216
649
652
655
656
661
168
0.97
15220
0.0
240
702
702
705
709
710
138
0.92
12515
0.0
264
714
712
715
717
721
114
0.77
10320
0.0
312
783
786
792
793
796
198
0.96
17983
0.0
336
802
813
813
809
812
96
0.29
8718
0.0
360
853
870
876
891
902
714
0.99
64888
0.2
384
739
741
745
751
759
300
0.95
27284
0.1
408
795
801
803
809
810
228
0.96
20751
0.1
0.0
Soil
-1
488
499
502
509
0
566
571
577
579
396
0.95
36129
0.1
581
228
0.95
20907
0.1
6
362
367
371
376
378
246
0.98
22552
0.1
24
466
469
478
493
505
612
0.95
55305
0.2
48
593
594
597
602
611
264
0.89
23830
0.1
72
738
741
750
757
762
384
0.98
34724
0.1
96
711
713
713
716
718
102
0.94
9221
0.0
144
892
903
926
951
973
1260
0.99
114334
0.3
168
764
777
781
789
795
444
0.97
40449
0.1
192
721
730
734
742
748
396
0.99
35972
0.1
216
692
703
717
728
751
858
0.98
77730
0.2
240
503
510
513
518
288
0.98
26119
0.1
264
901
903
908
911
210
0.98
19011
0.1
312
873
875
878
880
144
0.99
13078
0.0
336
772
784
801
819
837
990
0.99
89905
0.2
360
813
820
822
825
832
258
0.96
23447
0.1
384
845
850
852
857
859
210
0.98
19099
0.1
408
703
708
719
725
740
546
0.97
49692
0.1
237
Appendix E Photographs of slurry and amended slurry applied
to plots (Chapter 6)
238
Figure E Photographs of slurry and amended slurry applied to plots (Chapter 6)
Plot 2
No slurry applied
Plot 3
Alum amended slurry
19th October 2010
1st October 2010
17th September 2010
Plot 1
Lime amended slurry
239
Plot 4
Slurry-control
Plot 5
PAC amended slurry
Appendix F Results of plot study
240
Notation used in Table F.1
Plot: plot identification number
ttorun1: time from start of rain to runoff event 1
pHe1: pH of runoff water (average for each event)
ttorun2: time from start of rain to runoff event 2
ttorun3: time from start of rain to runoff event 3
intensity1: average rainfall intensity during rainfall event 1
intensity2: average rainfall intensity during rainfall event 1
intensity3: average rainfall intensity during rainfall event 1
slope%: slope of plot
Table F.1. Volume of runoff, concentrations of Cl (chlorine), NH4 (ammonium), NO2 (nitrite), DRP
(dissolved reactive phosphorus), total dissolved phosphorus (TDP), TP (total phosphorus) and TON
(total oxidized nitrogen).
Plot
Event
Treatment
Start
1
1
lime
-60
1
1
lime
1
1
lime
1
1
1
1
End
Volume
Cl
NH4
NO2
DRP
TDP
TP
TON
Vol runoff
mg/l
mg/l
mg/l
mg/l
mg/L
mg/L
mg/l
0
97.0
53.2
0.5
0.0
0.8
1.1
1.7
4.1
0
5
140.1
72.2
1.4
0.1
2.1
3.1
5.4
4.8
5
10
197.1
81.1
2.0
0.1
3.2
4.0
6.8
4.1
lime
10
15
217.4
83.5
2.4
0.1
3.7
4.7
8.4
3.9
1
lime
15
20
98.7
85.6
2.6
0.1
3.9
5.3
9.4
4.4
1
lime
20
25
149.8
83.2
2.2
0.1
4.1
5.3
9.5
4.3
1
1
lime
25
30
287.6
82.2
3.1
0.1
4.2
5.5
9.3
4.3
1
1
lime
1
2
lime
0
51.1
48.7
0.0
0.0
0.3
0.5
1
2
lime
0
10
19.0
55.2
0.0
0.0
0.3
0.3
2.6
1
2
lime
10
20
17.2
57.0
0.1
0.0
0.2
0.3
3.0
1
2
lime
20
30
40.7
57.3
0.2
0.0
0.2
1.4
2.8
1
2
lime
1
3
lime
1
3
lime
1
3
1
3
1
3
lime
2
1
soil
-19
0
2
1
soil
0
5
2
1
soil
5
2
1
soil
2
1
2
1
2
1187.6
t
3.2
127.9
t
0
150.2
45.7
0.0
0.0
0.1
0.1
0.2
4.4
0
10
200.0
43.5
0.0
0.0
0.1
0.1
0.2
4.4
lime
10
20
74.7
42.4
0.0
0.0
0.1
0.2
0.3
4.3
lime
20
30
112.2
40.8
0.0
0.0
0.1
0.2
0.3
4.1
47.4
28.8
1.2
0.0
0.0
0.0
0.1
5.0
52.9
28.5
1.0
0.0
0.0
0.0
0.1
4.5
10
36.9
26.2
1.2
0.0
0.0
0.0
0.0
4.5
10
15
42.4
26.4
1.3
0.0
0.0
0.0
0.0
4.6
soil
15
20
45.0
26.0
1.1
0.0
0.0
0.0
0.1
4.4
soil
20
25
35.5
26.4
1.0
0.0
0.0
0.0
4.5
1
soil
25
30
42.9
26.1
0.9
0.0
0.0
0.1
4.5
2
1
soil
2
2
soil
2
2
soil
2
2
soil
537.0
302.9
t
0
19.1
45.8
0.2
0.2
1.3
1.6
2.1
5.3
0
10
18.4
51.1
0.1
0.3
1.9
2.3
2.9
5.7
10
20
39.3
48.8
0.1
0.2
1.4
2.0
5.3
241
2
2
soil
20
2
2
soil
2
3
soil
2
3
soil
2
3
2
3
2
3
soil
3
1
alum
-30
3
1
alum
3
1
alum
3
1
3
3
30
31.0
47.9
0.1
0.1
1.5
0.4
5.0
107.7
t
0
95.7
49.0
0.2
0.0
0.0
0.0
0.2
3.9
0
10
84.5
46.9
0.0
0.0
0.0
0.1
0.2
3.8
soil
10
20
97.2
46.1
0.0
0.0
0.0
0.1
0.1
3.8
soil
20
30
52.3
45.8
0.0
0.0
0.0
0.0
0.1
3.7
84.0
2.1
0.1
1.6
3.2
5.3
4.5
329.7
0
50.0
0
5
34.0
82.8
2.3
0.0
2.3
7.7
9.2
4.9
5
10
54.0
169.9
5.2
0.2
5.0
8.0
15.1
2.9
alum
10
15
23.0
181.2
5.8
0.1
5.1
12.6
2.8
1
alum
15
20
45.0
175.6
10.0
0.0
6.2
14.7
4.2
1
alum
20
25
32.0
174.7
7.7
0.2
5.9
15.2
3.0
3
1
alum
25
30
35.0
160.9
5.6
0.1
6.0
15.4
2.0
3
1
alum
3
2
alum
0
106.0
63.6
0.2
0.1
0.1
0.3
0.4
6.8
3
2
alum
0
10
61.8
61.0
0.2
0.0
0.1
0.3
0.4
6.6
3
2
alum
10
20
76.4
57.9
0.1
0.0
0.2
0.3
0.5
6.1
3
2
alum
20
30
66.1
58.4
0.0
0.0
0.2
0.3
0.4
5.9
3
2
alum
3
3
alum
0.2
0.2
3.0
3
3
alum
0.2
3.0
3
3
alum
3
3
alum
4
1
slurry
4
1
4
1
4
7.1
273.0
t
310.3
t
0
48.6
38.3
0.0
0.0
0.0
0
10
15.9
36.6
0.0
0.0
0.1
20
30
17.6
35.6
0.0
0.0
0.1
3.3
82.2
0
5
17.0
29.6
0.9
0.0
0.0
0.1
0.2
5.0
slurry
5
10
23.1
48.1
2.3
0.0
0.0
0.1
0.3
5.5
slurry
15
20
37.2
40.2
2.1
0.0
0.0
0.2
5.6
1
slurry
20
25
29.2
42.2
2.6
0.0
0.0
4
1
slurry
25
30
36.1
40.2
2.5
0.0
0.0
4
1
slurry
4
2
slurry
4
2
slurry
4
2
4
2
4
2
slurry
4
3
slurry
4
3
slurry
4
3
slurry
4
3
slurry
20
4
3
slurry
5
1
pac
5
1
pac
5
1
pac
2.0
5.2
0.3
5.1
0.3
4.0
142.5
t
0
104.0
32.9
0.1
0.0
0.1
0.1
0
10
67.0
29.6
0.2
0.0
0.1
0.3
3.2
slurry
10
20
66.5
30.0
0.1
0.0
0.2
0.3
3.2
slurry
20
30
59.0
30.1
0.0
0.0
0.0
0.2
3.2
296.5
t
0
58.8
36.6
0.0
0.0
0.0
0.0
0.1
3.7
0
10
43.8
36.0
0.0
0.0
0.0
0.0
0.1
3.8
10
20
37.7
35.9
0.0
0.0
0.0
0.1
3.8
30
33.8
36.2
0.0
0.0
0.0
0.1
3.9
0.2
4.7
174.1
t
0
59.1
96.2
0.7
0.0
0.0
0
5
17.9
153.2
0.9
0.1
0.0
4.8
15
20
14.8
152.0
0.7
0.1
0.0
4.7
242
5
1
pac
20
25
23.0
240.2
0.3
0.1
0.0
5
1
5
1
5
0.3
3.9
pac
5
10
12.6
159.4
0.6
0.1
0.0
4.7
pac
10
15
14.7
163.8
0.5
0.1
0.0
5.2
1
pac
25
30
6.9
326.3
1.5
0.1
0.0
4.0
5
1
pac
5
2
pac
5
2
pac
5
2
5
5
149.0
t
0
106.2
35.6
0.0
0.0
0.1
0
10
33.9
34.4
0.1
0.0
pac
10
20
70.1
34.3
0.1
2
pac
20
30
67.4
35.0
2
pac
5
3
pac
5
3
pac
5
3
pac
5
3
pac
20
5
3
pac
6
1
slurry
-57
0
6
1
slurry
0
5
6
1
slurry
5
6
1
slurry
6
1
slurry
6
1
6
0.1
0.1
3.5
0.0
0.1
3.2
0.0
0.1
0.2
3.0
0.0
0.0
0.0
0.1
0.6
3.3
277.7
t
0
86.8
41.0
0.0
0.0
0.1
0.3
0.5
3.2
0
10
174.2
39.5
0.0
0.0
0.2
0.3
0.5
3.2
10
20
130.4
39.0
0.0
0.0
0.1
0.2
0.6
3.3
30
157.4
38.8
0.0
0.0
0.2
0.2
0.4
3.4
53.1
94.8
1.0
0.0
0.7
4.7
27.3
155.8
1.6
0.0
1.0
6.4
3.7
10
39.5
232.0
2.4
0.1
2.5
7.0
3.5
10
15
43.5
220.3
3.9
0.1
3.1
15
20
54.5
199.4
3.6
0.1
3.5
8.6
3.6
slurry
20
25
53.3
190.2
3.6
0.1
3.3
8.1
3.9
1
slurry
25
30
65.8
184.8
4.2
0.1
3.5
4.5
7.9
3.7
6
1
slurry
6
2
slurry
0.4
0.8
2.8
6
2
slurry
0.8
3.3
6
2
6
2
6
2
slurry
6
3
slurry
6
3
slurry
6
3
slurry
6
3
slurry
20
6
3
slurry
7
1
alum
7
1
alum
7
1
7
7
548.6
3.8
0.4
4.1
337.0
t
0
44.7
48.6
0.1
0.0
0.1
0
10
18.8
48.3
0.2
0.0
0.3
slurry
10
20
24.5
46.4
0.2
0.0
0.3
0.5
0.8
3.5
slurry
20
30
26.6
46.6
0.1
0.0
0.3
0.5
0.0
3.7
0.7
1.7
0.7
1.4
0.8
1.4
114.5
t
0
35.7
35.3
0.0
0.0
0.3
0
10
50.5
32.7
0.0
0.0
0.4
10
20
28.7
33.8
0.0
0.0
0.5
30
60.6
34.3
0.0
0.0
0.6
0.8
0.9
1.4
0.6
175.4
t
0
288.6
207.4
4.3
0.0
0.0
0.4
0.9
5.9
0
5
79.9
168.1
6.8
0.1
0.1
0.3
1.3
6.3
alum
5
10
142.1
84.8
5.5
0.1
0.1
0.3
1.0
5.7
1
alum
10
15
164.2
77.1
4.5
0.1
0.0
0.4
1.0
5.6
1
alum
15
20
165.2
65.6
4.1
0.1
0.1
0.5
0.7
5.5
7
1
alum
20
25
157.8
65.4
4.5
0.1
0.1
0.2
0.8
5.3
7
1
alum
25
30
118.1
70.8
5.7
0.1
0.1
0.2
3.0
5.2
7
1
alum
7
2
alum
7
2
alum
1115.7
t
0
0
25.2
36.5
0.0
0.0
0.0
0.6
10
28.4
46.6
1.2
0.9
1.1
2.0
243
4.6
2.3
3.2
7
2
alum
10
20
18.2
47.6
0.4
0.1
2.9
3.6
3.7
4.9
7
2
alum
20
30
52.6
48.1
0.5
0.1
2.9
3.5
3.6
4.9
7
2
alum
7
3
alum
7
3
alum
7
3
alum
7
3
alum
20
7
3
alum
8
1
soil
0
8
1
soil
0
5
8
1
soil
5
8
1
soil
8
1
soil
8
1
8
99.2
t
0
213.5
34.7
0.0
0.0
0.2
0.3
0.5
2.7
0
10
204.0
34.8
0.0
0.0
0.1
0.3
0.4
2.7
10
20
148.9
35.6
0.0
0.0
0.1
0.2
0.4
2.6
30
111.0
36.4
0.0
0.0
0.2
0.2
0.5
2.7
67.3
27.0
0.7
0.0
0.1
0.2
0.4
4.1
15.0
25.2
0.2
0.0
0.0
3.9
10
14.9
25.1
0.2
0.0
0.0
4.0
10
15
14.8
25.5
0.2
0.0
0.0
4.0
15
20
15.6
26.6
0.2
0.0
0.0
4.1
soil
20
25
15.7
25.0
0.2
0.0
0.0
3.7
1
soil
25
30
27.6
30.9
0.9
0.0
0.0
8
1
soil
25
30
27.6
42.1
0.1
0.0
0.2
8
1
soil
8
2
soil
8
2
soil
8
2
soil
8
2
soil
20
8
2
soil
8
3
soil
0
8
3
soil
0
10
8
3
soil
10
20
8
3
soil
20
30
8
3
soil
9
1
pac
9
1
pac
9
1
9
1
9
1
pac
9
2
pac
0
9
2
pac
0
10
9
2
pac
10
20
9
2
pac
20
30
9
2
pac
9
3
pac
9
3
pac
9
3
9
3
9
3
pac
10
1
lime
677.4
t
3.3
4.2
5.2
4.3
198.5
t
0
195.4
68.5
0.2
0.0
0.3
0.4
1.6
4.6
0
10
151.6
66.1
0.1
0.0
0.3
0.5
0.9
4.9
10
20
113.7
87.1
0.1
0.0
0.3
0.4
0.5
4.3
30
91.1
93.1
0.1
0.0
0.2
0.4
0.4
4.1
64.0
36.9
0.0
0.0
0.2
0.3
0.4
3.4
93.8
36.3
0.0
0.0
0.2
0.3
0.4
3.1
23.8
35.1
0.1
0.0
0.2
0.4
2.4
9.7
34.9
0.0
0.0
0.2
551.8
t
2.0
191.3
t
0
52.2
27.3
0.1
0.0
0.0
3.3
4.6
0
10
43.3
37.1
0.1
0.0
0.0
4.5
pac
10
20
163.7
42.0
0.2
0.0
0.0
5.2
pac
20
30
163.7
40.8
0.1
0.0
0.0
5.3
10.2
48.4
0.5
0.1
3.0
3.5
3.8
4.9
107.7
37.1
0.0
0.0
0.1
3.6
4.2
4.1
52.2
36.3
0.0
0.0
0.2
0.2
0.5
4.2
132.7
36.4
0.0
0.0
0.1
0.2
0.2
4.2
0.1
0.3
3.8
422.9
t
302.7
t
0
57.6
39.7
0.1
0.0
0.1
0
10
30.7
39.1
0.0
0.0
0.1
0.2
3.8
pac
10
20
17.6
40.0
0.0
0.0
0.1
0.2
3.7
pac
20
30
36.3
39.3
0.0
0.0
0.1
0.2
3.7
72.1
1.0
0.0
0.7
2.4
4.7
142.1
t
0
72.2
244
0.9
10
1
lime
0
5
33.0
92.0
0.7
0.0
1.3
10
1
10
1
10
4.0
4.6
lime
5
10
56.0
94.4
1.6
0.1
lime
10
15
53.8
94.6
1.4
0.1
2.1
8.4
4.5
2.5
10.2
4.8
1
lime
15
20
64.0
135.3
2.6
0.2
3.7
9.2
5.8
10
1
lime
20
25
78.3
87.8
10
1
lime
25
30
81.8
84.3
1.7
0.2
2.8
3.3
7.7
4.4
1.8
0.1
2.8
3.3
8.6
4.7
10
1
lime
10
2
lime
0.2
5.1
10
2
lime
10
2
lime
10
2
lime
20
10
2
lime
10
3
lime
10
3
lime
10
3
10
10
439.0
t
0
57.8
41.6
0.1
0.0
0.0
0
10
145.0
38.3
0.0
0.0
0.0
0.1
0.1
4.5
10
20
153.8
38.1
0.1
0.0
0.1
0.1
0.7
4.5
30
133.6
51.2
0.2
0.0
0.3
0.5
1.0
4.8
490.1
t
0
61.4
37.7
0.2
0.0
1.1
1.2
1.3
3.6
0
10
51.5
36.9
0.1
0.0
1.4
1.5
1.6
3.4
lime
10
20
23.0
36.6
0.1
0.0
1.2
1.4
3.1
3
lime
20
30
42.7
36.7
0.1
0.0
1.3
1.5
3.3
3
lime
11
1
pac
11
1
pac
11
1
pac
11
1
11
178.6
t
0
82.4
92.8
0.5
0.0
0.2
0.3
2.1
4.4
0
5
66.6
161.6
0.8
0.0
0.1
2.3
1.7
4.7
5
10
40.1
190.4
0.9
0.0
0.1
3.1
4.7
4.8
pac
10
15
54.8
190.5
0.8
0.0
0.1
3.0
1.3
4.7
1
pac
15
20
52.5
191.7
0.6
0.0
0.1
1.4
1.8
4.5
11
1
pac
20
25
59.3
181.2
0.2
0.0
0.0
0.9
4.4
11
1
pac
25
30
43.1
195.9
0.5
0.0
0.1
0.9
4.2
11
1
pac
11
2
pac
0
59.5
36.6
0.0
0.0
0.1
0.2
0.2
4.2
11
2
pac
0
10
93.0
38.5
0.0
0.0
0.1
0.2
0.2
3.1
11
2
pac
10
20
80.0
38.5
0.1
0.0
0.0
0.2
3.3
11
2
pac
20
30
52.0
37.2
0.0
0.0
0.0
0.2
2.9
11
2
pac
11
3
pac
11
3
pac
11
3
11
3
11
3
pac
12
2
lime
12
2
lime
12
2
lime
12
2
lime
20
12
3
lime
12
2
lime
12
3
lime
0
10
12
3
lime
10
20
398.7
t
284.5
t
0
76.5
37.1
0.0
0.0
0.1
0.2
0.2
4.3
0
10
98.5
37.3
0.0
0.0
0.1
0.2
0.2
4.3
pac
10
20
94.3
37.0
0.0
0.0
0.2
0.2
0.4
4.1
pac
20
30
62.4
34.4
0.0
0.0
0.2
0.2
0.5
4.2
331.7
t
0
50.4
39.0
0.0
0.0
0.0
0.2
3.0
0
10
24.1
36.4
0.1
0.0
0.0
0.1
4.3
10
20
22.0
36.1
0.0
0.0
0.0
0.0
4.2
30
16.9
33.4
0.0
0.0
0.0
0.3
3.7
55.5
34.9
0.0
0.0
0.0
0.2
3.4
13.4
30.1
0.0
0.0
0.1
3.1
16.1
32.5
0.0
0.0
0.1
3.2
t
0
0.2
113.4
245
12
3
lime
12
3
lime
13
1
slurry
13
1
slurry
13
1
13
1
13
20
30
9.3
33.5
0.0
0.0
0.1
3.1
38.7
t
0
35.0
147.8
1.1
0.1
2.4
0
5
34.0
162.0
1.1
0.0
slurry
5
10
43.0
141.0
1.3
slurry
10
15
39.0
133.3
0.9
1
slurry
15
20
43.0
138.1
13
1
slurry
20
25
14.8
13
1
slurry
13
2
slurry
13
2
slurry
13
2
13
2
13
2
slurry
13
3
slurry
13
3
slurry
13
3
slurry
13
3
slurry
20
13
3
slurry
14
2
alum
14
2
alum
14
2
14
14
2.6
6.3
4.0
2.8
7.0
4.1
0.0
2.7
6.8
4.5
0.0
2.4
6.1
4.4
0.8
0.1
2.0
6.4
4.2
137.5
0.8
0.0
2.1
4.3
208.8
t
0
251.7
32.1
0.0
0.0
0.0
0.1
3.7
0
10
101.4
37.1
0.0
0.0
0.3
0.6
0.7
4.0
slurry
10
20
40.2
37.2
0.0
0.0
slurry
20
30
42.2
36.9
0.0
0.0
0.3
0.5
0.6
3.5
0.3
0.5
0.7
3.7
435.5
t
0
70.4
31.5
0.1
0.0
0.7
0.8
1.0
3.9
0
10
42.8
33.3
0.0
0.0
0.6
0.8
0.9
4.0
10
20
70.3
33.5
0.0
0.0
0.6
0.7
0.9
4.1
30
44.2
34.9
0.0
0.0
0.5
0.6
0.6
4.1
227.7
t
0
114.7
37.1
0.0
0.0
0.4
0.5
0.7
3.6
0
10
60.2
44.7
0.4
0.0
0.1
0.6
0.9
4.6
alum
10
20
56.2
44.8
0.4
0.0
0.1
0.8
4.6
2
alum
20
30
42.2
44.9
0.2
0.0
0.1
0.2
0.8
4.6
2
alum
14
3
alum
43.4
29.7
0.0
0.0
0.1
0.1
0.2
2.1
14
3
alum
0
10
9.6
34.7
0.0
0.0
0.1
2.6
14
3
alum
10
20
12.6
34.5
0.0
0.0
0.1
2.3
14
3
alum
20
30
14.4
34.6
0.0
0.0
0.1
2.5
14
3
alum
15
2
alum
0
46.4
44.6
0.2
0.0
0.1
0.2
0.6
4.5
15
2
alum
0
10
18.0
37.0
0.0
0.0
0.1
0.2
0.3
4.2
15
2
alum
10
20
41.4
38.5
0.0
0.0
0.1
0.1
0.3
4.1
15
2
alum
20
30
29.3
47.8
0.2
0.0
0.3
3.2
4.4
15
2
alum
15
3
alum
0.3
4.1
15
3
alum
0.3
4.0
15
3
15
3
15
3
alum
16
1
slurry
0
16
1
slurry
5
10
16
1
slurry
15
16
1
slurry
20
273.3
t
0
80.0
t
135.1
t
0
52.1
34.6
0.0
0.0
0.1
0.1
0
10
21.6
34.7
0.0
0.0
0.1
alum
10
20
52.7
35.6
0.0
0.0
0.1
0.1
0.3
4.1
alum
20
30
45.4
36.3
0.0
0.0
0.0
0.1
0.2
4.1
87.4
55.2
0.9
0.0
0.4
5.4
30.0
70.9
0.3
0.0
1.3
4.7
20
12.3
68.4
0.6
0.0
1.4
5.0
25
18.6
68.4
0.3
0.0
1.6
4.8
171.7
t
246
16
1
slurry
10
15
18.6
68.7
0.2
0.0
1.6
16
1
slurry
16
1
slurry
0
5
30.0
62.7
0.6
0.0
0.8
25
30
19.1
66.3
0.1
0.1
1.5
4.4
16
1
slurry
0.0
0.0
16
2
slurry
0
44.0
43.5
0.0
0.0
0.1
16
2
slurry
0
10
2.5
38.1
0.0
0.0
0.1
4.5
16
2
slurry
10
20
2.6
38.1
0.0
0.0
0.1
4.4
16
2
slurry
20
30
1.9
42.3
0.0
0.0
0.0
4.5
16
2
slurry
16
3
slurry
16
3
slurry
16
3
16
3
16
3
slurry
17
1
alum
17
1
alum
17
1
alum
17
1
17
17
215.9
t
5.0
4.7
4.7
0.2
0.2
4.6
4.5
50.9
t
0
44.8
29.3
0.1
0.0
0.2
0.3
0.5
2.6
0
10
77.0
33.3
0.0
0.0
0.3
0.4
0.5
3.1
slurry
10
20
62.3
33.6
0.0
0.0
0.3
0.4
0.5
3.4
slurry
20
30
87.4
33.6
0.0
0.0
0.3
0.4
0.7
3.4
1.8
4.9
271.4
t
0
39.5
37.2
0.0
0.0
0.0
0
5
36.1
51.8
1.1
0.0
0.7
5
10
44.5
51.5
0.9
0.1
1.2
0.3
4.9
alum
10
15
51.0
52.9
0.6
0.0
0.1
0.4
5.0
1
alum
15
20
54.4
53.3
0.7
0.0
0.1
0.3
5.1
1
alum
20
25
52.9
52.5
0.5
0.0
0.0
0.3
4.9
17
1
alum
25
30
48.4
55.5
0.7
0.0
0.0
0.4
5.1
17
1
alum
17
2
alum
0
35.7
42.8
0.0
0.0
0.2
0.4
3.0
17
2
alum
0
10
13.7
39.6
0.0
0.0
0.2
3.1
17
2
alum
10
20
13.4
38.3
0.0
0.0
0.2
3.1
17
2
alum
20
30
16.5
39.2
0.0
0.0
0.2
3.0
17
2
alum
17
3
alum
17
3
alum
17
3
17
3
17
3
alum
18
1
soil
0
18
1
soil
0
5
18
1
soil
5
18
1
soil
18
1
18
1
18
0.3
5.1
326.7
t
79.3
t
0
41.3
39.3
0.3
0.0
0.1
0.2
4.2
0
10
15.4
37.7
0.2
0.0
0.1
alum
10
20
10.9
37.4
0.1
0.0
0.1
alum
20
30
42.8
30.6
0.0
0.0
0.1
0.3
0.4
1.7
105.5
59.9
1.3
0.1
0.1
0.3
1.0
5.3
19.9
49.0
1.4
0.1
0.5
4.9
10
16.2
42.4
0.5
0.0
0.0
4.5
10
15
24.2
42.2
0.5
0.1
0.1
soil
15
20
28.6
40.5
0.2
0.0
0.0
4.4
soil
20
25
34.5
40.2
0.3
0.0
0.0
4.4
1
soil
25
30
66.7
61.0
0.5
0.1
0.2
18
1
soil
25
30
31.2
40.2
0.2
0.0
0.0
4.5
18
1
soil
0
105.5
49.8
1.8
0.2
0.3
4.7
18
1
soil
15
20
24.2
40.5
0.4
0.1
0.2
4.7
18
1
soil
0
5
19.9
43.4
0.6
0.1
0.3
4.9
3.8
2.8
110.4
t
t
247
0.7
0.6
0.8
4.4
5.4
18
1
soil
20
25
28.6
40.4
0.1
0.1
0.1
4.7
18
1
soil
25
30
27.8
39.1
0.3
0.1
0.2
4.7
18
1
soil
10
15
16.2
40.2
0.3
0.1
0.2
4.8
18
1
soil
18
2
soil
0
49.2
37.4
0.0
0.0
0.0
18
2
soil
0
10
6.8
37.4
0.0
0.0
0.0
3.7
18
2
soil
10
20
9.3
36.9
0.0
0.0
0.0
3.6
18
2
soil
20
30
8.7
37.2
0.0
0.0
0.1
3.5
18
2
soil
18
3
soil
18
3
soil
18
3
18
3
18
3
soil
19
1
pac
19
1
19
1
19
295.6
t
0.1
0.1
3.8
73.9
t
0
38.5
43.3
0.0
0.0
0.0
0.2
3.9
0
10
8.0
40.4
0.0
0.0
0.0
3.3
soil
10
20
14.7
39.4
0.0
0.0
0.1
2.7
soil
20
30
14.9
38.3
0.0
0.0
0.1
2.6
76.2
0
5
34.7
54.0
0.4
0.0
0.1
0.1
1.2
5.2
pac
5
10
56.9
53.6
0.2
0.1
0.0
0.2
0.6
5.1
pac
10
15
50.9
56.0
0.3
0.1
0.1
0.2
0.4
5.2
1
pac
15
20
48.9
56.6
0.4
0.1
0.2
0.2
0.5
5.1
19
1
pac
20
25
65.6
59.6
0.4
0.1
0.1
0.2
0.4
5.1
19
1
pac
25
30
54.5
63.2
0.6
0.1
0.2
0.3
0.4
5.2
19
1
pac
19
2
pac
0.3
0.4
3.6
19
2
pac
19
2
pac
19
2
pac
20
19
2
pac
19
3
pac
19
3
pac
19
3
19
19
311.5
t
0
41.2
47.8
0.0
0.0
0.2
0
10
3.1
41.0
0.0
0.0
0.2
3.8
10
20
3.8
42.6
0.0
0.0
0.2
3.7
30
11.1
41.3
0.0
0.0
0.2
3.7
59.0
t
0
54.7
40.0
0.0
0.0
0.1
0.2
0.4
3.1
0
10
48.5
37.4
0.0
0.0
0.2
0.3
0.5
2.8
pac
10
20
56.7
37.8
0.0
0.0
0.2
0.3
0.5
2.8
3
pac
20
30
39.6
37.8
0.0
0.0
0.2
0.7
2.9
3
pac
20
1
lime
9.6
2.1
20
1
lime
3.4
20
1
lime
20
1
20
199.5
t
0
59.3
129.6
3.4
0.2
5.1
0
5
49.5
150.7
3.9
0.2
6.0
10.8
5
10
80.3
0.1
15.4
lime
10
15
96.7
6.2
14.2
1
lime
15
20
110.7
2.4
12.6
20
1
lime
20
25
276.5
172.7
4.2
0.1
5.3
3.5
20
1
lime
25
30
123.0
179.4
4.1
0.1
4.7
6.4
20
1
lime
20
2
lime
0
108.5
45.4
0.0
0.0
2.8
20
2
lime
0
10
21.5
45.3
0.0
0.0
2.8
20
2
lime
10
20
19.1
45.4
0.0
0.0
2.8
4.1
20
2
lime
20
30
17.0
43.4
0.0
0.0
3.0
4.1
178.2
4.4
0.1
7.2
2.3
796.0
t
248
3.0
3.4
4.1
3.3
4.2
20
2
lime
166.0
20
3
lime
0
38.0
36.7
0.0
0.0
1.0
20
3
lime
0
10
11.9
33.7
0.0
0.0
1.6
2.9
20
3
lime
20
30
14.3
34.2
0.0
0.0
1.5
2.9
20
3
lime
21
1
alum
21
1
alum
21
1
21
21
t
1.5
3.3
64.3
t
0
47.4
48.1
0.7
0.0
0.0
0
5
52.9
58.6
0.6
0.0
alum
5
10
36.9
112.1
6.6
1
alum
10
15
42.4
133.5
1
alum
15
20
45.0
141.2
21
1
alum
20
25
35.5
21
1
alum
25
30
42.9
21
1
alum
21
2
alum
21
2
alum
21
2
21
2
21
2
alum
21
3
alum
0
21
3
alum
0
10
21
3
alum
10
21
3
alum
20
21
3
alum
22
1
soil
22
1
soil
22
1
22
1
22
1
soil
22
2
soil
22
2
soil
22
2
soil
22
2
soil
20
22
2
soil
22
3
soil
22
3
soil
22
3
22
22
0.2
0.7
5.2
0.0
0.6
5.1
0.1
0.1
1.7
6.6
11.0
0.1
0.2
3.1
7.1
12.7
0.2
0.2
3.2
7.1
138.6
12.7
0.2
0.2
2.7
6.9
127.9
14.0
0.2
0.2
2.9
7.0
0.1
4.4
302.9
t
0
44.1
43.6
0.0
0.0
0.0
0.1
0
10
7.7
43.2
0.0
0.0
0.0
4.3
alum
10
20
8.3
42.6
0.0
0.0
0.1
4.3
alum
20
30
1.0
42.0
0.0
0.0
0.1
4.4
45.7
36.6
0.0
0.0
0.1
0.3
3.8
24.3
35.8
0.0
0.0
0.1
0.1
3.6
20
29.5
36.0
0.0
0.0
0.1
0.1
3.6
30
34.4
35.8
0.0
0.0
0.0
0.1
3.8
0.2
4.5
61.2
t
0.1
133.8
t
0
46.3
48.7
1.5
0.0
0.2
0
10
3.7
40.5
0.4
0.0
0.0
4.0
soil
10
20
14.1
39.9
0.4
0.0
0.0
4.2
soil
20
30
14.5
39.1
0.3
0.0
0.0
4.1
78.6
t
0
51.1
44.7
0.0
0.0
1.0
0
10
25.3
46.6
0.2
0.0
10
20
34.0
50.9
0.0
0.0
30
66.3
51.0
0.3
2.8
3.4
4.2
0.1
0.4
3.9
0.1
0.7
3.4
0.0
0.2
0.6
3.4
176.7
t
0
221.5
38.1
0.0
0.0
0.1
0.1
0.1
3.1
0
10
211.1
37.6
0.0
0.0
0.1
0.1
0.1
3.4
soil
10
20
208.0
37.6
0.0
0.0
0.1
0.1
0.2
3.1
3
soil
20
30
230.0
37.7
0.0
0.0
0.1
0.1
0.1
3.1
3
soil
23
1
slurry
23
1
slurry
23
1
slurry
23
1
23
1
870.5
t
0
57.7
62.4
0.5
0.0
0.3
0.6
1.4
4.4
0
5
31.2
88.4
0.5
0.0
0.7
0.9
2.8
4.7
5
10
25.5
86.5
1.0
0.0
1.1
1.6
4.7
slurry
10
15
37.3
92.1
0.7
0.1
1.6
2.8
4.7
slurry
15
20
41.4
108.2
1.6
0.1
2.2
3.7
4.8
249
23
1
slurry
20
25
59.8
105.9
1.7
0.0
2.0
4.8
4.7
23
1
slurry
25
30
39.9
92.3
1.5
0.1
2.0
4.1
4.9
23
1
slurry
23
2
slurry
23
2
slurry
23
2
23
23
292.8
t
0
100.2
55.2
1.4
0.1
8.3
9.8
10.5
4.4
0
10
73.3
56.7
1.2
0.1
8.0
9.4
10.4
4.4
slurry
10
20
68.9
59.3
0.8
0.1
7.4
8.9
9.9
4.3
2
slurry
20
30
52.6
52.8
0.4
0.1
4.6
5.3
5.9
3.7
2
slurry
23
3
slurry
103.7
35.1
0.0
0.0
1.0
1.1
1.2
2.2
23
3
slurry
0
10
72.0
36.6
0.0
0.0
1.2
1.4
1.5
2.5
23
3
slurry
10
20
139.8
36.4
0.0
0.0
0.9
1.0
1.2
2.9
23
3
slurry
20
30
146.3
36.5
0.0
0.0
0.5
0.6
3.5
23
3
slurry
24
1
lime
0
50.1
50.7
0.2
0.0
0.0
0.5
4.7
24
1
lime
0
10
15.5
116.8
0.4
0.0
0.3
0.6
3.2
24
1
lime
10
20
19.4
133.4
0.5
0.0
1.2
2.2
3.7
24
1
lime
20
30
43.5
146.3
1.3
0.0
3.3
24
1
lime
24
3
lime
24
3
lime
24
3
24
3
24
3
lime
25
1
pac
0
25
1
pac
0
5
25
1
pac
5
25
1
pac
25
1
25
1
25
295.1
t
0
461.7
t
6.3
4.3
128.4
t
0
64.3
37.5
0.0
0.0
0.3
0.6
0.6
3.5
0
10
145.4
35.5
0.0
0.0
1.2
2.5
2.6
2.7
lime
10
20
220.0
35.8
0.0
0.0
1.4
2.4
2.8
2.6
lime
20
30
117.0
35.8
0.0
0.0
1.4
1.6
1.7
2.6
64.3
87.2
0.2
0.0
0.0
0.4
4.1
44.9
127.2
0.4
0.0
0.0
0.5
3.8
10
56.5
122.0
0.4
0.0
0.0
0.5
3.8
10
15
49.5
117.2
0.2
0.0
0.0
0.4
4.0
pac
15
20
57.1
118.7
0.2
0.0
0.0
0.2
0.5
4.1
pac
20
25
64.9
99.8
0.2
0.0
0.0
0.2
0.6
4.3
1
pac
25
30
68.5
97.1
0.4
0.0
0.0
0.2
0.8
4.4
25
1
pac
25
2
pac
25
2
pac
25
2
25
25
546.7
t
405.7
t
0
83.2
50.1
0.0
0.0
0.2
0.7
3.4
0
10
221.4
80.6
0.3
0.1
0.1
0.7
3.5
pac
10
20
286.7
55.8
0.1
0.0
0.1
1.3
3.6
2
pac
20
30
295.7
48.6
0.1
0.0
0.0
1.4
2.2
3.9
2
pac
25
3
pac
0.3
2.2
4.0
25
3
pac
25
3
pac
25
3
pac
20
25
3
pac
887.0
t
0
46.0
39.1
0.0
0.0
0.0
0
10
41.0
38.9
0.0
0.0
0.1
0.3
3.5
10
20
32.5
39.3
0.0
0.0
0.1
0.3
3.2
30
41.5
37.6
0.0
0.0
0.1
0.4
3.0
161
250
Table F.2 Plot physical characteristics
Plot
ttorun1
pH e 1
ttorun2
ttorun3
intensity1
intensity2
intensity3
slope%
1
60
7.73
50
20
14.25
9.5
8.5
5.125
2
19
6.96
70
50
13.5
9.5
8.5
3.625
3
30
8
40
25
14
10
7.8
7.25
4
35
8
114
30
14.5
10
10.5
3.75
5
40
8.2
120
40
10.5
7
9.5
3.875
6
62
7.83
57
60
14.6
10
9.25
2.375
7
60
6.97
105
40
13.01
9.5
8.9
4.125
8
72
8.8
90
35
10.98
10
10.6
4.375
9
48
8.8
62
20
13.01
9
9.25
4.5
10
35
7
111
35
10.12
8
7.98
0.375
11
74
7.4
120
50
15.01
10
8.72
0.5
12
140
7.7
75
50
12.98
9
9.5
4.875
13
130
7.8
71
30
10.5
9.5
10
1.75
14
145
7.9
115
25
13.5
9.5
9.5
3.5
15
135
7.7
54
36
12.45
11.54
9.4
0.625
16
78
7.65
121
54
11.5
9.04
8.7
0.625
17
40
8
74
34
9.5
13.12
12
3.875
18
43
7.6
90
25
9.21
8.34
10
2.875
19
45
7.5
80
50
14.25
8.35
8.76
5
20
72
7.8
75
35
10.88
8.9
10.25
4
21
47
7.66
105
42
13.23
11
10.75
3.125
22
50
7.8
95
31
8.12
11
11.22
3.75
23
120
7.8
45
25
10.5
9.75
9.23
6
24
43
7.9
32
34
10.12
8.56
8.32
4.375
25
35
7.9
25
27
12.3
8.97
9.51
4.5
251
Table F 3 Rainfall simulator allocation, blocking and treatments
Application
sequence
plot
block
Sequence
of rainfall
simulations
treat
Allocation of simulators during events
1,2,3
sime1
sime2
sime3
treatment
3
1
1
5
6
2
1
2
lime
3
2
1
1
6
1
2
1
soil
3
3
1
3
7
2
1
2
alum
3
4
1
2
7
1
2
1
slurry
3
5
1
4
8
2
1
2
pac
2
6
2
2
3
2
1
2
slurry
2
7
2
3
4
1
2
1
alum
2
8
2
1
4
2
1
2
soil
2
9
2
4
5
2
1
1
pac
2
10
2
5
5
1
2
2
lime
5
11
3
4
11
1
2
2
pac
5
12
3
5
11
2
1
1
lime
5
13
3
2
12
1
2
2
slurry
5
14
3
3
12
2
1
1
alum
5
15
3
1
13
1
2
1
soil
1
16
4
2
1
2
1
1
slurry
1
17
4
3
1
1
2
2
alum
1
18
4
1
2
1
2
2
soil
1
19
4
4
2
2
1
1
pac
1
20
4
5
3
1
2
1
lime
4
21
5
3
8
1
2
1
alum
4
22
5
1
9
1
2
2
soil
4
23
5
5
9
2
1
1
lime
4
24
5
2
10
1
2
1
slurry
4
25
5
4
10
2
1
2
pac
252
Table F 4 Soil analysis results for the 25 plots potassium (K), lime requirement (LR), Mg
(magnesium) and pH at times t=0 days (before slurry application) and t=30 days after the last
rainfall simulation event.
plot
K0
LR0
Mg0
P0
pH0
K30
LR30
Mg30
P30
pH30
1
59.35
4
130.2
3.72
6.14
49.75
3
150.06
2.26
6.08
2
49.86
3.5
143.44
2.48
6.34
124.65
4
141.24
3.39
5.89
3
45.12
3.5
122.48
2.37
6.24
95.97
5
129.1
4.18
5.73
4
46.22
5.5
108.13
3.39
5.81
79.86
3.5
126.89
3.72
6.15
5
47.66
4.5
113.65
4.29
5.93
102.26
4
129.1
4.4
5.89
6
64.53
5.5
124.68
3.61
5.96
80.2
6.5
116.96
4.29
5.58
7
44.46
5
191.99
2.48
5.81
56.59
6
135.72
4.06
5.63
8
62.11
6
126.89
5.76
5.64
74.57
5
148.96
6.89
5.9
9
51.52
6
143.44
5.76
5.97
81.74
4.5
167.72
8.69
6.09
10
53.61
5.5
161.1
7.11
5.93
92.77
4.5
159.99
8.13
5.98
11
57.14
6.5
168.82
5.98
5.75
111.85
0.5
208.54
9.6
6.73
12
66.74
3
174.34
7.68
6.46
99.72
3.5
168.82
5.19
6.13
13
56.26
5
165.51
6.1
6
134.13
4
220.68
6.89
6.09
14
56.15
5.5
190.89
7.11
6
67.62
3.5
221.79
8.24
6.01
15
62.44
5
221.79
7.68
6.08
92.44
4.5
217.37
8.13
6.06
16
63.54
8
227.3
6.21
5.68
99.17
3
239.44
8.35
6.29
17
62.11
6
226.2
4.97
5.97
57.58
4.5
248.27
6.21
6.03
18
57.14
5
237.23
5.98
6.14
81.96
4
211.86
6.32
6.07
19
47.32
4.5
212.96
5.87
6.03
99.5
3.5
244.96
6.57
6.2
20
61.66
3.5
247.17
7.34
6.27
84.61
3.5
290.2
5.76
6.15
21
56.48
6.5
239.44
4.63
5.73
56.48
6
226.2
4.97
5.9
22
51.19
7
222.89
2.6
5.57
23
53.28
6
239.44
3.39
5.74
96.85
4
226.2
7.23
6.17
24
25
54.16
89.13
5
4
226.2
161.1
3.61
3.72
5.79
6.01
73.14
72.92
4.5
4
227.3
212.96
5.53
4.29
5.91
6
253
Table F 5 Slurry characterisation for plot study
Plot no.
WEP
-1
mg kg
1
3.572
2
0.000
3
Dry matter
%
pH
TN
-1
mg L
TP
-1
mg L
TK
-1
mg L
TAN
-1
mg L
9.2
9.9
4359
1319
5421
1311
0.002
10.3
6.6
3881
1306
5560
1319
4
3.509
9.4
7.2
2781
1188
4875
1368
5
0.022
10.1
6.8
2155
799
3317
1284
6
3.004
9.4
7.2
4671
1280
5640
1320
7
0.005
9.8
6.3
4979
1502
6052
1343
8
0.000
9
0.003
9.5
6.8
4810
1350
5823
1307
10
1.802
9.6
6.8
5000
1478
6304
1419
11
0.004
9.7
7.7
5360
1400
5480
1320
12
3.003
9.1
7.1
5142
1417
6032
1238
13
3.169
9.2
6.7
4488
1237
4700
1225
14
0.002
9.8
6.2
4019
1061
4502
1307
16
3.567
9.5
6.2
4032
1048
4222
1364
17
0.002
9.2
7.3
4035
1066
4669
1136
18
0.000
19
0.006
9.4
6.5
3245
897
4169
1315
20
1.125
10.0
9.8
4399
1168
4227
1404
21
0.003
8.8
6.4
5118
1378
5276
690
22
0.000
23
2.909
9.3
10.3
6147
1558
6061
690
24
2.683
8.2
7.9
3830
1447
6426
743
25
0.002
8.4
6.8
4324
1051
2883
661
15
254
Table F 6 Climate data from a weather station located in Johnstown close to study site.
Total
Natural
Mean
Solar
date_captured
rainfall
rainfall
windspeed
radiance humidity
01-Jul-10
12.5
12.5
9.6
1322
88.9
02-Jul-10
0
0
9.5
2660.2
83.5
03-Jul-10
0
0
7.4
2535
79.5
04-Jul-10
1.6
1.6
10.4
1892.7
79
05-Jul-10
0.4
0.4
5.1
2040.3
71.5
06-Jul-10
1
1
8.5
1133.3
84.5
07-Jul-10
2.9
2.9
10.6
2291.5
84.9
08-Jul-10
7.6
7.6
6.4
1273.8
86.1
09-Jul-10
7.5
7.5
9.5
937.8
96.1
10-Jul-10
6.7
6.7
10.2
445.7
97.9
11-Jul-10
0
0
5.6
1941
80.2
12-Jul-10
0
0
4.7
2177.6
80.2
13-Jul-10
10.8
10.8
5.6
327.1
95.1
14-Jul-10
2.7
2.7
7.6
1855
90.5
15-Jul-10
31.4
31.4
9.2
1419.3
91.8
16-Jul-10
6.9
6.9
7.1
1550.9
86.6
17-Jul-10
2.9
2.9
8.4
1969.7
81.7
18-Jul-10
18.7
18.7
12
625.8
98.2
19-Jul-10
19.5
19.5
8.1
695.1
97.8
20-Jul-10
0
0
5.5
1788.8
86.7
21-Jul-10
0.8
0.8
3.7
1750.7
86.7
22-Jul-10
7.7
7.7
5.3
1171.7
88.6
23-Jul-10
0
0
5
1924.2
81.9
24-Jul-10
1.9
1.9
6.6
678.5
98.1
25-Jul-10
0
0
4.3
1248.7
83.7
26-Jul-10
0
0
5.9
2288
84
27-Jul-10
0
0
4.8
1567.8
78.1
28-Jul-10
0
0
4.4
1158
78
29-Jul-10
0
0
4.9
1293.8
81.2
30-Jul-10
0.5
0.5
7.1
792.5
92.6
31-Jul-10
0.9
0.9
6.2
1549.2
83.9
01-Aug-10
0
0
3.8
998.1
83.5
02-Aug-10
0
0
4.3
1009.5
84.1
03-Aug-10
0.8
0.8
4.6
1669.1
80.6
04-Aug-10
0.1
0.1
6.6
1919.7
75.5
05-Aug-10
0.3
0.3
5.3
1190.9
80.2
06-Aug-10
2.3
2.3
7.4
885.2
94.9
07-Aug-10
0
0
5.1
1337.2
80.6
08-Aug-10
0
0
5.9
2099.7
73.9
09-Aug-10
0.9
0.9
7.2
2113.5
83.3
10-Aug-10
0
0
5
2144.1
68.2
11-Aug-10
0
0
4.5
1490
74.3
12-Aug-10
0
0
5.5
1051.8
72.6
13-Aug-10
0
0
7.6
2150.4
67
14-Aug-10
0
0
6.7
1910.2
75.1
15-Aug-10
0
0
5.1
1955
81.3
16-Aug-10
1.8
1.8
6.2
1071
80.2
17-Aug-10
0.2
0.2
5.7
1647
74.3
255
Atmospheric
pressure
999.9
1002.9
1012
1009.7
1017.7
1016.3
1009.1
1010.1
1007.3
1005.4
1008.2
1006.9
999
988.4
989.7
999
1012.1
1012.8
1009.4
1002.6
998.2
1007.1
1015.6
1014.2
1013.4
1013.2
1012.2
1013.3
1012.8
1006.7
1006.1
1008.7
1013.4
1009.4
1004.8
1007.9
1003.7
1010.5
1014.7
1005.9
1003.8
1009.6
1014.9
1017.1
1015.9
1018.3
1013.2
1005.8
18-Aug-10
19-Aug-10
20-Aug-10
21-Aug-10
22-Aug-10
23-Aug-10
24-Aug-10
25-Aug-10
26-Aug-10
27-Aug-10
28-Aug-10
29-Aug-10
30-Aug-10
31-Aug-10
01-Sep-10
02-Sep-10
03-Sep-10 plots
isolated
04-Sep-10
05-Sep-10
06-Sep-10
07-Sep-10
08-Sep-10
09-Sep-10
10-Sep-10
11-Sep-10
12-Sep-10
13-Sep-10
14-Sep-10
15-Sep-10
16-Sep-10
17-Sep-10 RS 1
18-Sep-10
19-Sep-10
20-Sep-10
21-Sep-10
22-Sep-10
23-Sep-10
24-Sep-10
25-Sep-10
26-Sep-10 RS 2
27-Sep-10
28-Sep-10
29-Sep-10
30-Sep-10
01-Oct-10
02-Oct-10
03-Oct-10
04-Oct-10
05-Oct-10
0.1
11
2.5
0.1
1.7
2.8
0
5.1
0
0
0
0
0
0
0.1
0.3
0.1
11
2.5
0.1
1.7
2.8
0
5.1
0
0
0
0
0
0
0.1
0.3
6.4
7.1
10.8
6.3
5.6
5.8
7.6
6.7
7
5.2
5.4
6.2
4
3.8
4.4
4.6
1717.4
546
1459.5
1657.3
1988.1
1855.6
1775
920
867.7
1552.6
1642.1
1306.9
1886.5
1625.8
1643.8
1667.4
80.2
94.9
94
88.1
87.4
78.4
72.7
86.9
83
70.1
71.8
68.4
73.6
81.5
85.6
82.4
1001.6
999.6
1001.8
1009.2
1005.6
995.9
1003.1
1004.4
1001.7
1009.4
1017
1015.8
1020.9
1018.3
1014.4
1013.9
0
1.8
11.5
60.5
1.3
6.5
5.5
10.4
4.3
0.7
0.3
1.8
0
0
19.42
0
0
0
0.1
3
0.7
0.1
0
17.5
0
8.2
0.1
2
7.7
8
5.2
3.6
4.6
0
1.8
11.5
60.5
1.3
6.5
5.5
10.4
4.3
0.7
0.3
1.8
0
0
0
0
0
0
0.1
3
0.7
0.1
0
0
0
8.2
0.1
2
7.7
8
5.2
3.6
4.6
4.6
6
8.6
8.1
5
4.4
7.2
10
5.8
4.8
11.8
9
7.2
3.8
5
7.2
10.3
6.9
7.4
8.9
5.8
6.7
5.7
3.1
2.5
5.4
4.4
6.5
7.9
7.3
3.8
8.2
8.7
1467.5
214.1
383.8
154.7
1365.9
1161.9
1498.7
481.2
1438.7
1168.8
609.7
1072.8
1347.8
702.2
1238.6
874.8
394.7
1108
929.7
412.1
980.6
706.9
1195.6
929.4
1224.4
425.7
1149.9
841.2
1112
581.8
1040.1
829.6
994.5
89.2
98.9
99.7
99.8
91.8
92.7
91.4
99.6
83.3
84.9
98.3
84
77.3
80.3
73.7
84.9
96
96.5
96.2
99.9
89.9
77.3
71.2
71
80.6
97.5
88.9
95
83.1
87
90.8
91.5
81.5
1013.2
1010.8
1005.5
993.2
990.8
996.3
1008.2
1005.1
1007
1019.1
1015.3
1009.3
1007.9
1009.6
1014.3
1012.9
1004.9
1005.9
1009.3
1004.3
999.3
1008.2
1015.2
1012.5
1009.3
1006.8
1007.1
1002.7
989.5
991.2
987.2
989.3
988.7
256
06-Oct-10
07-Oct-10
08-Oct-10
09-Oct-10
10-Oct-10
11-Oct-10
12-Oct-10
1.1
1
0
0
0
0.3
0.4
1.1
1
0
0
0
0.3
0.4
7.3
9.5
8.7
8.9
7.5
7
6.1
1070.3
1008.1
732.5
501.5
337.2
934.9
831.9
89.1
88.9
95.5
96.1
93.9
87.1
94.2
995.9
1005.2
1003.6
1006.1
1007.5
1013.7
1015.8
13-Oct-10
14-Oct-10 RS 3
15-Oct-10
16-Oct-10
17-Oct-10
18-Oct-10
19-Oct-10
21-Oct-10
22-Oct-10
24-Oct-10
25-Oct-10
26-Oct-10
28-Oct-10
29-Oct-10
30-Oct-10
31-Oct-10
01-Nov-10
02-Nov-10
03-Nov-10
04-Nov-10
05-Nov-10
06-Nov-10
07-Nov-10
08-Nov-10
09-Nov-10
10-Nov-10
11-Nov-10
12-Nov-10
13-Nov-10
14-Nov-10
15-Nov-10
16-Nov-10
17-Nov-10
18-Nov-10
19-Nov-10
20-Nov-10
21-Nov-10
22-Nov-10
23-Nov-10
24-Nov-10
25-Nov-10
26-Nov-10
27-Nov-10
0.3
10.45
0
0
0
0
0.5
0
7.3
0
1.1
10.8
3.5
8.8
3
17.8
3.7
2.9
4.4
0.1
2.2
1.7
16.3
5.2
3.3
1.2
9.7
0.2
2.9
0.1
2.4
12.9
20.2
0.6
6.8
0.2
3
1.7
0.5
0.4
0.4
0
9.5
0.3
0
0
0
0
0
0.5
0
7.3
0
1.1
10.8
3.5
8.8
3
17.8
3.7
2.9
4.4
0.1
2.2
1.7
16.3
5.2
3.3
1.2
9.7
0.2
2.9
0.1
2.4
12.9
20.2
0.6
6.8
0.2
3
1.7
0.5
0.4
0.4
0
9.5
4.3
5.5
6.4
5.9
4.4
5.7
5.5
4.7
7.8
6
7.7
13
11
11.7
5
7.7
7.2
11.8
7.6
14.5
3.5
5
10.2
6
10.3
6.8
14
8
5
2.9
2.7
9.4
10.4
6.9
3.8
7.3
6.7
6.5
5.9
6.1
8.5
8.1
7.9
486.2
268.8
743
727.5
840.4
491.8
620.5
813.5
362.9
861
710.3
213.9
199.8
163.3
484.1
220.6
143.5
134.5
202.7
113.6
177.5
530.6
468.5
418.8
250.1
610.5
513.1
270.3
340.3
550.1
431.5
282.1
425.8
444.5
235.4
83.9
190.7
221.9
418.8
340.1
440.7
386.3
111.3
92.6
79.7
78
81.9
81.6
85.7
85.1
76.6
90.1
76.7
75.8
98.2
95.2
94.7
91.9
93.6
95.7
91.3
95
97.6
91.6
89.9
85.6
90.6
82.8
77.2
81
84.1
89.9
88.2
93
86.7
87.5
87.7
94.9
89.6
90.4
91.8
89.2
90.4
83.6
84.9
90.4
1016.6
1017.2
1016.4
1018.2
1019.6
1014.8
1010.7
1016.3
1006.8
1013.6
1019.6
1008.2
1000.7
983.4
985.5
995.1
1005.2
999.4
1003.3
1007.4
1012.7
1011.2
998.6
960.3
977.4
993.9
977.4
985.5
984.5
990.2
1006
1006.2
988.2
992.5
1001.6
1006.8
1009.1
1007.3
1009.6
1007.6
1008.9
1003.5
1001.4
257
28-Nov-10
29-Nov-10
09-Dec-10
10-Dec-10
11-Dec-10
12-Dec-10
13-Dec-10
14-Dec-10
15-Dec-10
16-Dec-10
17-Dec-10
18-Dec-10
19-Dec-10
20-Dec-10
21-Dec-10
22-Dec-10
23-Dec-10
24-Dec-10
25-Dec-10
26-Dec-10
27-Dec-10
28-Dec-10
29-Dec-10
30-Dec-10
31-Dec-10
2.7
4.4
0
0
0
0
0.1
0
0
1
0
0
0
0
3
0.6
2
0.1
0
3.6
38.1
0.8
1.8
0.6
0
2.7
4.4
0
0
0
0
0.1
0
0
1
0
0
0
0
3
0.6
2
0.1
0
3.6
38.1
0.8
1.8
0.6
0
6
6.1
4.6
3.4
3.8
5.8
4.1
6.1
5.8
7.6
6.3
4.3
6.4
6.2
7.6
7.1
7.5
8.4
4.2
10.7
11.4
7.1
4.2
4.1
3.3
258
138.2
315.1
367
270.6
150.5
322
73.1
321.6
129.5
149.4
358.1
331.8
214.4
261.8
306.4
270
187.2
352.6
274.8
78.7
27
134.3
111.7
104.4
62.6
94.9
79.1
86.4
92.4
94.7
86
81.2
81.3
86.2
85.2
87.7
86.1
74.6
81.3
90.8
87.6
90.4
82.4
84.3
76.2
98.7
98.8
100
99.9
87.5
1000.5
1006.2
1027.6
1028.3
1022.5
1018.6
1022
1030.4
1033.3
1010.7
995.8
986.3
988.8
994
997.3
1003.5
1011
1017.9
1022.4
1014.5
999.4
1001.7
1009.8
1016.7
1020.5
Appendix G Incubation study results
259
Notation used in appendix G
Soils
A
B
C
D
E
Treatment
1. Soil only
2. Slurry only
3. Alum
4. Lime
5. PAC
6. FeCl
Cork
Wexford
Wexford
Galway
Sligo
Sandy loam
Clay loam
Clay loam
Silty loam
Peat
Table G. 1 Incubation study analysis results:
Soil type
Treatment
Perecent moisture
lost
Month
Sample
1
1
A
1
5.36
2.21
5.8
1
2
A
1
1.56
5.39
2.16
5.9
1
3
A
1
1.54
5.37
2.62
6.1
1
4
A
2
5.51
2.57
12.6
1
5
A
2
1.70
5.48
5.52
10.9
1
6
A
2
2.07
5.42
3.97
12.3
1
7
A
3
2.17
5.06
2.53
5.8
1
8
A
3
3.08
5.08
2.28
6.8
1
9
A
3
1.94
5.09
2.52
5.7
1
10
A
4
5.38
2.71
6.7
1
11
A
4
1.23
5.43
0.89
6.5
1
12
A
4
1.31
6.63
1.27
11.4
1
13
A
5
0.77
5.49
6.27
8.3
1
14
A
5
0.70
5.47
4.76
7.7
1
15
A
5
0.71
5.47
2.28
7.2
1
16
A
6
0.54
6.83
7.83
14.1
1
17
A
6
0.62
5.38
1.77
6.3
1
18
A
6
0.70
6.57
5.50
12.4
3
91
A
1
1.86
3.87
2.6
3
92
A
1
5.05
4.06
2.45
3
93
A
1
1.57
5.48
5.85
2.71
3
94
A
2
1.04
5.62
22.94
5.38
3
95
A
2
1.04
6.02
16.17
5.41
3
96
A
2
2.59
6.92
20.61
6.38
260
pH
WEP
Phos
3
97
A
3
0.99
3
98
A
3
7.18
5.71
5.44
3.41
3
99
A
3
6.46
5.58
4.55
4.68
3
100
A
4
2.06
6.66
5.79
5.55
3
101
A
4
1.54
7.11
8.13
3.76
3
102
A
4
0.85
5.51
8.60
7.81
3
103
A
5
2.30
6.03
9.70
2.95
3
104
A
5
1.46
5.32
9.25
5.61
3
105
A
5
1.09
5.7
7.61
8.96
3
106
A
6
2.60
5.69
2.24
8.73
3
107
A
6
0.54
7.49
3.81
13.12
3
108
A
6
1.17
5.54
0.67
8.5
6
181
A
1
5.33
5.22
3.81
6.55
6
182
A
1
4.41
5.21
3.17
6.09
6
183
A
1
13.28
5.17
3.30
5.97
6
184
A
2
4.14
5.1
8.63
12.17
6
185
A
2
0.39
5.14
8.61
12.64
6
186
A
2
0.24
5.1
8.09
11.7
6
187
A
3
2.41
4.71
3.89
6.32
6
188
A
3
3.91
4.67
4.33
7.14
6
189
A
3
4.91
4.71
3.92
6.79
6
190
A
4
4.65
4.95
3.84
7.02
6
191
A
4
3.05
4.97
4.38
6.67
6
192
A
4
4.89
4.96
3.98
6.67
6
193
A
5
0.82
4.97
5.86
8.43
6
194
A
5
2.33
4.99
7.01
8.43
6
195
A
5
1.56
4.99
5.87
8.9
6
196
A
6
3.08
6.4
10.19
25.87
6
197
A
6
8.46
6.92
10.89
22.3
6
198
A
6
5.67
4.84
3.37
16.32
9
271
A
1
5.59
5.4
2.59
6.09
9
272
A
1
5.63
5.28
2.61
6.32
9
273
A
1
3.49
5.32
4.58
6.32
9
274
A
2
3.07
5.25
4.92
12.31
9
275
A
2
3.28
5.2
6.35
12.07
9
276
A
2
6.40
5.15
6.88
12.31
9
277
A
3
3.34
4.82
3.25
8.36
9
278
A
3
4.58
4.7
3.54
8.36
9
279
A
3
2.26
4.72
3.21
8.12
9
280
A
4
5.61
4.94
3.49
7.28
9
281
A
4
-0.24
4.94
4.25
7.64
9
282
A
4
1.23
5.01
4.27
6.8
9
283
A
5
3.50
4.98
4.81
8.72
261
4.47
9
284
A
5
9.49
5.01
5.56
9
285
A
5
4.71
5.01
5.23
8.84
9
286
A
6
2.72
7.05
9.89
24.16
9
287
A
6
8.88
6.77
10.41
29.06
9
288
A
6
3.50
6.9
10.55
27.27
1
19
B
1
2.02
5.05
5.03
6.4
1
20
B
1
2.45
5.03
3.86
6.2
1
21
B
1
1.56
5.04
5.18
6.2
1
22
B
2
1.99
5.18
7.43
9
1
23
B
2
1.93
5.22
7.72
10.3
1
24
B
2
1.71
5.17
12.18
12
1
25
B
3
2.35
5.05
2.62
6.7
1
26
B
3
2.33
5.04
0.25
7.1
1
27
B
3
2.36
5.02
0.12
6.7
1
28
B
4
0.78
5.41
0.63
7
1
29
B
4
0.79
5.43
0.13
7.1
1
30
B
4
0.78
5.44
0.75
7.2
1
31
B
5
0.40
5.59
4.41
7.7
1
32
B
5
0.32
5.64
2.85
7.7
1
33
B
5
5.68
1.25
7.5
1
34
B
6
1.09
6.34
6.23
14.4
1
35
B
6
0.93
6.34
4.77
11.8
1
36
B
6
0.87
6.06
2.50
10.1
3
109
B
1
2.32
6.36
4.29
7.11
3
110
B
1
0.76
6.29
6.07
7.34
3
111
B
1
4.82
5.19
7.04
6.65
3
112
B
2
1.69
5.13
16.48
12.31
3
113
B
2
0.20
6.79
12.97
17.63
3
114
B
2
1.68
3
115
B
3
1.16
3
116
B
3
2.66
5.47
10.59
8.73
3
117
B
3
2.63
6.41
6.55
7.12
3
118
B
4
2.38
6.86
11.16
8.88
3
119
B
4
0.63
5.39
12.37
7.11
3
120
B
4
0.94
5.18
7.28
8.76
3
121
B
5
2.28
5.74
10.40
7.34
3
122
B
5
5.10
5.54
10.84
8.5
3
123
B
5
5.63
5.09
8.45
8.04
3
124
B
6
1.97
5.32
12.52
5.96
3
125
B
6
2.58
5.71
16.79
12.3
3
126
B
6
0.63
5.55
16.43
8.5
6
199
B
1
4.45
5.4
3.43
4.9
6
200
B
1
6.08
5.3
9.19
4.73
262
10.15
11.79
8.17
6
201
B
1
6
202
B
2
6.20
4.72
8.73
11.12
6
203
B
2
3.17
4.84
8.60
11.12
6
204
B
2
3.65
6
205
B
3
6.02
4.51
5.01
7.84
6
206
B
3
5.43
4.54
4.40
7.96
6
207
B
3
4.21
4.57
5.06
7.14
6
208
B
4
6.30
4.8
5.11
7.84
6
209
B
4
2.14
4.81
4.72
7.96
6
210
B
4
5.85
4.78
6
211
B
5
7.03
4.83
10.91
8.54
6
212
B
5
6.43
4.83
11.16
8.08
6
213
B
5
6
214
B
6
2.52
6.25
20.48
6
215
B
6
7.83
6.24
26.92
6
216
B
6
9
289
B
1
9
290
B
9
291
B
9
292
9
7.72
6.25
1.31
22.11
3.57
5.03
2.77
6.09
1
2.95
4.96
2.96
5.97
1
1.39
4.91
3.34
5.97
B
2
3.09
4.82
9.36
12.31
293
B
2
3.04
4.8
7.47
11.71
9
294
B
2
2.71
4.84
7.00
11.59
9
295
B
3
3.16
4.58
4.09
8.96
9
296
B
3
3.82
4.51
3.78
8.72
9
297
B
3
2.99
4.47
2.44
9.32
9
298
B
4
2.01
4.77
4.17
8
9
299
B
4
3.76
4.79
4.22
8.84
9
300
B
4
1.57
4.76
6.18
8.6
9
301
B
5
3.94
4.81
5.53
8.96
9
302
B
5
3.40
4.78
6.22
9.44
9
303
B
5
9
304
B
6
4.72
6.34
13.72
20.45
9
305
B
6
3.74
6.8
13.37
28.46
9
306
B
6
2.99
6.61
13.25
31.34
1
37
C
1
1.89
6.3
0.12
2.4
1
38
C
1
1.96
6.25
0.13
2.2
1
39
C
1
2.37
6.28
0.12
2.1
1
40
C
2
3.47
6.18
7.90
5.5
1
41
C
2
2.46
6.25
8.12
7.7
1
42
C
2
2.20
6.21
5.91
6.6
1
43
C
3
4.84
5.58
0.19
3.2
1
44
C
3
5.31
5.57
0.12
2.4
1
45
C
3
4.88
5.59
0.12
2.6
5.63
263
1
46
C
4
0.82
6.08
0.12
2.7
1
47
C
4
0.82
6.08
0.12
2.6
1
48
C
4
1.21
6.08
0.12
2.2
1
49
C
5
0.81
6.28
0.12
4.7
1
50
C
5
0.81
6.34
0.13
3
1
51
C
5
1.23
6.36
0.12
2.8
1
52
C
6
1.64
7.34
3.92
13.1
1
53
C
6
4.72
7.26
0.12
5.7
1
54
C
6
0.15
7.35
0.12
7.1
3
127
C
1
2.18
5.55
0.63
2.34
3
128
C
1
1.51
6.36
0.51
2.37
3
129
C
1
2.43
6.28
0.68
2.49
3
130
C
2
2.29
5.51
6.63
6.88
3
131
C
2
0.46
5.63
4.06
5.38
3
132
C
2
1.73
5.94
5.52
6.18
3
133
C
3
1.27
5.27
3.72
10.7
3
134
C
3
1.21
3
135
C
3
1.36
3
136
C
4
1.47
3
137
C
4
1.46
7.54
0.86
4.97
3
138
C
4
0.82
5.96
0.50
2.83
3
139
C
5
1.70
5.31
3.70
5.96
3
140
C
5
1.94
5.66
3.60
4.1
3
141
C
5
1.37
6.34
0.40
7
3
142
C
6
1.34
6.74
9.72
15.9
3
143
C
6
1.48
5.43
10.94
13.24
3
144
C
6
2.25
6
217
C
1
5.85
5.22
5.39
2.11
6
218
C
1
9.02
5.17
6.00
2.22
6
219
C
1
9.76
6.07
5.01
3.02
6
220
C
2
5.61
6.08
10.75
6.55
6
221
C
2
3.23
6.08
7.12
6.32
6
222
C
2
4.07
5.47
8.62
7.39
6
223
C
3
11.07
5.47
1.21
2.57
6
224
C
3
5.74
5.52
1.59
2.93
6
225
C
3
4.88
5.74
1.49
2.69
6
226
C
4
0.83
5.71
2.62
2.34
6
227
C
4
5.45
5.7
2.35
2.46
6
228
C
4
1.64
5.81
1.85
3.51
6
229
C
5
6.30
5.76
5.04
3.75
6
230
C
5
4.32
5.78
4.72
3.39
6
231
C
5
3.49
7.25
7.28
13.34
6
232
C
6
4.80
7.35
2.67
9.71
264
2.52
6.01
3.08
3.76
0.47
6
233
C
6
2.83
7.44
6
234
C
6
9.05
5.03
9
307
C
1
3.84
6.28
1.45
2.5
9
308
C
1
2.54
6.23
1.41
2.14
9
309
C
1
4.10
6.25
1.18
2.02
9
310
C
2
6.07
5.91
6.44
9
311
C
2
3.20
6.03
5.89
7.04
9
312
C
2
2.20
9
313
C
3
-4.44
5.4
2.78
3.69
9
314
C
3
4.06
5.46
2.27
3.57
9
315
C
3
2.63
5.41
1.52
3.57
9
316
C
4
2.50
5.6
1.46
3.33
9
317
C
4
2.59
5.61
2.07
2.85
9
318
C
4
3.53
5.65
1.18
2.61
9
319
C
5
3.29
5.68
1.19
4.41
9
320
C
5
2.30
5.72
2.14
3.81
9
321
C
5
3.60
9
322
C
6
3.48
7.28
5.60
16.02
9
323
C
6
2.04
7.43
6.04
15.54
9
324
C
6
2.18
7.28
6.21
11.83
1
55
D
1
1.98
5.33
0.24
5.2
1
56
D
1
2.07
5.3
0.14
4.5
1
57
D
1
2.19
5.34
0.28
4.5
1
58
D
2
4.08
5.6
6.07
9.6
1
59
D
2
3.16
5.56
8.16
9.4
1
60
D
2
1.48
5.51
3.85
8
1
61
D
3
4.31
5.58
0.54
5.8
1
62
D
3
4.24
5.51
0.30
5.5
1
63
D
3
3.80
5.47
0.13
5
1
64
D
4
0.75
6.12
0.23
6.1
1
65
D
4
0.80
6.07
0.14
5.6
1
66
D
4
0.95
6.11
0.14
6.2
1
67
D
5
1.24
6.34
0.32
9
1
68
D
5
1.10
6.27
0.95
7.2
1
69
D
5
1.03
6.23
0.14
7.2
1
70
D
6
1.02
6.85
4.30
16.1
1
71
D
6
1.26
6.76
0.68
11.2
1
72
D
6
0.80
6.62
3.36
10.9
3
145
D
1
2.30
5.64
5.05
5.05
3
146
D
1
1.13
5.57
4.88
4.89
3
147
D
1
2.22
3
148
D
2
0.76
3
149
D
2
1.59
265
2.34
12.99
4.56
5.38
1.83
4.34
10.58
5.72
9.91
16.81
3
150
D
2
2.82
7.22
11.25
23.01
3
151
D
3
0.51
5.52
0.60
5.61
3
152
D
3
1.43
5.5
0.56
5.61
3
153
D
3
1.09
3
154
D
4
1.16
6.87
0.55
7.82
3
155
D
4
0.44
5.68
0.55
3.64
3
156
D
4
0.74
5.71
5.89
8.73
3
157
D
5
3.43
5.72
11.37
5.96
3
158
D
5
-0.51
6.27
7.19
6.65
3
159
D
5
2.14
5.78
6.13
7.57
3
160
D
6
1.81
5.7
0.56
10.58
3
161
D
6
2.04
5.49
0.52
7.81
3
162
D
6
0.86
6.61
0.56
16.94
6
235
D
1
8.82
5.02
2.74
4.21
6
236
D
1
3.80
5.04
2.87
4.21
6
237
D
1
8.89
5.26
3.19
5.36
6
238
D
2
20.52
5.35
11.34
8.9
6
239
D
2
7.82
5.08
10.55
8.19
6
240
D
2
43.82
4.69
9.50
5.38
6
241
D
3
4.88
4.77
3.95
5.03
6
242
D
3
5.15
4.86
3.53
4.92
6
243
D
3
2.64
5.23
2.99
5.38
6
244
D
4
2.87
5.27
8.06
6
245
D
4
8.47
5.03
4.98
6
246
D
4
1.97
5.2
4.79
6.09
6
247
D
5
5.71
5.15
8.23
5.97
6
248
D
5
4.70
5.31
6.85
6.91
6
249
D
5
22.84
6.14
6
250
D
6
3.37
6.26
6.44
12.76
6
251
D
6
3.13
6.56
8.39
14.51
6
252
D
6
3.93
5.18
9
325
D
1
2.33
5.03
2.41
5.25
9
326
D
1
3.36
4.95
2.16
5.25
9
327
D
1
3.90
4.93
2.45
5.37
9
328
D
2
3.07
5.06
6.85
7.52
9
329
D
2
1.98
5.09
6.08
8.48
9
330
D
2
3.04
4.91
5.75
8.24
9
331
D
3
3.32
5.01
1.70
4.29
9
332
D
3
5.33
4.74
2.71
5.37
9
333
D
3
0.64
4.78
4.12
6.21
9
334
D
4
1.92
5.08
3.38
5.61
9
335
D
4
2.46
5.01
3.10
4.65
9
336
D
4
46.89
4.95
3.59
5.61
266
0.56
15.92
12.74
9
337
D
5
3.08
5.01
3.72
5.85
9
338
D
5
4.03
5.09
3.09
6.09
9
339
D
5
4.26
5.24
2.41
6.56
9
340
D
6
3.45
6.39
6.42
16.38
9
341
D
6
3.69
6.51
5.97
14.34
9
342
D
6
3.65
6.43
5.33
16.98
1
73
E
1
0.59
5.65
52.45
35.2
1
74
E
1
0.49
6.05
51.37
30.3
1
75
E
1
0.63
5.62
37.17
38.5
1
76
E
2
0.75
5.81
70.88
42.4
1
77
E
2
0.52
5.68
53.76
43.7
1
78
E
2
0.11
5.71
66.83
45.3
1
79
E
3
0.26
5.57
63.82
37.1
1
80
E
3
0.32
5.62
39.95
37.8
1
81
E
3
0.05
5.61
48.86
39.4
1
82
E
4
0.54
5.74
63.13
44.4
1
83
E
4
0.74
5.72
58.83
45
1
84
E
4
0.54
5.71
48.81
43.1
1
85
E
5
0.69
5.99
44.45
52.4
1
86
E
5
0.59
5.95
46.16
49.1
1
87
E
5
1.09
5.9
44.03
45.3
1
88
E
6
5.4
45
1
89
E
6
5.4
54
1
90
E
6
3
163
E
1
1.32
5.21
58.60
39.13
3
164
E
1
1.29
5.48
71.43
37.46
3
165
E
1
0.10
3
166
E
2
0.79
5.41
106.98
34.34
3
167
E
2
1.36
5.252
96.67
36.19
3
168
E
2
0.86
3
169
E
3
0.92
5.21
95.78
49.13
3
170
E
3
0.95
5.18
74.59
34.37
3
171
E
3
1.21
5.51
106.13
37
3
172
E
4
0.50
5.52
84.53
38.5
3
173
E
4
1.41
5.26
78.82
37.17
3
174
E
4
1.58
3
175
E
5
1.02
3
176
E
5
1.18
3
177
E
5
1.26
5.22
80.56
44.02
3
178
E
6
6.91
5.67
72.58
34.463
3
179
E
6
4.86
5.66
91.15
44.378
3
180
E
6
3.78
6
253
E
1
0.53
267
55.47
108.57
60.24
5.62
53.56
46.66
72.94
67.53
5.2
58.42
33.36
6
254
E
1
6.12
5.23
66.64
29.49
6
255
E
1
2.58
5.16
64.46
36.28
6
256
E
2
2.20
5.21
97.99
35.35
6
257
E
2
1.14
5.1
80.22
39.33
6
258
E
2
6.24
5.05
87.67
36.4
6
259
E
3
5.08
5.12
84.57
28.79
6
260
E
3
7.72
5.04
67.75
31.72
6
261
E
3
3.07
5.12
83.54
29.38
6
262
E
4
6.14
5.13
120.30
27.39
6
263
E
4
8.03
5.14
96.88
28.21
6
264
E
4
2.39
5.57
84.25
29.96
6
265
E
5
7.02
5.56
66.21
33.01
6
266
E
5
7.50
5.53
63.82
30.78
6
267
E
5
7.94
5.26
63.00
32
6
268
E
6
7.25
5.21
69.33
35
6
269
E
6
5.19
5.23
72.39
35
6
270
E
6
7.10
5.23
66.12
36
9
343
E
1
2.86
5.38
44.65
25.59
9
344
E
1
0.14
5.31
48.03
25.83
9
345
E
1
5.48
5.14
51.37
35.05
9
346
E
2
2.68
5.13
64.75
42.35
9
347
E
2
3.98
5.15
65.02
37.92
9
348
E
2
1.56
5.14
64.98
40.07
9
349
E
3
3.13
5.04
61.70
36.6
9
350
E
3
0.68
5.08
51.03
36.6
9
351
E
3
3.21
5.17
46.31
34.57
9
352
E
4
2.62
5.06
63.81
35.65
9
353
E
4
2.12
5.11
67.83
41.87
9
354
E
4
4.23
5.15
61.23
41.39
9
355
E
5
2.12
5.91
43.36
33.37
9
356
E
5
1.60
5.59
53.20
39.24
9
357
E
5
3.14
5.62
68.55
47.97
9
358
E
6
1.00
5.13
71.14
45.435
9
359
E
6
2.00
5.21
52.24
43.433
9
360
E
6
3.00
5.14
54.22
38.352
268
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