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Phosphorus forms and retention in a sandy soil receiving dairy waste effluent

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Title:
Phosphorus forms and retention in a sandy soil receiving dairy waste effluent
Creator:
Al-Shankiti, Abdullah, 1956-
Publication Date:
Language:
English
Physical Description:
xii, 126 leaves : ill. ; 29 cm.

Subjects

Subjects / Keywords:
Adsorption ( jstor )
Cropping systems ( jstor )
Crops ( jstor )
Leaching ( jstor )
Phosphorus ( jstor )
Soil horizons ( jstor )
Soil profiles ( jstor )
Soil samples ( jstor )
Soils ( jstor )
Sorption ( jstor )
Cropping systems -- Florida ( lcsh )
Dairy waste -- Florida ( lcsh )
Dissertations, Academic -- Soil and Water Science -- UF ( lcsh )
Soil and Water Science thesis, Ph. D ( lcsh )
Soils -- Phosphorus content -- Florida ( lcsh )
Suwannee River, FL ( local )
Genre:
bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 2000.
Bibliography:
Includes bibliographical references (leaves 118-125).
General Note:
Printout.
General Note:
Vita.
Statement of Responsibility:
by Abdullah Al-Shankiti.

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University of Florida
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University of Florida
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Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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022906831 ( ALEPH )
45068127 ( OCLC )

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PHOSPHORUS FORMS AND RETENTION IN A SANDY SOIL RECEIVING DAIRY
WASTE EFFLUENT
















By

ABDULLAH AL-SHANKITI


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA


2000














ACKNOWLEDGMENTS

Sincere appreciation and gratitude go to my major advisor, Dr. D. A. Graetz, for

giving me all the help I needed throughout the course of my study. I would also like to

thank my committee members-Dr. W. G. Harris, Dr. R. D. Rhue, and Dr. R. Nordstedt--

for their guidance, comments, and suggestions. I am grateful to Dr. V. Nair for her

insightful comments and suggestions, to Dr. K. R. Woodard for his help and support, and

to D. Lucas for her encouragement and support.















TABLE OF CONTENTS

pag

ACKNOW LEDGM ENTS ......................................................................................... iii

LIST OF TABLES .......................................................... ........................................ vi

LIST OF FIGURES........................................... ...................................................v.iii

ABSTRACT................................ .............................................................................. x

CHAPTERS

1 INTRODUCTION .............................................................................................. 1

Statement of the Problem ......................................................................................... 3
Objectives ................................................................................. ..................................4
Review of Literature............................................. ..............................................5
Soil Phosphorus .................................................. ............................................... 6
Phosphorus Accumulation......................................................................................8
Phosphorus Forms and Fractionation .................................................................. 11
Phosphorus Retention.......................................................................................... 13
Downward P movement.......................................................................................20
M anure M anagement..........................................................................................22
Dissertation Format .............................................................................................23


2 PHOSPHORUS ACCUMULATION IN A SANDY SOIL RECEIVING DAIRY
W ASTE EFFLUENT ....................................................................................................25

Introduction.........................................................................................................25
M materials and M ethods ........................................ ................ ............................. 27
Experiment Location and Design...................................................................... 27
Soil Selection and Sampling ....................................................... ..................27
Soil Characterization........................................................................................27
Effluent Application and Characterization .............................................................28
Statistical Analysis........................................................................................... 28
Results and Discussion........................................................................................... 30
Soil Properties Prior to Effluent Application.........................................................30
Effect of Application Rate and Cropping Systems.................................................33
Summary and Conclusions ........................................................................................42








3 PHOSPHORUS FORMS AND FRACTIONATION IN A SANDY SOIL
RECEIVING DAIRY WASTE EFFLUENT ............................................................44

Introduction...................................................................... ...................................44
M materials and M methods ...............................................................................46
Experiment Location and Design....................................................................46
Soil Selection and Sampling ............................................ ................................46
Fractionation Scheme .................................................. ....... ........................47
Statistical A nalysis....................................... ....................................................48
Results and D discussion ..................................... ..... ..............................................48
Study Site............... .. ....................................................................................... 54
Summary and Conclusions .................................................................61


4 PHOSPHORUS RETENTION IN A SANDY SOIL RECEIVING DAIRY WASTE
EFFLU EN T ................................................ ............................................................ 63

Introduction........................ .................................................................................63
M materials and M ethods ........................................................................................ 65
Experiment Location and Design .....................................................................65
Soil Selection and Sampling ...................................... ..............65
Soil Characterization........................................ ....................................65
Calculations.... ...... ...................... .....................................- 67
Statistical Analysis............................................................. ......... 68
Results and D discussion ............................................................................... ......... 68
Relative Phosphorus Adsorption (RPA) ...........................................................68
Degree of Phosphorus Saturation (DPS) ............................................................. 71
Langmuir Adsorption Parameters.....................................................................73
Summary and Conclusions ..................................................................................77


5 DOWNWARD PHOSPHORUS MOVEMENT ASSESSMENT IN A SANDY SOIL
RECEIVING DAIRY WASTE EFFLUENT .................................................... 81

Introduction........... ......................... .. ........................... ........................................ 81
Materials and Methods ......................................... ........... ................... 83
Experiment Location and Design............................ ............ ................. 83
Soil Selection and Sampling ..................................................................83
Soil Characterization........................................................................... 84
Statistical Analysis.......................................................................... ....................... 84
Results and Discussion ........................................................................ ....... ... 85
Summary and Conclusions ......................................................... ................. 95


6 UTILIZATION OF DAIRY WASTE EFFLUENT THROUGH SEQUENTIAL
CR O PPIN G ............................................................ ............................................... .. 97









Introduction............................................. .................... .....................................97
M materials and M ethods ........................................................................ .............. 98
Experiment Location and Design..................................................................... ... 98
Sampling and Analysis .....................................................................................99
Results and discussion.......................................................................................... 100
Summary and Conclusions ................................................................................. 105


7 SUM M ARY AND CONCLUSIONS .................................................................... 108

APPENDIX

SELECTION OF SOIL: SOLUTION RATIO ........................................................ 114

LIST OF REFERENCES....................................................................................... 118

BIOGRAPHICAL SKETCH .................................................................................... 126














LIST OF TABLES


Table Page

Table 2-1. Average annual concentrations (mg/L) of ammonium nitrogen (NH4 -N), total
Kjeldahl nitrogen (TKN), soluble reactive P (SRP), and total P (TP) in
effluent applied to the study site. Numbers in parentheses are standard
deviations................................................................................. ......28

Table 2-2. Selected characteristics of typical Kershaw sand (Soil Survey Staff, Gilchrist
County, Florida, 1973) compared to the study site....... ............................ 31

Table 2-3. Mehlich I-extractable elements concentrations and total P (TP) in "native" soil
(n = 3 profiles) and study site (n = 12 profiles) soil profiles prior to beginning
of the study..................................................................... ... ....... 32

Table 2-4. Statistical evaluation of TP data for the three-year study period. .....................34

Table 2-5. Regression equation relating Mehlich I-P to the independent variables Mehlich
I-Ca, Mg, and Fe. (n=432)....................................................................42

Table 3-1. P values (mg/kg) in each fraction within a soil depth increment at the
beginning (1996) and end of the study period (1998) (n = 12 profiles). Values
are Least Square M eans (LSM )......................................................................49

Table 3-2. Percentage of P in each fraction within a soil depth increment at the beginning
(1996) and end of the study period (1998)(n = 12 profiles). Values are Least
Square M eans (LSM ). ................................... ..............................................50

Table 3-3. Increases in each fraction within a soil depth increment between the beginning
(1996) and end of the study period (1998) ..... ............................................52

Table 3-4. Mean concentration of Mehlich I extractable elements (mg/kg) in the soil
profile of the study site in 1996 prior to the application of effluent (n = 12
profiles) ................................................................ .....................................54

Table 3-5. P values (mg/kg) in each of the fractions within a soil depth increment at the
native site (n = 3 profiles). Values are Least Square Means (LSM)...................55








Table 3-6. Percentage of P in each of the fractions within a soil depth increment at the
native site (n = 3 profiles). Values are Least Square Means (LSM)................... 55

Table 4-1. RPA values within the soil profile of the study site (n = 12 profiles) prior and
after to application of effluent compared to the "native soil" (n = 1 profile).
Values are Least Square Mean (LSM). ...........................................................69

Table 4-2. Multiple regression equations relating RPA to a) Mehlich I (DA) Al, Fe and P,
b) Oxalate Al, Fe, and P in 1996 (prior to the application of effluent) (n = 72). 72

Table 4-3. DPS It % values within the soil profile of the study site (n = 12 profiles)
prior and after to application of effluent compared to the "native" soil (n = 1
profile). Values are Least Square Means (LSM). .................................... ..72

Table 4-4. DPS 21 % values within the soil profile of the study site (n = 12 profiles)
prior and after to application of effluent compared to the "native" soil (n = 1
profile). Values are Least Square Means (LSM). ................................. ..74

Table 4-5. Comparison of Langmuir parameters (Sm, EPCo, k) and So mean values of
different horizons within the soil profile prior to the application of effluent in
1996 and after two years of effluent application in 1998...................................76

Table 5-2. Mehlich I-extractable elements concentrations and total P (TP) in "native" soil
(n = 1 profile) and study site soil profiles (n = 12 profiles) prior to the start of
the study ................................................................................................... 87

Table 5-3. Changes in WSP concentration within the soil profile under high application
rate after the application of effluent (1998) vs. prior to the application of
effl uent (1996)..... ........................................................................................ 90

Table. 5-4. Changes in WSP concentration within the soil profile under the low
application rate after the application of effluent (1998) vs. prior to the
application of effluent (1996) ...................................................................... 90

Table 6-1. P removed (kg/ha) by the corn-forage sorghum-rye cropping system under
high and low application rates during the 1996-97 and 1997-98 seasons. (Data
obtained from Woodard et al. 2000) ........................................................... 101

Table 6-2. P removed (kg/ha) by the perennial peanut-rye cropping system under high
and low application rates during the 1996-97 and 1997-98 seasons. (Data
obtained from Woodard et al. 2000)............................................................... 103

Table 6-3. Average dry matter yield of the corn-forage sorghum-rye during the 1996-97
and 1997-98 seasons .................................................. ......... ........................... 106

Table 6-4. Average dry matter yield of the perennial peanut-rye during the 1996-97 and
1997-98 seasons............................................................................................... 106














LIST OF FIGURES


Figu Page

Figure 2-1. Average total P (TP) concentrations in the soil profile under the high rate
application prior to application of effluent (1996) and after effluent
application (1997 and 1998). Values are LSM Std. Error..............................36

Figure 2-2. Average total P (TP) concentrations in the soil profile under the low rate
application prior to application of effluent (1996) and after effluent
application (1997 and 1998). Values are LSM Std. Error...............................37

Figure 2-3. Mehlich I-extractable P concentrations in the soil profile prior to start of the
study and after two years of effluent application (1998). Values are LSM
Std. Error....................................................................................... .......38

Figure 2-4. Mehlich I-extractable P concentrations for cropping systems under the high
rate effluent application in 1998. Values are LSM Std. Error........................40

Figure 2-5. Mehlich I-extractable P concentrations for cropping systems under the low
rate effluent application in 1998. Values are LSM Std. Error........................41

Figure 3-1. Al-Fe-associated P (mg/kg) within the soil profile at the beginning 1996 and
end of the study period (1998). Values are LSM Std. Error..........................51

Figure 3-2. Labile P values (mg/kg) within the soil profile at the beginning (1996) and
end of the study period (1998). Values are LSM Std. Error..........................57

Figure 3-3. Ca-Mg associated P values (mg/kg) within the soil profile at the beginning
(1996) and end of the study period (1998). Values are LSM Std. Error...........58

Figure 3-4. Residual-P values (mg/kg) within the soil profile at the beginning (1996) and
end of the study period (1998). Values are LSM Std. Error ..........................60

Figure 4-1. Relationship between Degree of P saturation (DPS 1) calculated from
oxalate extractable-P and Degree of P Saturation calculated from Mehlich I
(DPS 2) for soil samples from the study site..............................................75








Figure 4-2. Relationship between Degree of P saturation calculated from oxalate
extractable-P (DPS 1) and equilibrium P concentration (EPCo) for soil
samples from the study site .................................................................. ..... 78

Figure 4-3. Relationship between Degree of P saturation calculated from oxalate
extractable-P (DPS 1) and soluble P (Po) mg/L for soil samples from the
study site........................................................................................... .... 79

Figure 5-1.Mean water soluble P (WSP) concentrations within the soil profile of the
study site under the high rate effluent application prior to the application of
effluent in 1996 and after effluent application in 1998. Values are LSM Std.
Error. ........................................................................................... ....... 88

Figure 5-2. Mean water soluble P (WSP) concentrations within the soil profile of the
study site under the low rate effluent application prior to the application of
effluent in 1996 and after effluent application in 1998. Values are LSM Std.
Error. ....................................................................................................... 89

Figure 5-3. Mean water soluble P (WSP) concentration within the soil profile of the study
site prior to the application of effluent in 1996 and after effluent application in
1998. Values are LSM Std. Error. ...........................................................92

Figure 5-4. Labile-P concentration within the soil profile of the study site prior to the
application of effluent in 1996 and after effluent application in 1998. Values
are LSM Std. Error.................................................................................. ... 93

Figure 6-1. P removal (kg/ha) of corn-forage sorghum-rye during the 1996-97 and 1997-
98 seasons.................................................... ....... ..................................... 102

Figure 6-2. P removal (kg/ha) of perennial peanut-rye during the 1996-97 and 1997-98
seasons...................................................................................................... 104














Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

PHOSPHORUS FORMS AND RETENTION IN A SANDY SOIL RECEIVING DAIRY
WASTE EFFLUENT

By

Abdullah Alshankiti

May 2000
Chairman: D.A. Graetz
Major Department: Soil and Water Science

Currently there are major concerns about the potential negative effects of nutrient

losses from the waste of dairy farms on surface and ground water quality. In many

confined livestock production systems, manures are normally applied at a rate designed

to meet crop N requirements. However, this often results in a buildup of soil P above

amounts required for optimal crop yield and increases the chances for P losses from

source areas to water bodies.

This research, conducted at a dairy farm in north Florida, investigates the status of

soil P under two main treatments of dairy waste effluent and two cropping systems. The

N application rates were 448 and 896 kg/ha/yr which correspond to P loading of 112 and

224 kg/ha/yr. The cropping systems were perennial peanut-rye (P-R) and corn- forage

sorghum-rye (C-FS-R). The objectives were to: (1) examine the accumulation of P in the

soil profile, (2) quantify and characterize P forms in the soil profile, (3) quantify and








characterize P retention in the soil profile, (4) determine P uptake by the cropping

systems, and (5) assess the downward movement of P.

The study site, mapped as Kershaw sand, appears to have been heavily loaded

with animal waste (47 mg/kg Mehlich I-extractable P (MI-P) in the native area vs. 283

mg/kg in the study site surface soils). The MI-P increased significantly with high effluent

rate application, particularly under the P-R cropping system, which suggests that the C-

FS-R cropping system may be more effective in P removal than the P-R cropping system.

Total P (TP) increased from 343 mg/kg in 1996 to 689 mg/kg in 1998. Water soluble P

(WSP) increased but primarily in the lower depths of the soil profile under both

treatments.

Al- and Fe-associated P constituted the major proportion (up to 60%) of the TP in

the soil profile. Labile-P accounted for 18 to 30%, and Ca- and Mg-associated P

accounted for about 10% of TP. Water soluble- and labile-P concentrations from 1996

and 1998 indicated a downward movement ofP in the soil profile. These same data

coincided with a decrease in retention capacity as determined by "Relative Phosphorus

Adsorption" (RPA). Degree of P Saturation (DPS) data indicated that the surface horizon

is more likely to release P than the deeper depths. The conclusions drawn from DPS were

in agreement with the conclusions arrived at from the soil adsorption capacity and

equilibrium phosphorus concentration (EPCo).

Phosphorus removal was higher for the C-FS-R than for the P-R cropping system.

The removal values agreed with published P uptake for such crops, but crop uptake did

not alter the high level of soil P that was already present before application. When soil

test P levels in the soil exceed optimum values for crop production, the application of








dairy waste based on estimated N requirement may not be appropriate on heavily P

loaded sandy soil such as the soil at the study site.













CHAPTER 1
INTRODUCTION

The impact of current agriculture management practices in farmland or animal-

related activity on water quality is well documented. Runoff from agricultural land is one

of the major sources of nonpoint-source pollution. The USEPA has identified agriculture

nonpoint-source pollution as the major source of stream and lake contamination that

prevents attainment of water quality goals identified in the Clean Water Act (Parry, 1998;

USEPA, 1996). The transport of phosphorus (P) to surface water can lead to accelerated

eutrophication of these waters, which limit their use for fisheries, recreation, industry, or

drinking. Although nitrogen (N) and carbon (C) are also associated with accelerated

eutrophication, most attention has focused on P because P often limits eutrophication and

its control is of prime importance in reducing the accelerated eutrophication of surface

water (Thomann and Mueller, 1987)

Most P in agriculture soils is found either as insoluble precipitates of Ca, Fe and/

or Al or as a constituent of a wide range of organic compounds. Water moving across or

through soils removes both soluble P and sediments enriched with P, usually with the

lighter, fine sized particles such as clays and organic matter. The soluble or particulate P

then either can enter a flowing water body where it can be deposited as sediment or can

be carried directly into a lake or pond. Phosphorus can also leach downward in the soil,

perhaps to a tile drainage system or to ground water, where subsurface transport can then

discharge the P into a stream or lake (Sharpley and Halvorson, 1994).








Most of the P that enters aquatic ecosystems comes from agricultural use. Phosphorus is

added to lands as fertilizers, organic solids, wastewater, and feeds. It is estimated that

42,660 Mg of fertilizers was used during 1996 in Florida (Reddy et al., 1999). Fertilizer P

is primarily in inorganic form, which is bioavailabile and can be a major source of P for

many ecosystems. For example, fertilizer P accounted for 51% of P imports to the

Okeechobee Basin (Boggess et al., 1995). Another significant source ofP input to the

lake was the dairy farming and beef cattle ranching north of the lake which accounted for

about 49% of the TP input to the lake (Federico et al., 1981). Thus, optimal dairy waste

management practices are more necessary than ever; more cows on limited land area

increase the likelihood of environmental problems resulting from mismanagement of

dairy farm wastes. A dairy waste management system should account for the fate of

nutrients that may be of environmental concern. The overall goal of sound agronomic

and environmental management programs for soil P is to maximize plant growth, while

minimizing losses of P to surface waters (Lanyon, 1994). It is important, therefore, to

understand the role of soil reactions in controlling the availability of soil P for plant

uptake or loss in erosion, surface runoff, and leaching. Amounts of P exported from

watersheds are tied to watershed hydrology, soil P content, and amount of P added as

fertilizer or manure. This assumes in most cases that P export from watersheds occurs in

surface rather than subsurface runoff, although it is recognized that in some regions of the

US dominated by sandy or organic soils P can be transported in subsurface drainage

waters. Generally, the P concentration in water moving through the soil profile is small

due to sorption ofP, except in acid organic or peaty soils where the adsorption affinity

and capacity for P retention are low (Sims et al., 1998). Similarly, sandy soils with low P








sorption capacities, waterlogged soils, and soils with preferential flow through

macropores and earthworm holes are susceptible to P movement (Sharpley and Syers,

1979).


Statement of the Problem

In 1990, the Middle Suwannee River area was approved as a Hydrologic Unit

Area project based on data generated by the Florida Department of Environmental

Protection. These data showed an elevated concentration of nitrate-nitrogen in the

Floridan Aquifer in the Suwannee River Basin, especially in areas of intensive

agricultural activity. Phosphorus concentrations in the Suwannee River ranged from 0.40

to 0.49 mg/L which were 6.4 times the median regional value of north Florida streams.

The Hydrologic Unit Area program was developed to reduce or prevent water quality

degradation of the Floridan Aquifer and the Suwannee River resulting from agricultural

operations. Management of nutrients (potential contaminants) in dairy waste effluent

through spray field crop production systems is an important component in the overall

scheme for protecting ground and surface water from elevated levels of N and P. The use

of inappropriate crop management technology under a dairy effluent irrigation system

can lead to the loss of N to the ground water. Uptake of nutrients by agronomic crops

sequenced over time is an effective, economical, and environmentally sound means of

nutrient recovery. Cropping systems designs are needed to meet environmental demands

by maximizing nutrient uptake while meeting the needs of dairy producers.

The Use of Dairy Manure Effluent in A Rhizoma (Perennial) Peanut Based

Cropping Systems for Nutrient Recovery and Water Quality Enhancement is a research

project established under the Hydrologic Unit Area project (HUA). The objective of this








project was to evaluate five cropping systems grown under a dairy effluent disposal

irrigation system, comparing their effectiveness in nutrient recovery and maintenance of

acceptable levels of N and P in ground water. The cropping systems were corn-forage

sorghum-rye, corn-bermudagrass-rye, bermudagrass-rye, perennial peanut-rye, and corn-

perennial peanut-rye. The N application rates were 448, 672 and 896 kg/ha/yr which

correspond to P loadings of 112, 168 and 224 kg/ha/yr. My study was a component of

this project and addressed P forms and retention in the soil profile under two cropping

systems (corn-forage sorghum-rye and perennial peanut-rye) and two N application rates

(448 and 896 kg/ha/yr) which correspond to P loadings of 112 and 224 kg/ha/yr.

In order to achieve the objectives mentioned below, two cropping systems were

chosen from the main study: corn-forage sorghum-rye and perennial peanut-rye. The

workload associated with evaluating each treatment in the overall project would have

been prohibitive, therefore treatments were selected which provide representative data

with regard to the fate of P in the various cropping systems. The former is commonly

used by North Florida dairies (Staples, 1997). Recently, perennial peanut has been

identified as promising for its potential of continuous nutrient recovery over an extended

period of the year and for production of high quality forage


Objectives

The main objective of this research was to study the effect of dairy waste effluent

application on P accumulation, forms, and retention in the soil profile of a sandy soil

under two cropping systems. The cropping systems were corn-forage sorghum-rye, which

represent the traditional crops for the Middle Suwannee River area, and perennial peanut-








rye, an improved cropping system to be introduce to the area. The specific objectives and

hypotheses of this research were as follow:

Objective 1: Quantify and characterize inorganic P forms in the soil profile of the

chosen cropping systems with increasing effluent P application.

Hypothesis: Application of dairy waste effluent will increase P levels in the soil

resulting in an accumulation ofP in the soil profile.

Objective 2: Quantify and characterize P retention capacity in the soil profile.

Hypothesis: Soil retention capacity will decrease with continuous addition of

dairy waste effluent and may induce a downward movement of P.

Objective 3: Determine P uptake by the chosen cropping systems under two rates

of effluent application.

Hypothesis: P accumulation in soil profile will decrease with increasing plant

uptake.


Review of Literature

Phosphorus (P) is an integral and essential part of the food production system, but

P doesn't occur abundantly in most soils. Total P concentration in surface soils varies

between about 0. 02 and 0.10% (Tisdale et al., 1993). The native P compounds are mostly

unavailable for plant uptake, some being highly insoluble. When soluble sources of(P) as

those in fertilizer and manure are added to soils, they are fixed or are changed to

unavailable forms and in time, react further to become highly insoluble forms. Farmers

commonly apply more P in fertilizers and manure than is removed by the crops. In time,

soil P levels increase often to high enough levels to reduce significantly future








requirements for P fertilizers and cause a buildup of P reserves in the soil profile (Brady,

1990).

Soil Phosphorus

Phosphorus in agriculture soils is found in inorganic and organic forms. Inorganic

forms represent 50-70% of soil P, although this fraction can vary from 10 to 90%

(Pierzynski et al., 1994). Inorganic forms are typically hydrous sesquioxides and

insoluble precipitates of Ca, Fe and/or Al. Organic P varies between 15 and 80% in most

soils (Tisdale et al., 1993). The quantity of organic P in soil generally increases with

increasing C and /or N. Many of the organic P compounds in soils have not been

characterized, but most are esters of orthophosphoric acid and have been identified

primarily as inositol phosphate, phospholipids, and nucleic acids. Organic P turnover in

soils is a result of P mineralization and immobilization reactions which, in general, are

similar to those of N as both processes occur simultaneously in soils. The initial source of

soil organic P is plant and animal residue, which is degraded through microbial activity to

produce other organic compounds and release inorganic P (Tisdale et al., 1993).

There is an interrelationship between the various forms of P in soils. The decrease

in soil solution P concentration with absorption by plant roots is buffered by both

inorganic and organic fractions in soil. Primary and secondary P minerals (nonlabile P)

dissolve to resupply H2P04-/ HP042- in solution. Inorganic P adsorbed on mineral and

clay surfaces as H2P04 or HP042- (labile inorganic P) also can desorb to buffer P in

solution P.

Numerous soil microorganisms digest plant residues containing P and produce

many organic P compounds in soil. These organic P compounds can be mineralized

through microbial activity to supply inorganic P. Soil solution P is often called the








'intensity factor', while the inorganic adsorbed P and organic labile P fractions are

collectively called the 'quantity factor'. Maintenance of solution P concentration or

(intensity) for adequate P nutrition in the plant depends on the ability of labile P

(quantity) to replace soil solution P taken up by the plant. The ratio of quantity to

intensity is called the 'capacity factor' which expresses the relative ability of the soil to

buffer changes in soil solution P. Generally, the larger the capacity factor, the greater the

ability to buffer solution P. The P cycle can be simplified to the following relationship:

Soil solution <----- Labile P<------- nonlabile P

Labile P is the readily available portion of the quantity factor that exhibits a high

dissociation rate and rapidly replenishes solution P. Depletion of labile P causes some

nonlabile P to become labile, but at a slow rate. Thus, the quantity factor comprises both

labile and nonlabile fraction (Tisdale et al., 1993).

The division of P in the soil's solid phase into the labile and nonlabile forms

comes about from a kinetic consideration. From a mechanistic point of view, P in the

soil's solid phase can be classified by yet another way into adsorbed P and crystalline P.

The first refers to P adsorbed on active surfaces in the soil, and the second to distinct P

compounds either formed as reaction products, or inherently present in the soil matrix.

The two types of categorization (i.e., labile vs. nonlabile and adsorbed vs.crystalline) are

not synonymous, although a great deal of overlap exists between the two. The labile P

does not represent a precisely distinct phase of solid phase P, but one that has arbitrary

boundaries of time and other procedural factors. Any loss of precision in defining labile P

is paralleled by an equal uncertainty in defining the remaining P (Olsen and Khasawneh,

1980). Phosphorus amendments, in either organic or inorganic form, are needed to








maintain adequate available soil P for plant uptake. Once applied, P is either taken up by

the crop or becomes weakly or strongly adsorbed onto Al, Fe and Ca surfaces. With the

application of P, available soil P content increases as a function of certain physical and

chemical soil properties, such as clay, organic C, Fe, Al and calcium carbonate content.

The continual application of P can result in an increase in soil test P above levels required

for crop uptake, which has an environmental ramifications.

Phosphorus Accumulation

In many parts of the world, concern and research focuses on manure application,

where the amount ofP added often exceeds crop removal rate on an annual basis. Many

areas with intensive confined animal operations, such as the Netherlands, Belgium, north-

eastern USA and Florida, now have soil P levels that are of environmental rather than

agronomic concern (Sharpley et al., 1994b). In 1994, Kingery et al. (1994) reported P

leaching to a depth of-60 cm in tall fescue pastures in the Sand Mountain region of

northern Alabama that had received long term-application (15-28 yr) of poultry litter.

Soil test P (Mehlich I) values in topsoils were extremely high (-230 mg/kg) relative to

optimum values for crop production in this region (25 mg/kg) (Cope et al., 1981).

Similarly, Eghball et al. (1996) measured soil test P (Olsen P) in the profile ofa Tripp

very fine sandy loam (a coarse-silty, mixed, mesic Aridic Haplustoll) that had received

long-term (>50 yr) application of cattle feedlot manure and/or fertilizer P. Crops grown

included sugarbeet, potato, and corn. Increases in soil test P were reported and the

increases were associated with P leaching to -75 cm with fertilizer P (superphosphate)

and to -1.0 m for manure or manure plus fertilizer P. Mozaffari and Sims (1994)

measured soil test P (Mehlich I) values with depth in cultivated and wooded soils on

farms on a coastal plains watershed dominated by intensive poultry production and








frequent applications of poultry litter, and observed P leaching to depth of-60 to 75 cm

in agricultural fields and a high soil test P values in topsoils relative to those considered

optimum for most agronomic crops (25 mg/Kg) (Sims and Gartley, 1996). In North

Carolina, King et al. (1990) examined the effect of 11 years of swine lagoon effluent

application on P distribution within the profile of a Paleudult soil used for coastal

bermuda grass pasture, and reported soil test P (Mehlich I) values much greater than

required for crop production (225-450 mg/kg as a function of effluent rate, vs. an

optimum soil test value of -20-25 mg/kg). Soil test P at the 15 to 30, 30 to 45, 45 to 60,

and 60 to 75 cm depths was <5 mg/kg in nearby unfertilized pasture. However, at the

same depths, soil test P was about 120, 75, 25, and 5 mg/kg at the lowest effluent rate

(335 kg N/ha per year) and 350, 175, 125, and 50 mg/kg at the highest effluent rate (1340

kg N/ha per year).

The same trend of P accumulation and leaching has also been shown in Florida

which has intensive agricultural activity, humid climate, frequent heavy rainfall, and

widespread use of irrigation and drainage. Several studies have shown the extent of P

leaching that can occur in deep, sandy soils. For example, a study by Wang et al. (1995)

found that high levels of P could be leached from surface (Ap) horizons of four sandy

Florida soils heavily loaded with dairy manure despite high pH and abundant Ca2 in

solid and solution phases. Total P (TP) ranged from 3144 to 1595 mg/kg. Further

investigation on the composition of the same samples by Harris et al. (1994) showed that

the dominance of noncrystalline Si and lack of crystalline Ca-P in the intensive area Ap

horizons constitute an unfavorable environment for P retention in these soils. The

crystallization of Ca-P may be inhibited by manure-derived component such as Mg,








organic acids, and Si. Nair et al. (1995) also studied the forms of P in soil profiles from

dairies of south Florida. The dairies selected were active (still operating at the time of

sampling) and abandoned (dairies that had not been operating for 4, 12, 18 yr prior to

sampling). Three components of each active dairy were sampled: intensive areas (areas

next to the barn where cattle are held immediately prior to milking), pasture (areas used

for grazing), and forage areas (used for forage production). Their result showed a TP for

the A horizon ranging from 3028 mg/kg for the active-intensive areas to 2933 mg/kg for

the abandoned-intensive areas. Total P content of the unimpacted soils (native) was in the

range of 15-59 mg/ kg for all horizons, with low values observed in the E horizon and

high values in the Bh horizon. Labile P content (defined as P in sorbed phase, which is

potentially mobile and bioavailable) in the Bh horizon of native forage and pasture areas

were less than 2% of the TP, while up to 10% of TP was found as labile P in surface

horizons. In intensive areas, up to 40% of the P was in the labile pool. Soil P content

varied both with soil depth and land use. Total P stored in the soil profile increased with

intensity of land use, with native unimpacted areas containing 44 g P m-2 (average profile

depth 99 cm), followed by forage (46 g P m'2; soil depth 94 cm) pasture (102 g P m'2; soil

depth 119 cm) and intensive areas (766g P m-2; soil depth 136 cm). Dairy lagoon effluent,

though its composition and P content is quite different from dairy manure could also

elevate the level of P in the soil. Dooley (1996) studied P accumulation and retention in a

wetland impacted by approximately 20 years of dairy lagoon effluent application and

showed that the wetland appeared to be exporting P to an adjacent stream. His study

concluded that in order to accomplish acceptable levels of treatment, the assimilative

capacity of the wetland must be considered.








Numerous studies on accumulation of P in soils amended with commercial

fertilizers and /or organic wastes, including some of the above-mentioned studies, have

been reviewed recently by Sims et al. (1998). He indicated clearly that the most common

agricultural situation associated with significant downward movement ofP has been the

accumulation of P to "very high" or "excessive" levels in soils from continuous

application of organic wastes (manure, litter, and municipal or industrial wastes and

waste waters).

Phosphorus Forms and Fractionation

In order to understand the potential for P transport, P forms have to be examined

and evaluated to develop an understanding of the stability of P in the soil of the area

adjacent to the water body. The objectives ofP fractionation in general are to provide

insight into the fate and transformation of P added to soils as fertilizers or manure,

estimate the availability of P to plants for agronomic purposes, estimate the potential for

P movement from erosion and through leaching, and provide information regarding the

interaction between P in sediments and the overlaying water in the case of aquatic

systems (Graetz and Nair, 1999). Fractionation schemes using various chemical extracts

have been developed through the years to quantify the different forms of P in soils. The

underlying assumption here is that inorganic P in soil consists of varying proportions of

three discrete classes of compounds, namely, phosphates ofFe, Al and Ca, some of which

could be occluded or enclosed within coatings of Fe oxides and hydrated oxides. These

chemical P forms are operationally defined and subject to broad interpretations.

Nevertheless, they offer a convenient means for obtaining significant information on P

chemistry of soils. For example, through a modification of Hieltjes and Lijklema (1980)

fractionation method Nair et al. (1995) examined soil phosphorus in soil from dairies of








south Florida and fractionated it into labile P, inorganic Fe/Al-P, Ca/Mg-P and residual-

P. This fractionation scheme offered significant information on the forms of P in soil

profiles from dairies of south Florida. The Hieltjies & Lijkiema (1980) scheme uses 1 M

NH4Cl to extract loosely bound and labile P. This fraction is believed to contain the water

soluble portion and the plant- available portion of TP in the sample. Sodium hydroxide is

the next step in the fractionation procedure. This extract contains both organic and

inorganic P forms. The inorganic P portion of the extract is believed to be associated with

Fe and Al, while the organic portion is believed to be fulvic-and humic bound.

Hydrochloric acid is the third step to remove calcium-bound phosphate. The remaining

soil can then be digested to measure any residual P. This portion of P is considered to be

highly resistant, organically bound.

The forms of P in soil profiles from dairies of south Florida illustrate the fate and

transport of P in these systems Nair et al. (1995). They identified the P forms in the soil

profile of differentially manure-impacted soils in the Okeechobee watershed of south

Florida. All soils were Spodosols, and soils were collected by horizon, A, E, Bh, and Bw.

Their results showed no statistical differences in the percentage of labile P (NH4Cl-

extractable P), the P that would most likely move from A horizon of the various

components. More P will be lost from the heavily manure-impacted intensive areas with

high TP values, than from the less impacted pasture, forage and native areas. They also

observed that the P would continue to be lost from dairies that have been abandoned for

considerable period of time. The P that leaves the surface horizon might be lost through

surface and subsurface drainage, and the portion that reaches the spodic (Bh) horizon will

be held as Al- and Fe-associated P, either in the inorganic or in the organic fraction. The








high percentage ofHCl-extractable P (Ca- and Mg-associated P) in the A horizon of the

intensive dairy component was also of potential concern. This P could be continuously

extracted by NH4CI or by water (Graetz and Nair, 1995), suggesting that about 80% of

the total soil P had the potential to move eventually with drainage water into Lake

Okeechobee.

Fractionation of P forms has been particularly useful in understanding the

transformation ofP added to soil, either in inorganic or organic amendments such as

manures. Zhang and Mackenzie (1997) used P fractionation and path analysis to compare

the behavior of fertilizer and manure-P in soils. Their results showed that P behaves

differently when added as manure, compared to inorganic fertilizer, which may affect the

depth of P movement through the soil profile. Simard et al. (1995) reported that a

significant portion of the P moving downward in soils receiving substantial amounts of

animal manure accumulated in labile forms such as water-soluble, Mehlich-3, and

NaHCO3 extractable P forms. Eghball et al. (1996) found that P from manure moved

deeper in the soil than P from chemical fertilizer in long term (>50 yr) studies.

Phosphorus Retention

P retention in soils is a result of many soil physical and chemical properties, such

as mineralogy, clay content, pH and organic matter content, that influence the P solubility

and adsorption reactions. Consequently, these soil properties also affect solution P

concentration., P availability and recovery of P fertilizer by crop (Tisdale et al., 1993).

The term frequently used to describe surface adsorption and precipition reactions

collectively is P fixation or retention. The term adsorption and chemisorption also have

been used to describe P reaction with mineral surfaces, where chemisorption generally

represents a greater degree of bonding to the mineral surface. The term sorption has been








used to describe adsorption and chemisorption collectively. Adsorption is the preferred

term (Tisdale et al., 1993). There is considerable evidence suggesting that, P retention is a

continuous sequence of precipitation and adsorption. With low-solution P concentration,

adsorption probably dominates, while precipitation reaction proceed when the

concentration of P and associated cations in the soil solution exceeds that of the solubility

product (Ksp) of the mineral. Mineral solubility represents the concentration of ions

contained in the mineral that is maintained in solution. Each P mineral will support a

specific ion concentration which depends on the solubility product of the mineral. The

most common P minerals found in acid soil are Al-and Fe-P minerals, while Ca-P

minerals predominate in neutral and calcareous soils. But, the specific P minerals present

in the soil and the concentration of solution P supported by these minerals are highly

dependent on solution pH (Tisdale et al., 1993).

Phosphorus sorption may be determined by single point adsorption isotherm or

multi-point adsorption isotherms and can be described by several different adsorption

equations; all are based on the fundamental equation:

q = f(C)

where q is the quantity of P adsorbed at P concentration C.

One of the earliest equations used in soil studies is the Freundlich equation,

q= acb

The amount of P adsorbed per unit weight of soil is q, c is the P concentration in

solution, and a and b are constant which vary from soil to soil. The Freundlich equation

was introduced as a purely empirical equation. It implies that the energy of adsorption

decrease exponentially with increasing saturation of the surface. However, no maximum








capacity of adsorption can be calculated because the amount of adsorption increases with

the adsorbing ions in the solution (Yuan and Lucas, 1982). Therefore, it applies well only

over a limited concentration range of ions to be adsorbed. For this reason, the Langmuir

equation, which is based on the assumption that adsorption is on localized sites, the

energy of adsorption is constant, and the maximum adsorption possible corresponds to a

complete monomolecular layer is often preferred for the description of soil P adsorption.

In its linear form, the regression line would provide a means to calculate not only the

maximum adsorption but also a constant which is assumed to be related to the bonding

energy of the surface for P in solution. The equation describes a finite limit to adsorption

so that a maximum value may be obtained (Yuan and Lucas, 1982). Although there are

several linear forms, they are all derived from the basic expression:

q = kbc/(1+kc)

where q and c are as in the Freundlich equation, b is the "P adsorption maximum", and k

is a constant related to bonding energy.

The Temkin equation, as proposed for use in soil-P system by Bache and

Williams (1971), also implies that the energy of adsorption decreases as the amount of P

sorbed increases. In the middle range of P sorption, the equation may be expressed as

q/b = (RT/B)ln Ac

where A and B are constant and b, c and q are as in the Langmuir equation. All three

equations require that equilibrium conditions exist, a state that is rarely achieved in soil-P

adsorption studies. Another assumption common to the three equations is that the

adsorption is reversible; however some portion of the P adsorbed by soil is irreversibly

adsorbed. Despite these and other disadvantages, the three equations have been useful in








describing the relationship between c and q over limited range of concentrations (Olsen

and Khasawneh, 1980).

In Florida, the P retention characteristics of upland and wetland soils and stream

sediment in the Lake Okeechobee Watershed (maximum P retention capacity [Smax] and

equilibrium P concentration [EPCo]) have been a point of interest for several studies

(Reddy et al., 1996). The Smax of Bh horizons was about three to four times higher than

the surface A and E horizons. High EPCo (equilibrium concentration when net adsorption

equal zero) values for soils in the A and E horizons suggest poor retention capacity, while

low EPCo values of the Bh horizon indicate strong affinity for P. The Swxwas found to

be highly correlated with oxalate-extractable Fe and Al, and total carbonate of the soil.

Oxalate-extractable Fe and Al represent amorphous and poorly crystalline forms. Many

soils effectively retain P due to the presence of mineral components with high surface

affinity for orthophosphate. However, movement of P from dairy farms to aquatic

systems does occur under certain conditions, and has been linked to eutrophication of

surface water. This movement may be related to erosion or to subsurface transport.

Subsurface transport of P can be significant in sandy soils due a paucity of P-retaining

components (Reddy et al., 1996).

Sandy soils generally retain less P than finer textured soils because of a deficiency

of mineral components having surface affinity for orthophosphate. In a 1982 study by

Yuan and Lucas pertaining to the retention of phosphate by thirty Florida sandy soil as

evaluated by adsorption isotherms showed that the simple linear Freundlich equation

describe the P adsorption properties of sandy soil more successfully than the Langmuir

equation. The adsorption maximum values obtained from the Freundlich equation were








correlated with soil properties. A significant relationship was found with clay content but

not with double acid extractable Al, Fe, Ca and Mg, individually or combined. However,

for soils with a pH below 5.5, the adsorption maximum had a significant relationship with

extractable Al. A study on P retention as related to morphology and taxonomy of sandy

coastal plain soil materials by Harris et al (1996) distinguished between two groups of

uncoated Quartzipesamments (< 5% silt-plus-clay); those having "clean" (coating-free)

and "slightly-coated" grains. All clean samples readily desorbed P regardless of origin or

amount adsorbed. Sand-grain coatings significantly enhanced P adsorption and resistance

to desorption. Thus, clean sands pose a greater hazard for P leaching than sands with

grain coatings. Clay content was closely related to P adsorption, but silt content was not.

The P-retention distinction between clean and other Quartzipsamments is more marked

than uncoated vs. coated family criterion. The distinction between clean and other sandy

materials was more discrete and consistent for P desorption behavior than for adsorption.

A P-adsorption measurement such as the RPA (Rapid Chemical Assessment of Relative

Phosphorus Adsorption [single-point isotherm]) would provide a reasonably valid

assessment of P retention for slightly-coated and coated sand materials if appropriately

calibrated. The RPA effectively arrayed sandy Florida soil samples with respect to

relative P adsorption. A single-point isotherm could effectively index these sandy

materials. It does not directly provide values for maximum P adsorption, but it closely

relates to such values derived from P adsorption isotherm for the same sandy soil studied

(Harris et al., 1996).

A recent study by Nair et al. (1998) conducted on Spodosols in the Lake

Okeechobee basin to evaluate the P retention capacity of manure impacted Bh horizons








under aerobic and anaerobic conditions found that a high watertable decreased the P

retention for the majority of the soils in that study. High manure-impacted areas have Bh

horizons with high P concentrations as a result of P movement from the surface A

horizon through the eluted E horizon. The P appeared to be temporarily retained and

could be released upon prolonged contact with water. Another study by Nair et al. (1999)

of Spodosols in the same basin showed that the surface A and E horizons of manure-

impacted soils had essentially no sorbing capacity while the Bh (spodic) and Bw horizons

had mean Smx values 430 and 385 mg/kg, respectively. The P retention characteristics of

these soils were determined by using both single-point (1000 mg P/kg or 100 mg P/L)

and traditional Langmuir isotherms. Phosphorus sorption values using a single high P

solution had approximately a 1:1 relationship with values obtained for the maximum

retention capacity (Sma) obtained from Langmuir isotherms.

In response to the fact that the P sorption capacity of soils is not unlimited, and

based on documented accumulation and leaching of P in soils of areas dominated by

concentrated animal production, a new approach to sorption capacity was developed. The

concept of Degree of P Saturation (DPS) is based on the fact that the potential for soil-P

desorption increases as sorbed P accumulates in soil (Van der Zee et al., 1987;

Breeuwsma and Silva, 1992). Degree of P saturation is defined as the ratio of extractable

P to the sum of extractable Fe and Al expressed as an percentage. The critical DPS

threshold has been defined as the saturation percentage that should not be exceeded to

prevent adverse effect on ground water quality with the specific goal that the phosphate

concentration in the ground water should not exceed 0.01 mg/L of orthophosphate at the

level of the mean high watertable (Breeuswma et al., 1995). A critical DPS value of 25%








has been used in the Netherlands to determine the surplus of P that can be applied to

varying soil types before P saturation, and thus significant P export in subsurface runoff,

can be expected to occur.

Operationally, DPS is defined as oxalate-extractable P divided by the phosphate

sorption capacity of the soil that is estimated from equations including oxalate-

extractable Fe and Al (Breeuwsma et al., 1995).


DPS = Extractable soil P X 100
P sorption maximum


The extractable P (Pox) is determined by extraction by 0.2 M ammonium oxalate

buffered to pH 3.0. Phosphorus sorption capacity is determined by standard P adsorption

isotherms or estimated by oxalate-extractable Al (Alox) and Fe (Feox ) and the DPS

expressed as:

Pox
DPS = X 100
a (Fe ox + Al x)


The saturation factor a, as defined by Sjoerd et al. (1988), is the ratio of the

amount of P that is sorbed in laboratory experiments and the P already present as Pox to

(Feox + Alox). Thus a is a variable that allows comparison of different soils with respect to

P saturation, and the result will then be normalized with respect to the reactive soil

constituents. However, as pointed out by Sjoerd et al. (1988), the proportionality factor a

is both concentration and time dependent. Pautler and Sims (1998) used an a value

ranging from 0.4-0.6 for soils of the Atlantic coastal plain.








An added advantage of the DPS approach is that it not only describes the potential

for P release from soil but also indicates how close the P-sorption sites of a soil are to

being saturated (Sibbesen and Sharpley, 1997). Citing data from numerous studies in the

Netherlands, showed that more than 80% of the soils in a watershed with intensive

livestock production were saturated with P (Breeuwsma et al., 1995). During winter

months, when groundwater discharge to surface waters was highest, concentration of TP

in the shallow groundwater to exceeded surface water quality standards (0.15 mg/L of

TP). Lookman et al. (1995) applied the DPS approach to a 700 Km2 area (primarily

grassland used for intensified animal agriculture) in northern Belgium. Based on a critical

DPS value of 25%, they estimated that >75% of the soils were considered to be saturated

with P to the depth of the highest average groundwater table. Lookman et al. (1996)

showed that the DPS of the same soils of their 1995 study (Lookman et al., 1995) at the

0-30 cm depth was highly correlated with soluble P in these soils. Sharpley (1995) also

found a single relationship (r2 of 0.86) describing the concentration of dissolved

phosphate (DP) as a function of P-sorption saturation for ten soils ranging from sandy

loam to clay in texture. He used Mehlich-3 as extractable soil P and the Langmuir P-

sorption maximum as P-sorption capacity in his calculation of P-sorption saturation.

Comparison of short-and long-term sorption kinetics in Atlantic coastal plain soils

showed that the potential for P loss from over-fertilized soils can be improved by a

knowledge of the degree of P saturation of the soils (Pautler and Sims, 1998).

Downward P movement

Loss of P from land can occur in three ways; as water-soluble and/or particulate P

in surface runoff, as water-soluble and/or particulate P in subsurface runoff (leaching),

and as water-soluble and/or particulate P in flow to groundwater, referring to P picked up








by water that passes to the water-table and which is subsequently discharged to streams,

rivers or lakes as seepage (Ryden et al., 1973). Phosphorus leaching has normally been

considered to be inconsequential in most soils, but recent studies show that there are

combinations of agriculture management practices, soil proporities, and climatic

conditions that can result in significant accumulation in subsoils. Whether or not P that

leaches into subsurface horizons is later transported to water bodies depends on the depth

of leaching and the hydrological connections of the watershed (Sims et al., 1998). As

mentioned above in the section on P accumulation, numerous studies on accumulation of

P in soils amended with commercial fertilizers and/or organic wastes have been reviewed

recently by Sims et al., (1998). This indicated clearly that the most common agricultural

situation associated with significant downward movement ofP has been the accumulation

of P to "very high" or "excessive" levels in soils from continuous application of organic

wastes (manure, litter, and municipal or industrial wastes and waste waters). Studies by

Kingery et al. (1994), Eghball et al. (1996), Mozaffari and Sims (1994), and King et al.

(1990) report P leaching to-75 cm depending upon other factors such as soil type and P

accumulated in the surface horizon. Furthermore, Eghball et al. (1996) suggested a

greater downward mobility for organic forms of P. Previous studies from Florida also

illustrated the extent of P leaching that can occur in deep, sandy soils. One of the earliest

studies in Florida was of Bryan (1933) who reported P leaching to depths of at least 90

cm in heavily fertilized citrus groves of varying ages. Humpherys and Pritchett (1971), in

their study of six soil series in northern Florida, 6 to 10 years after applying

superphosphate, reported extensive P leaching and subsequent accumulation in the spodic

horizon of a Leon fine sand and that all fertilizer P had leached below a depth of 50 cm in








Pomello and Myakka soil series. A study by Wang et al. (1994) found that high levels of

P could be leached from surface (Ap) horizons of four sandy Florida soils heavily loaded

with dairy manure despite high pH and abundant Ca2" in solid and solution phases.

Graetz and Nair (1995), Nair et al. (1995), Nair et al. (1998), and Nair et al. (1999), in a

series of studies on Spodosols in the Lake Okeechobee basin of Florida, concluded that P

that leaves the surface (A) horizon might be lost through surface and subsurface drainage,

and the portion that reaches the spodic (Bh) horizon will be held as Al- and Fe-associated

P, either in the inorganic or in the organic fraction. The high percentage of HCl-

extractable P (Ca- and Mg-associated P) in the A horizon of the intensive dairy

component was also of potential concern. This P could be continuously extracted by NH4

Cl or by water, suggesting that about 80% of the total soil P had the potential to move

eventually with drainage water into Lake Okeechobee (Graetz and Nair, 1995).

Recently, Sims et al. (1998) reviewed some current research on P leaching and

loss in subsurface runoff in Delaware, Indiana, and Quebec and concluded that the

situation most commonly associated with extensive P leaching, and thus the increased

potential for P loss via subsurface runoff, has been the long-term use of animal manures.

Manure Management

Developing manure management plans that are agronomically, economically, and

environmentally sound is a challenge because issues like accelerated eutrophication, P or

N limitation, transport mechanisms, source management, soil P level, environmental soil

testing for P, manure management and land application of manure have to be considered.

This review of the literature shows the urgent need for research especially in areas of

intensified dairy production and deep, coated sandy soil. Many factors can be involved in

developing an environmentally sound plan for manure management. Animal manure can








be a valuable resource if it can be integrated in cost effective best management practices.

Uptake of nutrients by agronomic crop sequenced over time is an effective, economical,

and environmentally sound means of nutrient recovery, especially if the cropping system

met the environmental concerns. The environmental concerns can be meet by maximizing

nutrient uptake by the crops while meeting the need of dairy producers.

A recent two years study on the use of dairy manure effluent in a rhizoma

(perennial) peanut based cropping system (French et. al. 1995) suggests that, ifN

pollution is the major concern in a particular area, then the PP-R cropping system (year-

round perennial peanut and rye) would be a good choice since it performed as well or

better than the C-FS-R (corn, forage sorghum, and winter rye) and C-PP-R (corn planted

into a perennial peanut sod, perennial peanut, and rye) systems. However, if P is the

major concern, the C-FS-R and C-PP-R systems would be better choices. The C-FS-R

and C-PP-R systems were superior to the PP-R rotation in P removal values. Though P

level in perennial peanut forage were generally higher than those in corn and forage

sorghum, they were not high enough to compensate for the much lower annual dry matter

yield of the perennial peanut system.


Dissertation Format

The subsequent chapters in this dissertation were prepared as individual

manuscripts. In this chapter, a general introduction, statement of the problem, review of

literature, and research objectives were presented. In chapter 2, the accumulation of P in a

sandy soil receiving dairy waste effluent was investigated. In chapter 3, the forms and

fractionation of P in the area under study were examined. In chapter 4, the retention

capacity of the soil was evaluated. In chapter 5, downward P movement was examined.





24


In chapter 6, plant uptake of the cropping systems under study was investigated. Chapter

7 provides a summary and conclusion of results presented in previous chapters.













CHAPTER 2
PHOSPHORUS ACCUMULATION IN A SANDY SOIL RECEIVING DAIRY
WASTE EFFLUENT


Introduction

The number of soils with plant-available P exceeding the levels required for

optimum crop yield has increased in areas of intensive agriculture and livestock

production (Sims, 1992; Snyder et al., 1993). In many parts of the world, concern and

research focuses on manure application, where amounts of P added often exceeded crop

removal rate on an annual basis. Many areas with intensive confined animal operations,

such as the Netherlands, Belgium, north-eastern USA and Florida, now have soil P levels

that are of environmental rather than agronomic concern (Sharpley et al., 1994b). In

1994, Kingery et al. (1994) reported P leaching to a depth of -60 cm in tall fescue

pastures in the Sand Mountain region of northern Alabama that had received long term-

application (15-28 yr) of poultry litter. Soil test P (STP) (Mehlich I) values in topsoils

were extremely high (-230 mg/kg) relative to optimum values for crop production in this

region (25 mg/kg) (Cope et al., 1981). Similarly, Eghball et al. (1996) measured STP

(Olsen P) in the profile ofa Tripp very fine sandy loam (a coarse-silty, mixed, mesic

Aridic Haplustoll) that had received long-term (>50 yr) application of cattle feedlot

manure and/or fertilizer P. Crops grown included sugarbeet, potato, and corn. Increases in

STP were reported and the increases were associated with P leaching to -75 cm with

fertilizer P (superphosphate) and to -1.0 m for manure or manure plus fertilizer P.

Mozaffari and Sims (1994) measured STP (Mehlich I) values with depth in cultivated and








wooded soils on farms in a coastal plains watershed dominated by intensive poultry

production and frequent applications of poultry litter, and observed P leaching to depth of

-60 to 75 cm in agricultural fields. STP (Mehlich I)values in these soils were very high

in topsoils relative to those considered optimum for most agronomic crops (25 mg/kg)

(Sims and Gartley, 1996). In North Carolina, King et al. (1990) examined the effect of 11

years of swine lagoon effluent application on P distribution within the profile of a

Paleudult used for coastal bermudagrass pasture. They reported STP (Mehlich I) values

much greater than required for crop production 225-450 mg/kg vs. an optimum soil test

value of-20-25 mg/kg. Soil test P at the 15 to 30, 30 to 45, 45 to 60, and 60 to 75 cm

depths was <5 mg/kg in nearby unfertilized pasture. However at the same depths, STP

was about 120, 75, 25, and 5 mg/kg at the lowest effluent rate (335 kg N/ha per year) and

350, 175, 125, and 50 mg/kg at the highest effluent rate (1340 kg N/ha per year).

Phosphorus loading from dairy lagoon effluent to soils in the Lake Okeechobee Basin,

Florida resulted in significant accumulation of P. In some cases; P concentrations were

about 50 times that ofunimpacted areas (Graetz and Nair, 1995).

A considerable body of research now shows that STP levels influence the amount

of P in runoff water and subsurface drainage (Pote et al., 1996 ; Sharpley et al., 1977;

Heckrath et al., 1995). Therefore, STP could help identify areas of potential losses of P.

This study was initiated to investigate the accumulation ofP in the soil profile

during application of dairy waste effluent to two cropping sequences at two N rates in a

deep sandy soil.








Materials and Methods

Experiment Location and Design

The study was located at the North Florida Holstein Dairy facility, which is two

miles south of Bell, Florida. A randomized block design containing three blocks and

arranged as a split plot was used as the experimental design. Main plots were N loading

rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste effluent

was used as the N source. The N application rates were 448 and 896 kg/ha/yr which

correspond to P loadings of 112 and 224 kg/ha. The cropping systems were corn- forage

sorghum-rye and perennial peanut-rye.

Soil Selection and Sampling

The soil was mapped as a Kershaw sand (sandy, thermic, uncoated Typic

Quartzipsamments). Soil profile samples (0-15, 15-30, 30-45, 45-60, 60-80, 80-100 cm)

were collected from each treatment in 1996 (prior to effluent application) and in 1997 and

1998 (after effluent application). Soil from three profiles in each subplot was collected,

composite, mixed thoroughly and a 1-kg subsample was brought to the laboratory for

analysis. Soil samples were air-dried and sieved (2mm) prior to analysis. Soil samples

were also collected in a similar manner from an adjacent native area believed to be

unimpacted by manure or fertilization application.

Soil Characterization

Texture was determined using the pipette method (Day, 1965). Total phosphorus

(TP) was determined by ashing 1.0 g of soil for 3 hours and then solubilizing with 6 M

HCI (Anderson, 1976). Double-acid (Mehlich I)-extractable P, Al, Fe, Ca and Mg were

obtained with a 1:4 soil/double acid ratio (Mehlich, 1953). Phosphorus (P) in solution

was analyzed by the molybdenum-blue method (Murphy and Riley, 1962). Soil pH was








determined on 1:2 soil/water ratio, and the organic carbon content of the air-dried

samples was determined by combustion (Broadbent, 1965).

Effluent Application and Characterization

Effluent was taken directly from the dairy waste pond on the farm in which the

manure flushed from the milking parlor and feed barn is collected. The effluent was

applied to the experimental area through a center pivot irrigation system. The annual

application of effluent ranged between 355 to 500 mm depending on N application rate

and the concentration ofN in the effluent. The average annual concentration ofTP

ranged from 56 mg/L in 1996 to 49 mg/L in 1998, and the soluble reactive phosphorus

(SRP) from 44 in 1996 to 47 mg/L in 1998 (Table 2-1).


Table 2-1. Average annual concentrations (mg/L) of ammonium nitrogen (NH4 -N), total
Kjeldahl nitrogen (TKN), soluble reactive P (SRP), and total P (TP) in effluent applied to
the study site. Numbers in parentheses are standard deviations.

NH4-N TKN SRP TP
YEAR
mg/L

1996 172(48) 258(84) 44(14) 56(20)

1997 176(40) 302(75) 44(12) 55(18)

1998 192(51) 280(69) 47(6) 49(20)



Statistical Analysis

Data analyses were done using SAS program (SAS Institute Inc. 1985) (PROC

MIXED) procedure (SAS Institute Inc. 1992). The PROC MIXED procedure was

selected based on the fact that it is designed for a mixed effect model where random








terms are incorporated into inference from the outset. Contrast, least square means and

estimates of linear combinations are reported with correct standard errors. The GLM

(General linear Model) which is designed for a fixed effect model, with allowance for

certain adjustments in the presence of random terms, needs special attention to be given

to least square means and contrast since their standard errors are not necessarily correct.

This is true, for example, for split-plot design as is the case for the experimental design in

this study (Schabenberger, 1996).

The main difference between of PROC MIXED and PROC GLM is that PROC

MIXED estimation of variance is based on maximum likelihood while PROC GLM is

based on method of moments estimation (ANOVA method) of solving expected mean

squares for the variance components (Schabenberger, 1996). Another advantage of PROC

MIXED is that it allows data that are missing at random while PROC GLM requires

balanced data, and ignore subjects with missing data (Wolfinger and Chang, 1996). This

criteria for PROC MIXED was of interest in handling the analysis of this study. This

study is a component of a larger project, which include three main treatments (effluent

application rate) and five cropping systems as a sub treatments in a split plot design with

the aim of comparing their effectiveness in nutrient recovery and maintenance of

acceptable levels of N and P in ground water. However, for the purpose of this study, two

effluent application rate and two cropping systems were selected under the original

experimental design. The selection of PROC MIXED to analyze data of the study offered

a means of dealing with unbalanced data. The model used in the analysis included: date,

block, rate, crop, and depth and their interactions such as date*rate, date*crop, crop*rate,








date*depth, rate*depth, crop*depth, date*crop*rate, date*rate*depth, date*crop*depth,

crop*rate*depth, and date*crop*rate*depth.


Results and Discussion

The study site soil was mapped as Kershaw sand (sandy, thermic, uncoated Typic

Quartzipsamments) in the Gilchrist County soil survey report (Soil Survey Staff, Gilchrist

County, Florida, 1973). Since the publication of the report, the criterion for coated vs.

uncoated family placement has been changed for the USDA soil taxonomic system (Soil

Survey Staff, 1999). The sandy materials sampled in this study would meet the criterion

for coated (5 percent silt plus 2 times the clay content), based on the particle size analysis

(Table 2-2). Also, some auger borings to 2 m revealed spodic horizons which indicated

inclusions of Spodosols, and dark colors in the surface horizon in some areas qualify it to

be an Umberic epipedon, which would result in classification as an Inceptisol (Umbrept)

rather than a Psamment. Nevertheless, the soil was consistently sandy and similar to

Kershaw sand with respect to use and management.

Soil Properties Prior to Effluent Application

The soil from the study site prior to effluent application had a different chemical

composition than a soil samples from a native site (Table 2-3). Double acid (Mehlich I)-

extractable elements and TP concentrations for the study site prior to the application of

effluent were higher than the concentrations in soil from the native site (Table 2-3). For

example, Mehlich I-extractable Ca for the study site ranged from 968 mg/kg at the

surface horizon to 75 mg/kg at the lower depth of the profile (100 cm). Comparable

values for the native site were 12 and 4 mg/kg, respectively (Table 2-3). Differences in

Ca and Mg content between the native site and the study site prior to the application of











Table 2-2. Selected characteristics of typical Kershaw sand (Soil Survey Staff, Gilchrist
County, Florida, 1973) compared to the study site.

Location Horizon Depth pH Org. C SAND SILT CLAY
cm


Native A 0-18 4.8 0.99 96.5 1.1 2.4

C1 18-76 5.0 0.39 96.1 1.8 2.1

C2 76-147 4.9 0.16 97.3 0.4 2.3

C3 147-203 5.0 0.10 96.1 2.0 1.9

Study Site Al 0-15 6.2 1.54 93.1 4.8 2.0

A2 15-30 6.0 0.79 94.1 4.2 1.7

C1 30-45 6.5 0.71 95.3 3.1 1.6

C1 45-60 6.5 1.58 95.0 3.8 1.2

C2 60-80 6.6 0.54 95.4 2.7 1.9

C2 80-100 6.5 0.43 95.9 2.4 1.7











Table 2-3. Mehlich I-extractable elements concentrations and total P (TP) in "native" soil
(n = 3 profiles) and study site (n = 12 profiles) soil profiles prior to beginning of the
study.
Location Depth Ca Mg Al Fe P TP
cm

(mg/ kg)

Native 0-15 11.7 1.9 267 18.4 47 214

15-30 5.1 1.1 317 20.7 52 270

30-45 6.0 0.8 330 19.1 39 241

45-60 4.7 0.7 337 16.3 36 184

60-80 4.7 0.8 308 16.3 39 181

80-100 4.1 0.7 280 14.3 33 173


Study 0-15 968 115 301 23.5 283 328
Site
15-30 522 69.3 280 22.8 184 254

30-45 208 34.1 203 19.6 75 154

45-60 135 25.7 161 17.9 37 254

60-80 103 22.9 133 15.9 20 218

80-100 75 19.2 117 14.5 12 192








effluent were also reflected in a higher pH in all horizons in the study site. The higher

pH and organic C in all horizons of the soil from the study site prior to effluent

application could be attributed to a previous manure application. Dairy manure can

appreciably elevate not only the P, but also other components in soils (Dantzman et al.,

1983; Wang et al., 1995). The elevated level ofP (TP and Mehlich I- extractable P) in the

soil of the study site indicated a previous manure application (Table 2-3). The site

appeared to havebeen heavily loaded with animal waste prior to the start of this study (47

mg/kg Mehlich I-extractable P in the native area vs 283 mg/kg Mehlich I-extractable P in

study site surface horizon soils). Several studies (Sims, 1992; Snyder et al., 1993;

Sharpley et al., 1994b; Kingery et al., 1994; Graetz & Nair, 1995; Wang et al., 1995)

have shown that manure application usually results in an increase in TP, STP and other

components in soil.

Effect of Application Rate and Cropping Systems

Statistical evaluation of TP data (Table 2-4) shows that date and depth were

significant at the 0.0001 probability level, but date*depth and date*crop was also

significant at 0.0001. However, neither the single effect of crop (cropping system), nor

the rate (effluent application rate) was significant. Therefore, a higher level of

significance such as date*depth and date*crop will be reported and interpreted, when it

was appropriate. Means comparison was done when there was a significant interaction by

SAS code (pdiff) for differences between least squares means (LSM).

Total P (TP) increased over time (1996 vs. 1998). The effect of date*depth was

significant (P <0.01) to the depth of 45 cm which reflects a buildup of total P in the soil

profile. Also, the effect ofdate*crop was significant (P<0.01) which might imply a role





34-


Table 2-4. Statistical evaluation of TP data for the three-year study period.

Source NDF DDF Type II F Pr > F

Date 2 96 36.31 0.0001
Block 2 2 0.46 0.6867
Rate 1 2 0.37 0.6063
Date*Rate 2 96 2.65 0.0760
Crop 1 44 0.15 0.7001
Date*Crop 2 96 7.47 0.0010
Crop*Rate 1 44 1.18 0.237
Date*Crop*Rate 2 96 0.83 0.4412
Depth 5 44 46.25 0.0001
Date*Depth 10 96 15.82 0.0001
Rate*Depth 5 44 1.21 0.3226
Date*Rate*Depth 10 96 1.14 0.3395
Crop*Depth 5 44 0.84 0.5263
Date*Crop*Depth 10 96 1.69 0.0937
Crop*Rate*Depth 5 44 0.6 0.6410
Date*Crop*Rate*Depth 10 96 1.08 0.3853








for the cropping system on P removal. The application of effluent at both rates (448 and

896 kg N/ha per year) increased TP content of the s6il and the increase was dependent on

the effluent application rate. Total P in the surface horizon increased from 312 to 753

mg/kg at the end of the study under the high application rate (Fig. 2-1) and from 343 to

485 mg/kg under the low application rate (Fig. 2-2). A higher TP content in soil impacted

by dairy waste application is common. Graetz and Nair (1995) reported up to 1885 mg/kg

of TP in the soil surface horizon of dairy intensive areas.

The application of effluent also had an effect on Mehlich I-extractable P. The

effect of date*depth (P<0.05) and rate*crop (P<0.01) on Mehlich I-extractable P were

significant. During the two year of effluent application, Mehlich I-extractable P

decreased in the surface horizon but increased in the lower horizons (Fig. 2-3). The

decrease of Mehlich I-extractable P in the surface horizon and the increase in the lower

depths of the profile may be attributed to both crop uptake of P and the leaching effect of

effluent irrigation. Mozaffari and Sims (1994) measured soil test P (Mehlich I) values

with depth in cultivated and wooded soils on farms impacted by poultry litter

applications, and observed leaching to depth of- 60 to 75 cm. Soil test P values were

very high in topsoils relative to those considered optimum for most crops. Also, King et

al. (1990) examined the effect of 11 years of swine lagoon application on P distribution

and reported soil test P (Mehlich I) values much greater than required for crop production

(225-450) mg/kg. Soil test P at the 15-30, 30-45, 45-60, and 60-75 cm depth was 120,

75,25, and 5 mg/kg at the lowest effluent rate (335 kg N/ha per year) and 350, 175, 125,

and 50 mg/kg at the highest effluent rate (1340 kg N/ha per year). Soil test P (Mehlich I)

values for soil samples from the study site at 15-30, 30-45, 45-60, and 60-80 cm depth
























TP, mglkg
0 100 200 300 400 500
0


20



E4-

60 -


80


100


120


600 700 800 900


-*-1996 -- 1997 -A-1998
Figure 2-1. Average total P (TP) concentrations in the soil profile under the high rate
application prior to application of effluent (1996) and after effluent application (1997 and
1998). Values are LSM Std. Error.






















0 100 200


TP, mgkg
300 400


-1996 -0-1997 -4-1998
Figure 2-2. Average total P (TP) concentrations in the soil profile under the low rate
application prior to application of effluent (1996) and after effluent application (1997 and
1998). Values are LSM Std. Error.






















DA-P, mglkg
50 100 150 200


250 300 350


Figure 2-3. Mehlich I-extractable P concentrations in the soil profile prior to start of the
study and after two years of effluent application (1998). Values are LSM Std. Error.








were 197, 93, 55, and 32 mg/kg at the highest rate (896 kg N/ha per year) and 157, 62, 41

and 22 at the lowest rate (448 kg N/ha per year). These values of soil test P for the soil

samples from the study site after two year of effluent application should be looked at in

the context of high Mechlich I extractable P existing prior to the start of the study (Table

2-3). However, as for the rate*crop effect, Mehlich I-extractable P concentration was

higher for P-R (perennial peanut-rye) than for C-FS-R (corn-forage sorghum-rye)

cropping system under the high rate application (Fig. 2-4). This finding suggests that the

C-FS-R (corn-forage sorghum-rye) cropping system may be more effective in P removal

than the P-R cropping system. Only a slight change in Mehlich I-extractable P between

the two cropping systems was observed under the low application rate (Fig. 2-5). In spite

of the suggested higher P removal by the C-FS-R cropping system than the P-R cropping

system, the level of double acid (Mehlich I)-extractable P concentration in the study prior

to effluent application is considered to be extremely high relative to the optimum for crop

production when compared to levels reported by other studies (Kingery et al., 1994;

Mozaffari and Sims, 1994) and the removal by the cropping systems did not alter the high

level of STP. Such high level of STP can lead to leaching to a deeper depth in the soil

profile.

Although double acid may not extract the total amounts of reactive elements for P

retention, double-acid (Mehlich I)- extractable P was highly correlated with Ca, Mg, Al,

and Fe extracted by Mehlich I solution, with 93% of variability explained by this

relationship (Table 2-5).






40
















P, mglkg
0 50 100 150 200 250


1


300 350 400 450 500


-*-P-R --C-FSR

Figure 2-4. Mehlich I-extractable P concentrations for cropping systems under the high
rate effluent application in 1998. Values are LSM Std. Error.






























P, mglkg
0 50 100 150 200 250 300

0

20


40


so-
U'


s0


100


120-

I -P-R -I- C-FS-R

Figure 2-5. Mehlich I-extractable P concentrations for cropping systems under the low
rate effluent application in 1998. Values are LSM Std. Error.


--











Table 2-5. Regression equation relating Mehlich I-P to the independent variables Mehlich
I-Ca, Mg, and Fe. (n=432).
Equation ._____________ Model R
M I-P = -56.9 + 0.272 M I-Ca*** 0.284 M I-Mg* + 0.233 M I-Al*** + 0.932***
1.55 M I-Fe***
***, *, Significant atp< 0.001, andp< 0.05 respectively. N.S. Not significant.




Summary and Conclusions

The soil at the study site has been mapped as Kershaw sand and is considered

uncoated. However, some coatings are evident based on the color of the sand grain and

the USDA taxonomic criterion of>5% silt plus (2 times the clay content) for coated

family placement (Soil Survey Staff, 1999). Sands that retain coating components should

have a higher affinity to retain P than do bare quartz grains (Harris et al., 1996), a

criterion that is favorable for this study. The soil at the study site appeared to have been

heavily loaded with animal waste prior to the start of this study. Mehlich I-extractable P

in the surface horizon of the native area was 47 mg/kg vs. 283 mg/kg Mehlich I-

extractable P in the study site surface horizon soils. Mehlich I-extractable P levels in

topsoils at the study site was high relative to those considered optimum for agronomic

crops and raise the question about the suitability of the effluent application rates used.

The effluent application rates selected were based mainly on estimated N removal for the

forage crops within the cropping systems and experimental purposes outlined in the main

project objectives.

The previous application of dairy manure to the study site prior to the start of the

study resulted also in a higher Ca+2 and Mg+2 content throughout the soil profile








compared to the native site, although the amount and date could not be established. The

application of dairy waste effluent at both rates (448 and 896 kg N/ha per year) over a 2-

year period increased the TP content in the soil profile to the 45 cm depth. The increase

in TP was significant and dependent on the effluent application rate. The application of

effluent also had an effect on the Mehlich I-extractable P. The effect ofdate*depth and

rate*crop on Mehlich I-extractable P were significant. During the two year of effluent

application Mehlich I-extractable P decreased in the surface horizon but increased in the

lower horizons. The decrease of Mehlich I-extractable P in the surface horizon and the

increase in the lower depths of the profile may be attributed to both crop uptake of P and

the leaching effect of effluent irrigation. However, as for the rate*crop effect, Mehlich I-

extractable P concentrations were higher for P-R (perennial peanut-rye) than for C-FS-R

(corn-forage sorghum-rye) cropping system under the high rate application. This finding

suggests that the C-FS-R (corn-forage sorghum-rye) cropping system may be more

effective in P removal than the P-R cropping system. Only a slight change in Mehlich I-

extractable P between the two cropping systems was observed under the low application

rate. However, the removal by the cropping systems did not alter the high level of STP

that already existed. Thus, to prevent an accumulation of excessive P content in the soil

profile, history of the land, application rate, and cropping systems estimated removal of P

should be considered.













CHAPTER 3
PHOSPHORUS FORMS AND FRACTIONATION IN A SANDY SOIL RECEIVING
DAIRY WASTE EFFLUENT


Introduction

Sequential extraction schemes using various chemical extracts have been

developed through the years to quantify and fractionate the different forms of P in soils.

The objectives ofP fractionation in general are to provide insight into the fate and

transformation of P added to soils as fertilizers or manure, estimate the availability of P to

plants for agronomic purposes, estimate the potential for P movement from erosion and

through leaching, and provide information regarding the interaction between P in

sediments and the overlaying water in the case of aquatic systems (Graetz and Nair,

1999). The underlying assumption here is that inorganic P in soil consists of varying

proportion of three discrete classes of compounds, namely, Fe, Al and Ca phosphate,

some of which could be occluded or enclosed within coating of Fe oxides and hydrated

oxides. These chemical P forms are operationally defined on the basis of reactivity of a

particular phase in a given extractant and subject to several interpretations. Nevertheless,

they offer a convenient means for obtaining significant information on P chemistry of

soils (Nair et al., 1995). Fractionation of P forms has been particularly useful in

understanding the transformation of P added to soil, either in inorganic or organic

amendments such as manures. Zhang and Mackenzie (1997) used P fractionation and

path analysis to compare the behavior of fertilizer and manure-P in soils. Their results

showed that P behaves differently when added as manure, compared to inorganic








fertilizer, which may affect the depth of P movement through the soil profile. Simard et

al. (1995) reported that a significant portion of the P moving downward in soils receiving

substantial amounts of animal manure accumulated in labile forms such as water-soluble,

Mehlich-3, and NaHCO3 extractable P forms. Eghball et al. (1996) found that P from

manure moved deeper in the soil than P from chemical fertilizer in long term (>50 yr)

studies. Nair et al. (1995) studied the forms of P in soil profiles from dairies of south

Florida and illustrated the fate and transport of P in these systems. They identified the P

forms in the soil profile of differentially manure-impacted soils in the Okeechobee

watershed, Florida. All soils were Spodosols, and soils were collected by horizon, A, E,

Bh, and Bw. Their results showed no statistical differences in the percentage of labile P

(NH4 Cl-extractable P), the P that would most likely move from the A horizon of the

various components. The labile P form for the A horizon of all dairy components

averaged 9%. However, more P will be lost from the heavily manure-impacted intensive

areas with high total P values, than from the less impacted pasture, forage and native

areas. They also observed that the P would continue to be lost from dairies that have been

abandoned for a considerable period of time. The P that leaves the surface horizon might

be lost through surface and subsurface drainage, and the portion that reaches the spodic

(Bh) horizon will be held as Al- and Fe-associated P, either in the inorganic or in the

organic fraction. The high percentage ofHCl-extractable P (Ca- and Mg-associated P) in

the A horizon of the intensive dairy component was also of potential concern. Such P

could be continuously extracted by NH4CI or by water, suggesting that about 80% of the

total soil P had the potential to move eventually with drainage water into Lake

Okeechobee (Graetz and Nair, 1995).








Recently, other watersheds in Florida such as the Middle Suwannee River area

have become the focus of attention. Soils in this area include Entisols; soils lacking

diagnostic horizons and other features that are specifically defined and required for other

orders of the USDA taxonomic system (Soil Survey Staff, 1994). Quartzipsamments, the

only Psamment Great Group which occurs in Florida, are in central northern peninsular

Florida and most prevalent on well to excessively drained landscapes (Harris and Hurt,

1999). The sandy nature of Quartzipsamments result in relatively low P retention or

capacity. Therefore, an understanding of P forms in such soil receiving dairy manure

effluent application could help identify areas of potential losses of P.


Materials and Methods


Experiment Location and Design

The study site was located at North Florida Holstein Dairy facility, which is two

miles south of Bell, Florida. A randomized block design containing three blocks and

arranged as a split plot was used as the experimental design. Main plots were N and P

loading rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste

effluent was used as the N source. The N application rates were 448 and 896 kg/ha/yr,

which correspond to P loading of 112 and 224 kg/ha/yr. The cropping systems were corn-

forage sorghum-rye and perennial peanut-rye.

Soil Selection and Sampling

The soil was mapped as Kershaw (sandy, thermic, uncoated Typic

Quartzipsamments). Soil profile samples (0-15, 15-30, 30-45, 45-60, 60-80, 80-100 cm)

were collected in 1996 (prior to effluent application) and in 1997 and 1998 (after effluent

application). Soil from three profiles in each subplot was collected, composite, mixed








thoroughly and a 1-kg subsample was brought to the laboratory for analysis. Soil samples

were air-dried and sieved (2mm) prior to analysis. In addition to soil samples from the

study site, soil samples were also collected in a similar manner from an adjacent native

area believed to be unimpacted by manure or fertilization application.

Fractionation Scheme

The scheme used to fractionate soil-P was a modification of that ofHieltjes and

Lijklema (1980) by Nair et al., (1995). A 1-g air dried sample was sequentially extracted

twice with 25 mL of 1 MNH4CI (adjusted to pH 7.0) with two hours shaking, 0.1 M

NaOH with seventeen hours shaking, and 0.5 MHCI with 24 hours shaking. The 1: 25

soil: solution ratio was selected based on preliminary investigations as shown in

APPENDIX. After each extraction, the content were centrifuged for 15 min at 3620 x g

and filtered through a 0.45-pm filter. All extractions were carried out at room

temperature. Residual P was determined by ashing previously extracted soil sample for

three hours and then solubilizing with 6 M HCI (Anderson, 1976). A 5 mL of the NaOH

extract was also digested by persulfate-sulfuric acid mixture at 3800C (APHA, 1985) to

determine moderately labile organic P as the difference between P in digested and

undigested NaOH extract. NH4Cl-extractable P was defined as labile P (Petterson and

Istvanovics, 1988), NaOH-extractable P as Fe-Al-associated P, and HCl-extractable P as

Ca-Mg-associated P. Residual P is the P that is not readily removed by any of the above

chemical extractants. Total phosphorus (TP) was determined by ashing 1.0 g of soil for 3

hours and then solubilizing with 6 MHC1 (Anderson, 1976). Double-acid (Mehlich I)-

extractable P, Al, Fe, Ca and Mg were obtained with a 1:4 soil/double acid ratio

(Mehlich, 1953). Phosphorus (P) in solution was analyzed by the molybdenum-blue








method (Murphy and Riley, 1962) on a spectrophotometer at wavelength of 880 nm.. Soil

pH was determined on 1:2 soil/water ratio, and the organic carbon content of the air-dried

samples was determined by combustion procedure (Broadbent, 1965). Texture was

determined using the pipette method (Day, 1965).

Statistical Analysis

Data analyses were done using SAS program (SAS Institute Inc. 1985) (PROC

MIXED) procedure (SAS Institute Inc. 1992). Relationships among parameters were

evaluated using linear correlation. Multiple regression was used to examine the strength

of the relationships between parameters.


Results and Discussion

Inorganic Fe/Al associated P constituted the major proportion of TP in the soil

profile of the study site prior to effluent application. As concluded from Chapter 2, the

soil at the study site appeared to have been heavily loaded with animal waste prior to the

start of this study, although amount and dates could not be established. Phosphorus

originally present in the soil profile in 1996 (prior to effluent application) was largely in

the form of inorganic Fe/Al-associated P, which ranged from 292 mg/kg in the surface

horizon to 76 mg/kg in lower depth (100 cm) (Table 3-1). These values of Fe/Al- P

corresponded to 62% and 49% of TP, respectively (Table 3-2). The application of

effluent increased this fraction to 362 mg/kg in the surface horizon in 1998 with smaller

increase throughout the soil profile (Fig. 3-1). A comparison ofFe/Al-P mean

concentration in each depth within the soil profile at the beginning (1996) and end of the

study period (1998) showed that the increase was statistically significant (P <0.001-

P<0.05) at the surface and down to the 45 cm depth (Table 3-3). The predominance of











Table 3-1. P values (mg/kg) in each fraction within a soil depth increment at the
beginning (1996) and end of the study period (1998) (n = 12 profiles). Values are Least
Square Means (LSM).
Depth Labile Al-Fe Ca-Mg Residual
(cm) mg/kg

1996
0-15 85 292 50 36
15-30 61 221 30 22
30-45 36 146 21 16
45-60 44 106 12 25
60-80 37 87 09 29
80-100 37 76 12 25

1998

0-15 97 362 52 59
15-30 93 317 30 40
30-45 80 205 17 28
45-60 77 137 13 23
60-80 71 101 07 23
80-100 69 81 07 19











Table 3-2. Percentage of P in each fraction within a soil depth increment at the beginning
(1996) and end of the study period (1998)(n = 12 profiles). Values are Least Square
Means (LSM).
Depth Labile-P Al-Fe-P Ca-Mg-P Residual-P Sum of
(cm) % P fraction
mg/kg

1996
0-15 18.3 62.6 10.8 8.30 463
15-30 18.4 65.3 9.20 7.10 334
30-45 16.8 64.5 10.5 8.20 219
45-60 24.8 54.9 7.00 13.3 187
60-80 24.3 52.3 5.80 17.0 162
80-100 26.3 49.4 8.20 16.1 150

1998

0-15 17.0 63.5 9.1 10.3 570
15-30 19.4 66.0 6.2 8.30 480
30-45 24.2 62.1 5.1 8.50 330
45-60 30.8 54.8 5.2 9.20 250
60-80 35.1 50.0 3.5 11.4 202
80-100 39.2 46.0 4.0 10.8 176


























50 100 150


P, mg/kg
200 250


300 350 400 450
)L---- -----*---


1996 1998

Figure 3-1. Al-Fe-associated P (mg/kg) within the soil profile at the beginning 1996 and
end of the study period (1998). Values are LSM Std. Error.


0
20


20


40


60


80


100
loO
so~















Table 3-3. Increases in each fraction within a soil depth increment between the beginning
(1996) and end of the study period (1998).
Depth Labile Al-Fe Ca-Mg Residual
(cm) mg/kg mg/kg mg/kg mg/kg
0-15 11.75* 69.76** NS 22.31**
15-30 31.62** 95.69** NS 17.69**
30-45 44.55** 59.03** NS 23.9**
45-60 33.38** 31.0* NS NS
60-80 34.52** NS NS NS
80-100 31.44** NS NS NS
*, ** Significant at the .05 and .001 probability levels, respectively; NS = none
significant.








Fe/Al-associated P in surface horizon and throughout the profile was a reflection of the

properties of soil and the dairy waste effluent used. The soil at the study site, as

mentioned in Chapter 2, was classified as coated sand with low clay content, low organic

matter, pH of 6-6.5, and a higher Mehlich I- extractable P (Table 3-4) in comparison to

soil from a native area (283 vs. 47 mg/kg). The soil from the native area, which has a low

content of clay, organic matter, moderately low pH (4-4.5), and a high Mehlich I-

extractable Al/Fe, compared to the rest of cations in the soil, was a typical example of

predominance of P retention by Al/Fe oxides. Further more, P fractionation of soil

samples from the native area showed that up to 62% of TP was in the form of Al/Fe-

associated P (Tables 3-5 and 3-6).

The predominance of Al/Fe-associated P in the soil samples from the study site

was a reflection of its original properties, and its increase after effluent application could

be a consequence of adsorption under continuous application of a soluble P. The dairy

waste effluent contained 55 mg P/kg, 78% of which was soluble reactive P (SRP). The

difference between pH values of soil sample from the study site and native area, and the

presence of a higher Mehlich I-extractable Ca content in soil samples from the study area

did not seem to alter the predominance ofAl/Fe-associated P in the P fractionation

scheme.

Labile-P or easily removable P as defined by (Petterson and Istvanovics, 1988)

constituted 18-40% ofTP in the soil profile of the study site. Prior to effluent application

in 1996, labile-P ranged from 85 mg/kg in the surface horizon to 37 mg/kg in the lower

depth (100 cm) (Table 3-1) which corresponds to 26 and 18% of TP, respectively (Table

3-2). The application of effluent increased this fraction to 97 mg/kg in surface horizon


















Table 3-4. Mean concentration ofMehlich I extractable elements (mg/kg) in the soil
profile of the stud site in 1996 prior to the application of effluent(n = 12 profiles).
Mehlich I Extractable Elements (mg/kg)
................................................................. ...... .. ... .................................................................
Depth Ca Mg Al Fe
Location (cm)_
Study Site 0-15 968 115 301 23

15-30 522 69 280 23

30-45 208 34 203 20

45-60 135 26 161 18

60-80 103 23 133 16


75 19


117 14


80-100


___~__________________ ~___I~~_______________I__~











Table 3-5. P values (mg/kg) in each of the fractions within a soil depth increment at the
native site (n = 3 profiles). Values are Least Square Means (LSM).

Depth Labile Al-Fe Residual Ca-Mg Sum of P
(cm) P P P P Fractions
mg/kg mg/kg
0-15 68 125 3 6 202
15-30 59 195 20 12 26
30-45 58 166 4 13 241
45-60 58 136 17 8 219
60-80 58 150 17 9 234
80-100 61 149 16 9 235


Table 3-6. Percentage of P in each of the fractions within a soil depth increment at the
native site (n = 3 profiles). Values are Least Square Means (LSM).

Depth Labile Al-Fe Ca-Mg Residual
(cm) P P P P

0-15 33 62 3 2
15-30 20 68 4 7
30-45 23 69 5 2
45-60 26 62 4 8
60-0 24 64 4 7
80-100 26 63 4 7








and 69 mg/kg in the lower depth (100 cm) (Table 3-1) and (Fig. 3-2). Labile-P (Fig. 3-2)

increased in the surface horizon and throughout the profile over time (1996 vs. 1998)

with a substantial increase in the lower depth accounting for 40% of TP in 1998 (Table 3-

2). A comparison of labile-P mean concentration in each depth within the soil profile at

the beginning (1996) and end of the study period (1998) showed that the increase was

statistically significant (P <0.001- P<0.05) at the surface and throughout the profile

(Table 3-3). The previous mentioned studies by Nair et al. (1995) and Graetz and Nair

(1995) has reported that labile P form for the A horizon of Spodosol in all dairy

components averaged 9% in a single NH4Cl extraction and 1: 10 soil: solution ratio. The

higher percentage of labile P form in this study throughout the profile and its substantial

increase in the lower depth after effluent application is likely due to rapid movement ofP

through the profile.

In this study, the Ca and Mg-associated P fraction was the only fraction that

remained constant and did not show change with the application of effluent over time

(Table 3-1 and 3-2); (Fig. 3-3) in spite of considerable Mehlich I extractable-Ca content

throughout the soil profile as shown in Table 3-4. Though the stability of P forms is not

addressed in this study, Harris et al. (1994) reported an absence of Ca-P minerals despite

high pH and years of high Ca and P additions in soils from intensive areas of dairies in

south Florida. The lack of crystalline Ca-P could be related to kinetics, or to a poisoning

effect of component such as Mg, Si and organic acids in the dairy soil system (Wang et

al., 1995). The absence of a significant change in the Ca/Mg-associated P pool, in this

study, could be due to the factors mentioned by Wang et al., 1995 or due to analytical






57














P, mglkg
0 20 40 60 80 100 120
0


20


40
E
so
S60

0


100


120
-- 1996 --1998

Figure 3-2. Labile P values (mg/kg) within the soil profile at the beginning (1996) and
end of the study period (1998). Values are LSM Std. Error.






















P, mg/kg
0 10 20 30 40 50 60
0





40





808





120

Figure 3-3. Ca-Mg associated P values (mg/kg) within the soil profile at the beginning
(1996) and end of the study period (1998). Values are LSM Std. Error.








limitation. Nair et al. (1995) noticed that the labile P fraction increased if the soil was

repeatedly extracted with the 1 MNH4CI solution, with a corresponding decrease being

noted for the HCI P fraction (Ca/Mg-associated P pool).

Residual-P, the P fraction that is not readily removed by any of the chemical

extractants, constituted 7 to 17% of TP in the soil profile of the study site in 1996 prior to

the application of effluent (Table 3-1). This percentage corresponded to 25 and 36 mg

P/kg, respectively (Table 3-2). The application of effluent increased this fraction to 59

mg P/kg at the surface horizon in 1998 (Table 3-1) and (Fig. 3-4). However, as a

percentage of TP this amount constituted 10% of total P (Table 3-2). Bowman et al.,

1998 used both terms resistant P and residual P to mean that pool which is extracted with

great difficulty, or by difference from the whole when a soil residue yields essentially no

more acid- and base-extractable inorganic P (Pi) and organic P[ Po, as determined by

difference (Pt Pi)]. They reported an average of about 26% of TP as resistant, with the

more weathered soil containing about 50% resistant P. Nair et al. (1995) studied the

distribution of P forms of two abandoned dairies (12 and 18 yr) compared with the

youngest active (8 yr) dairy and reported an increase in Ca/Mg-associated P (61-74 %)

and a decrease in residual P (20 to 11%) in the A horizon of the abandoned dairies in

south Florida. They related this trend to a possible gradual mineralization of the residual

P, if the residual P is primarily recalcitrant organic P. However, the trend of increasing

residual P content in this study could be related to certain components in the effluent

used. The fractionation scheme used in this study did not offer a way of fractionating

residual P into organic and inorganic forms.

The trend of distribution of different P pools in this two year study was




















P, mglkg
0 10 20 30 40 50 60 70
0-


20


40


S60 -
so


80 -


100 -1996 -1998


120

Figure 3-4. Residual-P values (mg/kg) within the soil profile at the beginning (1996) and
end of the study period (1998). Values are LSM Std. Error.








that Al-Fe- associated P constituted the major proportion of TP in soil profile followed

by labile-P (prior to effluent application) and that both showed an increase with the

application of effluent. The increase of labile-P in the lower depth of the soil profile after

effluent application could be an indication of downward P movement in the soil profile.

Previous research in forms of P in soil profile from dairies of south Florida by

Graetz and Nair (1995) reported a predominance of Al/Fe-P (49% of TP) in the A

horizon of Spodosol soils from nonimpacted areas. However, the predominant form of P

in the A horizon of highly manure-impacted areas (active dairies for up to 32 years) was

Ca/Mg-P which reflect the predominance of Ca/Mg in cattle manure in their case. They

also reported that high percentage ofHCl-extractable P (Ca/Mg-associated P) in the A

horizon of the intensive dairy component was of potential concern. This P could be

continuously extracted by NH4 Cl or by water, suggesting that about 80% of the total soil

P had the potential to move eventually with drainage water into Lake Okeechobee (Nair

et al., 1995).


Summary and Conclusions

Most of P in the soil profile of the study site (prior to effluent application)

consisted of Fe/Al-associated P, which accounted for 49-62% of TP. The application of

effluent resulted in an increase in this fraction throughout the soil profile. Labile-P

constituted 18-26% of TP in the soil profile of the study site prior to effluent application,

and the application of effluent increased this fraction significantly up to 40% ofTP at the

lower depth of the profile (100-cm). The increase in labile-P at the lower depth (100-cm)

of the soil profile after two years of effluent application could be an indication of

downward P movement in the soil profile. Ca/Mg-associated P was the only fraction that





62

remained constant and did not show change with the application of effluent over time.

However, the absence of a significant change in Ca/Mg-associated P in this study could

be due to analytical limitation. Nair et al. (1995) noticed that the labile P fraction

increased if the soil was repeatedly extracted with the 1 MNH4CI solution, with a

corresponding decrease being noted for the HCl- P fraction (Ca/Mg-associated P pool).













CHAPTER 4
PHOSPHORUS RETENTION IN A SANDY SOIL RECEIVING DAIRY WASTE
EFFLUENT


Introduction

Sandy soils generally retain less P than finer textured soils because of a deficiency

of mineral components having surface affinity for orthophosphate. Thus, subsurface

transport of P can be significant in sandy soils due to low surface area or a paucity of P-

retaining components (Reddy et al., 1996). However, sand-grain coatings could

significantly enhance P adsorption and resistance to desorption (Harris et al., 1996).

Phosphorus retention in such soil has been the focus of a number of studies due to its

relevant environmental consideration in areas of intensified animal-based agriculture

(Mozaffari and Sims, 1993; Harris et al., 1994; Graetz and Nair, 1995; Nair et al., 1998;

Nair et al., 1999). Furthermore, attempts has been made to use a single-point isotherm to

characterize P retention in such soils (Mozaffari and Sims, 1993; Harris et al., 1996; Nair

et al., 1998). A single point isotherm indexing approach, termed the relative phosphorus

adsorption (RPA) index, effectively arrayed sandy Florida soil samples with respect to

relative P adsorption (Harris et al., 1996).

Although the equilibrium P concentration in the soil solution is generally

relatively low, recent studies have shown that the P concentration in the soil solution can

increase significantly well before the soil adsorption maximum has been reached

(Breeuwsma and Silva, 1992). The Dutch have developed a test referred to as the








"Degree of P Saturation" (DPS) which relates the soil P sorption capacity to an

extractable P concentration as follows:

DPS = Extractable soil P x 100
P sorption maximum


Operationally, DPS can be defined as oxalate-extractable P divided by the

phosphate sorption capacity of the soil that is estimated from equations including oxalate-

extractable Fe and Al (Breeuswma et al., 1995) as follows:

DPS = Pox x 100
Fe ox + Alox


The Dutch used a reference soil solution concentration of 0.1 mg P/L as a critical

concentration based on water quality studies. They found that a DPS value of 25% would

generally result in soil solution concentration equal to greater than 0.1 mg P/L. Pautler

and Sims (1998) study on comparison of short-and long-term sorption kinetics in Atlantic

coastal plain soils concluded that the potential for P loss from over-fertilized soils can be

improved by a knowledge of DPS of soils.

Sharpley (1995) found a single relationship (r2 of 0.86) to describe the

concentration of dissolved phosphate (DP) as a function of P-sorption saturation for ten

soils ranging from sandy loam to clay in texture. The Mehlich-3 extractant was used for

extractable soil P and the Langmuir P-sorption maximum as P-sorption capacity in the

calculation of DPS.

This study was conducted to evaluate the P retention of a sandy soil under dairy

effluent application using traditional multipoint isotherms, RPA, and DPS.








Materials and Methods

Experiment Location and Design

The site of the study was located at North Florida Holstein Dairy facility, which is

two miles south of Bell, Florida. A randomized block design containing three blocks and

arranged as a split plot was used as the experimental design. Main plots were N loading

rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste effluent

was used as the N source. The N application rates were 448 and 896 kg/ha/yr which

correspond to P loading of 112 and 224 kg/ha/yr. The cropping systems were corn-forage

sorghum-rye, and perennial peanut-rye.

Soil Selection and Sampling

The soil was mapped as a Kershaw sand (sandy, thermic, uncoated Typic

Quartzipsamments). Soil profile samples (0-15, 15-30, 30-45, 45-60, 60-80, 80-100 cm)

were collected in 1996 (prior to effluent application) and in 1997, and 1998 (after effluent

application). Soil from three profiles in each subplot was collected, composite, mixed

thoroughly and a 1-kg subsample was brought to the laboratory for analysis. Soil samples

were air-dried and sieved (2mm) prior to analysis. Soil samples were also collected in a

similar manner from an adjacent native area believed to unimpacted by manure or

fertilization application.

Soil Characterization

Rapid chemical assessment of relative phosphorus adsorption (RPA) was done by

procedure developed by Harris et al., (1996). Ten- gram samples of air-dry soil were

weighed into 20-mL scintillation vial and 2 mL of a 2000 mg/L P solution was added.

The content of the vials were mixed by vigorous shaking, and allowed to equilibrate for

24 hours at room temperature. The contents was transferred from the vials to centrifuge








tubes, and centrifuged at 1500 g for 5 min. The centrifuge tubes had small holes drilled

through the bottom. During centrifugation, solution passed through the holes into small

cups attached to the bottom of the centrifuge tubes. Solution was removed from the cups

and passed through a 0.45-ptm syringe filter. Phosphorus in the solution was determined

by the method of Murphy and Riley (1962) at an absorbance at 880 nm. The relative P

adsorption capacity was quantified by dividing the absolute amount ofP adsorbed by the

maximum possible under these conditions, which was 400 mg/kg.

Phosphorus multipoint adsorption isotherms were measured using 2 g of an air-

dried soil treated with 20 mL of 0.01M KCI solution containing various levels of P (0,

0.2, 0.5,1, 5, 10, 40, and 100 mg/L) in 50-mL centrifuge tubes. The tubes were placed on

a mechanical shaker for 24 hours equilibration period. At the end of 24 hours period, the

soil was centrifuged at 3620 x g for 10 min. The supernatant was then filtered through a

0.45-p.m membrane filter and the filtrate analyzed for P (Murphy and Riley, 1962).

Total phosphorus (TP) was determined by ashing 1.0 g of soil for 3 hours and

then solubilizing with 6 MHC1 (Anderson, 1976). Double-acid (Mehlich I)-extractable P,

Al, Fe, Ca and Mg were obtained with a 1:4 soil/double acid ratio (Mehlich, 1953).

Phosphorus in solution was analyzed by the molybdenum-blue method (Murphy and

Riley, 1962). Soil pH was determined on 1:2 soil/water ratio, and the organic carbon

content of the air-dried samples was determined by combustion (Broadbent, 1965).

Texture was determined using the pipette method (Day, 1965).

Oxalate-extractable P, Al, and Fe were determined by extraction with an

ammonium oxalate (0.1 Moxalic acid + 0.175 Mammonium oxalate) solution adjusted to

pH 3.0 (McKeague and Day, 1966). The suspension was equilibrated for 4 hours with








continuous shaking, centrifuged, filtered through a 0.45-jim filter and analyzed for P, Al,

and Fe.

Calculations

Degree of P saturation (DPS) was calculated as oxalate-extractable P divided by

the P sorption capacity of the soil, which is estimated as the sum of oxalate-extractable Fe

and Al (Breeuwsma et al., 1995). This DPS is referred to in this study as (DPS 1). Also,

DPS was calculated as double acid (Mehlich I)-extractable P divided by the P sorption

capacity of the soil, estimated from the sum of oxalate-extractable Fe and Al. This DPS is

referred to as (DPS 2).

Extractable soil P x 100
DPS = P- sorption capacity


P sorption capacity was estimated from oxalate-extractable Al and Fe.

Adsorption parameters were calculated using the Langmuir adsorption equation:

C/S = 1/kSmax + C/Smax

Where

S = S' + So the total amount ofP sorbed, mg/kg

S' = P sorbed by the solid phase, mg/kg

So = originally sorbed on the solid phase, mg/kg

C = concentration ofP after 24 h equilibration, mg/L

Smx = P sorption maximum, mg/kg

k = constant related to the bonding strength, L/mg P

So was estimated using a least square fit ofS' measured at low equilibrium

concentration, C. At these concentrations, the linear relationship between S' and C can be








described by S' = K C So where K is the linear adsorption coefficient (Graetz and Nair,

1995). Po ( soluble P) referred to P in solution after a 24-h equilibrium period when no P

was added.

Equilibrium P concentration (EPC), was defined as the concentration ofP in

solution where adsorption equal desorption and was the value of C when S' = 0.

Statistical Analysis

Data analyses were done using SAS (SAS Institute Inc. 1985) program (PROC

MIX) procedure (SAS Institute Inc. 1992). Relationships among parameters were

evaluated using linear correlation. Multiple regression was used to examine the strength

of the relationships between parameters.


Results and Discussion

Relative Phosphorus Adsorption (RPA)

After two years of effluent application, RPA values of soil samples from the study

site did not show any significant change and remained in the same range reported before

effluent application (Table 4-1). The absence of significant differences in RPA values pre

and after effluent application, indicated that effluent application did not influence P

sorption capacity for this soil which has been heavily loaded with animal manure prior to

the start of the study.

The RPA values of soil samples from the study site ranged from 0.5 to 0.6

throughout the profile pre-and post effluent application (Table 4-1). The samples from

native area adjacent to the study site showed an RPA value of 0.8 to 0.9 through out the

soil profile (Table 4-1). However, part of this difference could be due to differences in

clay content between native and study site samples as shown in Chapter 2 (Table 2-3).















Table 4-1. RPA values within the soil profile of the study site (n = 12 profiles) prior and
after to application of effluent compared to the "native soil" (n = 1 profile). Values are
Least Square Mean (LSM).
Depth 1996 1997 1998 Native
............. .. ................................. ................................. ...... ........................... ...
0-15 0.47 0.57 0.58 0.82

15-30 0.52 0.58 0.60 0.93

30-45 0.54 0.59 0.61 0.93

45-60 0.62 0.60 0.61 0.93

60-80 0.63 0.60 0.57 0.90

80-100 0.64 0.63 0.57 0.89








In the study by Rhue et al., 1994, RPA for Quartzipsamment was correlated with clay

content (R2 = 0.87).

RPA = -10.076 + 128.769 log (clay + 1)

Assuming that the relationship would apply to the soil at the study site and using the clay

contents in (Table 2-3), the RPA for native soil should have been about 0.60 while that

for the study site soil should have been about 0.45, showing the relative effect of clay

content on RPA. Why these measured RPA values were higher than those predicted by

the equation of Rhue et al., (1994) is not known. The effect of P loading on RPA has not

yet been explored. The relative contribution of clay and P loading cannot be related from

this data. The lower RPA values of the study site compared to the RPA values of the

native site indicated lower relative P adsorption capacity of the study site. Single-point

isotherm has been used to effectively index sandy materials. For example, Harris et al.

(1996) stated that RPA effectively arrayed sandy Florida soil samples with respect to

relative P adsorption. Their soil samples included five taxonomic groups for sandy

surface and subsurface horizon groupings. The RPA values were 0.74 and 0.69 for A and

Bt horizons ofPaleudults, 0.54 for coated Quartzipsamments (defined as coated) in the

surface horizon and 0.58 in the subsurface, 0.48-0.47 for uncoated Quartzipsamments

(defined as slightly coated) surface and subsurface horizons, 0.26-0.08 for uncoated

Quartzipsamments (defined as clean) surface and subsurface, and 0.05-0.01 for Alaquods

surface and subsurface horizons, respectively. They also pointed out that RPA does not

directly provide values for maximum P adsorption, but it closely relates to such values

derived from P adsorption isotherms. Mozaffari and Sims (1994) also have evaluated

single-point isotherms after Bache and Williams P sorption index (PSI) and indicated








that PSI may be a viable alternative to sorption isotherms for the purpose of a rapid

means to assess the ability of a soil profile to retain additional P. The PSI in their case

was found to be highly correlated (r2 = 0.94) with the Langmuir P sorption maxima

except when PSI exceeded 1400 mg/kg, where significant non-linearity was observed.

Recently, Nair et al., (1998) found that single point sorption values measured at 1000 mg

P/kg for soils of the Bh and Bw horizons from a low manure-impacted (pasture) and a

high manure impacted (holding) areas were comparable (r2 = 0.98) to the Smax values

calculated using a Langmuir equation and concluded that a single point sorption value

was a very convenient and quick means of characterizing the soils for maximum P

sorption capacity.

In this study, values of RPA for soil samples from the study site compared to the

RPA values from a native site indicated clearly a low sorption capacity for the soil

samples from the study site throughout the profile to Im depth. The absence of

significant differences in RPA values for different horizons within the profile could be

due to the absence of differences in soil constituents known to be responsible for P

sorption, such as clay content, between horizons within the profile. However, RPA values

were correlated r2 = 0.65 with double acid (Mehlich I)-extractable P, and Al (Table 4-2).

Similarly, RPA also correlated with oxalate-extractable P, Al, and Fe (r2 = 0.63, n = 72).

Degree of Phosphorus Saturation (DPS)

Degree of phosphorus saturation (DPS 1) values of soil samples in the study site

varied with depth in the soil profile. DPS 1 indicated a 50% saturation in surface

horizon, 26% at the 30-45 cm depth, 13-17 % at the 45-60 cm depth, and about 10-13%

at lower depths of 80 and 100 cm pre-and post effluent application (Table 4-3). However,












Table 4-2. Multiple regression equations relating RPA to a) Mehlich I (DA) Al, Fe and P,
b) Oxalate Al, Fe, and P in 1996 (prior to the application of effluent) (n = 72)._
No. Equation Model
R2

a) RPA = 0.314+ 0.0022DA-Al*** + 0.01181 DA-Fe 0.65***
0.00021 DA-P***


b) RPA = 0.515 + 0.0015 OX-A1*** 0.00167 OX-Fe** 0.63***
0.00087 OX-P***


Table 4-3. DPS 1t % values within the soil profile of the study site (n = 12 profiles)
prior and after to application of effluent compared to the "native" soil (n = 1 profile).
Values are Least Square Means (LSM).
Depth, cm 1996 1997 1998 Native
0-15 49.63 40.14 48.25 18.70
15-30 42.46 41.00 41.52 15.30
30-45 26.53 26.02 25.12 12.43
45-60 13.30 21.95 17.89 10.94
60-80 9.98 12.03 13.93 12.43
80-100 9.07 10.24 11.82 10.89
tDPS 1% = (Pox /(Feox + Alox))x 100








the soil samples from native area adjacent to the study site showed DPS Ivalue of about

19% to 11% through out the soil profile (Table 4-3).

The DPS 2 values for soil samples of the study area ranged from about 37% at

the surface to 4% at a depth of 100 cm compared to 9% to 5% for soil samples from the

native area, respectively (Table 4-4). Values of DPS 1 and DPS 2 for soil samples of

the study area were highly correlated in strong relationship (r2 =0.92, n = 144) (Fig. 4-1).

These results indicated that the surface horizon is more likely to release P than the deeper

depths. Sharpley (1995) found that a P saturation of 25%, the critical value used in the

Netherlands, would support a DP (Dissolved-P) concentration in surface runoff of 0.69

mg/L using Mehlich-3. Phosphorus sorption saturation, in his study, was calculated from

Mechlich-3 extractable-P and Langmuir P-sorption maximum. However, in Florida,

Mehlich I is the common soil P-test and the use of a common STP to express the DPS

might be practically useful. If the DPS can be determined by a standard soil test

procedure and commonly used as Mehlich I, the DPS can become a useful tool for

evaluating and comparing areas of potential P losses. Also, the strong relationship

between DPS 1 and DPS 2 suggested by this study, could be used to compare values

of both DPS if this relationship is similar enough in other soils.

Langmuir Adsorption Parameters

Surface horizons from the study site prior to the application of effluent showed a

lower Langmuir P- sorption maximum (55 mg/kg) associated with higher equilibrium P

concentration (EPCo) and a higher P originally sorbed (So) compared to subjacent

horizons (Table 4-5). These differences were significant (P<0.01) for equilibrium P














Table 4-4. DPS 2t % values within the soil profile of the study site (n = 12 profiles)
prior and after to application of effluent compared to the "native" soil (n = 1 profile).
Values are Least Square Means (LSM).
Depth, cm 1996 1998 Native
0-15 36.08 37.07 8.79
15-30 31.29 29.68 6.63
30-45 10.98 15.59 4.85
45-60 9.32 7.975 3.94
60-80 5.57 5.57 4.85
80-100 3.58 3.77 4.49
? DPS 2 % = (Mehlich I extractable-P / (Fe,, + Alox)) x 100



















90

80 y = 1.0544x + 6.0035
R= 0.9214
70

60

S50

0 40

30 -

20 *




I0 I *
0 10 20 30 40 50 60 70 80
DPS -2

Figure 4-1. Relationship between Degree of P saturation (DPS 1) calculated from
oxalate extractable-P and Degree of P Saturation calculated from Mehlich I (DPS 2) for
soil samples from the study site.











Table 4-5. Comparison of Langmuir parameters (Smx, EPCo, k) and So mean values of
different horizons within the soil profile prior to the application of effluent in 1996 and
after two years of effluent application in 1998.
Year Horizon Sma So EPCo k
mg/kg mg/kg mg/L L/mg

1996 A 55 28.39a* 8.81a 0.15
0-15cm (13.2-76.3) (14.9-39.6) (2.31-14.89) (0.04-0.40)

Cl 100 5.16a 1.19b 0.37
30-45cm (72.5-154) (1.1-8.8) (0.05-3.87) (.048-0.64)

C2 95 4.23b 0.79b 0.54
45-60 cm (37-142.8) (0-4.23) (0-0.79) (0.2-0.99)


1998 A 88 25.63a 5.02a 0.12
0-15 cm (70.5-97.1) (18.11-31.4) (3.85-6.18) (0.04-0.42)

Cl 95 10.05b 1.64b 0.68
30-45 cm (27.7-153) (2.29-25.8) (0.5-4.0) (0.07-2.8)

C2 96 4.67b 0.57b 0.74
45-60 cm (18.9-175) (2.1-8.34) (0.04-2.0) (0.09-2.44)


* LS mean values for given parameters followed by the same latter are not significantly
different (p<0.01). Numbers in parentheses are the highest and lowest value for the
parameter (n = 18).








concentration (EPCo) and P originally sorbed (So). There were no significant difference in

Langmuir parameters between 1996 and 1998. The same trend of a lower Langmuir P-

sorption maximum associated with higher equilibrium P concentration (EPCo) and a

higher P originally sorbed (So) continued in 1998 after the application of effluent. The

absence of differences in Langmuir parameters at the beginning and end of the study

period could be attributed to the variability usually associated with such measurements,

the study time limitation, and the fact that this site was heavily loaded with animal

manure prior to the start of the study. However, equilibrium P concentration (EPCo)

showed a strong relationship (r2 = 0.94) with DPS 1 (Fig. 4-2). Based on this

relationship, a DPS 1 value of 20 % corresponds to an EPCo value of approximately 1

mg/L. Another parameter, from the isotherm study Po (P in solution after a 24-h

equilibrium period when no P was added (soluble P)), also showed a strong relationship

(r2 =0.92) with DPS 1(Fig. 4-3). Based on this relationship, a DPS 1 value of 20%

corresponds to a Po of approximately 5 mg/L. Such correlation between DPS and

Langmuir parameters suggests that an integration of such tools could be used in the study

of the assessment of the tendency of this soil to release P.


Summary and Conclusions

This study demonstrated the possibility of integrating a numbers of tools to

characterize soil P retention at the study site. The use of a single point isotherm such as

relative P adsorption (RPA) showed that the soil at the site has a lower relative adsorption

for P compared to soils samples from a native site. After two years of effluent

application, RPA values of soil samples from the study site did not show any significant

change and remained in the same range reported before effluent application. The absence

















7


6 *
y = 0.161x 1.9555
Fe= 0.9408
5."



















extractable-P (PS 1) and equilibrium P concentration (EPC0) for soil samples from the
3s


2 -


1 9


0
0 10 20 30 40 50 60
DPS-1

Figure 4-2. Relationship between Degree of P saturation calculated from oxalate
extractable-P (DPS 1) and equilibrium P concentration (EPCo) for soil samples from the
study site.


















25


y=0.5078x-4.5994
20 R= 0.9257



15

E











0 10 32 30 40 5) 60
DPS-1

Figure 4-3. Relationship between Degree of P saturation calculated from oxalate
extractable-P (DPS 1) and soluble P (Po) mg/L for soil samples from the study site.
extractable-P (DPS 1) and soluble P (Po) mg/L for soil samples from the study site.








of differences in RPA values pre-and post effluent application, indicated that effluent

application did not influence P sorption capacity for this soil which has been heavily

loaded with animal manure prior to the start of the study.

The degree of phosphorus saturation (DPS) showed that soil samples from the

study site were 50% saturated at the surface compared to about 19% for the surface soil

samples from the native site. These results indicated that the surface horizon is more

likely to release P than the deeper horizons.

The isotherm study for this soil was also in agreement with the above finding

where surface horizon showed a lower Langmuir P- sorption maximum (55 mg/kg)

associated with higher equilibrium P concentration (EPCo) and a higher P originally

sorbed at the solid phase (So) compared to subjacent horizons. The same trend of a lower

langmuir P- sorption maximum associated with higher equilibrium P concentration

(EPCo) and a higher P originally sorbed at the solid phase (So) continued in 1998 after the

application of effluent, however no significant changes were observed between the two

years.

Values of degree of P saturation (DPS 1) and (DPS 2) were highly correlated

(r2 =0.92), which suggest the possibility of integrating the most common STP in the

region (Mehlich I) into the useful approach of degree of P saturation. Also, DPS 1 was

highly correlated with equilibrium P concentration (EPCo) (r2 = 0.94), and with soluble P

(Po) (r2 =0.92). However, further research is needed to determine whether these

relationships are similar enough in other sandy soils to be valuable as a tool in predicting

the tendency of soil to release P.













CHAPTER 5
DOWNWARD PHOSPHORUS MOVEMENT ASSESSMENT IN A SANDY SOIL
RECEIVING DAIRY WASTE EFFLUENT


Introduction

Loss of P from land can occur in three ways; as water-soluble and/or particulate P

in surface runoff, as water-soluble and/or particulate P in subsurface runoff (leaching),

and as water-soluble and/or particulate in flow to groundwater, referring to P picked up

by water that passes to the water-table and which is subsequently discharged to streams,

rivers or lakes as seepage (Ryden et al., 1973). P leaching has normally been considered

to be inconsequential in most soils, but recent studies have found that there are a

combination of agriculture management practices, soil properties, and climatic conditions

that can result in significant P accumulation in subsoils. Whether or not P that leaches

into subsurface horizons is later transported to water bodies depends on the depth of

leaching and the hydrological connections of the watershed (Sims et al., 1998). The

association of P accumulation with its downward movement has been the subject of

numerous studies in soils amended with commercial fertilizers and /or organic wastes.

Studies by King et al. (1990), Kingery et al. (1994), Mozaffari and Sims (1994), and

Eghball et al. (1996) reported P leaching to -75 cm depending on factors such as soil

type and the amount of P accumulated in the surface horizon. Furthermore, Eghball et al.

(1996) suggested a greater downward mobility for organic forms of P. Previous studies

from Florida also illustrated the extent of P leaching that can occur in deep, sandy soils.

One of the earliest studies in Florida was that of Bryan (1933) who reported P leaching to








depths of at least 90 cm in heavily fertilized citrus groves of varying ages. Humphreys

and Pritchett (1971), in their study of six soil series in northern Florida, 6 to 10 years

after applying superphosphate, reported extensive P leaching and subsequent

accumulation in the spodic horizon of a Leon fine sand. They noted that all fertilizer P

had leached below a depth of 50 cm in the Pomello and Myakka soil series. A study by

Wang et al. (1994) found that high levels of P could be leached from surface (Ap)

horizons of four sandy Florida soils heavily loaded with dairy manure despite high pH

and abundant Ca2+ in solid and solution phases. Graetz and Nair (1995), Nair et al.

(1995), Nair et al. (1998), and Nair et al. (1999), in a series of studies on Spodosols in the

Lake Okeechobee basin of Florida, concluded that the P that leaves the surface (A)

horizon might be lost through surface and subsurface drainage. The P portion that reaches

the spodic (Bh) horizon will be held as Al-and Fe-associated P, either in the inorganic or

in the organic fraction. The high percentage of HCl-extractable P (Ca-and Mg-associated

P) in the A horizon of the intensive dairy component was also of potential concern. The

HCI extractable P could be continuously extracted by NH4 Cl or by water (Graetz and

Nair, 1995), suggesting that about 80% of the total soil P had the potential to move

eventually with drainage water into Lake Okeechobee. Recently, Sims et al. (1998)

reviewed current research on P leaching and loss in subsurface runoff in Delaware,

Indiana, and Quebec. They concluded that the situation most commonly associated with

extensive P leaching, and thus the increased potential for P loss via subsurface runoff, has

been the long-term use of animal manures.

The most common soil P tests used to assess P status are the traditional agronomic

soil tests for P such as Mehlich I, Mehlich 3, Bray I, and Olsen. These tests are often well








correlated with environmentally oriented P tests such as biologically available P (BAP)

and dissolved reactive P (DRP) in runoff (Pote et al., 1996). Water soluble P (WSP) in

particular has been characterized as an appropriate environmental soil P test (Sharpley et

al., 1996, Moore et al., 1998). Therefore, this study was initiated to assess the vertical

movement ofP in the soil profile during application of dairy waste effluent to two

cropping sequences in a deep sandy soil, using WSP and labile P concentrations within

the profile as indicators of downward P movement.


Materials and Methods

Experiment Location and Design

The study site was located at North Florida Holstein Dairy facility, which is two

miles south of Bell, Florida. A randomized block design containing three blocks and

arranged as a split plot was used as the experimental design. Main plots were N loading

rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste effluent

was used as the N source. The N application rates were 448 and 896 kg/ha/yr which

correspond to P loading of 112 and 224 kg/ha/yr. The cropping systems were corn-forage

sorghum-rye, and perennial peanut-rye.

Soil Selection and Sampling

The soil was mapped as Kershaw sand (sandy, thermic, uncoated Typic

Quartzipsamments). Soil profile samples (0-15, 15-30, 30-45, 45-60, 60-80, 80-100 cm)

were collected in 1996 (prior to effluent application) and in 1997, and 1998 (after effluent

application). Soil from three profiles in each subplot was collected, composite, mixed

thoroughly and a 1-kg subsample was brought to the laboratory for analysis. Soil samples

were air-dried and sieved (2mm) prior to analysis. Soil samples were also collected in a








similar manner from an adjacent native area believed to unimpacted by manure or

fertilization application.

Soil Characterization

Texture was determined using the pipette method (Day 1965). Total phosphorus

(TP) was determined by ashing 1.0 g of soil for 3 hours and then solubilizing with 6 M

HCI (Anderson, 1976). Double-acid (Mehlich I)-extractable P, Al, Fe, Ca and Mg were

obtained with a 1:4 soil/double acid ratio (Mehlich, 1953). Phosphorus (P) in solution

was analyzed by the molybdenum-blue method (Murphy and Riley, 1962). Soil pH was

determined on 1:2 soil/water ratio, and the organic carbon content of the air-dried

samples was determined by combustion (Broadbent, 1965).

Water soluble P was extracted using a 1: 10 (soil: 0.01 M Ca Cl2) ratio, by

shaking the sample end- over-end for 1 hour, centrifuging for 20 min (1000 g), and

filtering (0.45 um). Phosphorus in solution was analyzed by the molybdenum-blue

method (Murphy and Riley, 1962). Labile P was obtained using a fractionation scheme.

The scheme used to fractionate soil-P was a modification by Nair et al. (1995) of that of

Hieltjes and Lijklema (1980). A 1-g air- dried sample was extracted twice with 25 mL of

1 MNH4Cl (adjusted to pH 7.0) (two hours shaking). After each extraction, the content

were centrifuged for 15 min at 3620 x g and filtered through a 0.45-p.m filter. All

extractions were carried out at room temperature. P determination was done using the

procedure of Murphy and Riley (1962) on a spectrophotometer at wavelength of 880 nm.

NH4Cl-extractable P was defined as labile P (Petterson and Istvanovics, 1988).

Statistical Analysis

Data analyses were done using SAS program (PROC MIXED) procedure (SAS

Institute Inc. 1985). Relationships among parameters were evaluated using linear








correlation. Multiple regression was used to examine the strength of the relationships

between parameters.


Results and Discussion

The soil from the study site showed a higher content of WSP prior to the

application of effluent in 1996 compared to the WSP in the soil profile of the native soil

collected from an adjacent site. WSP for soil samples from the study site ranged from

19.6 mg/kg at the surface to 1.9 mg/kg at 100 cm compared to 0.4 mg/kg at the surface

and <0.1 mg/kg at lower depths of the native soil (Table 5-1). This higher content of

WSP in the soil samples of the study site was associated with higher Mehlich I-

extractable P as shown in (Table 5-2).

The effect of date*rate (P< 0.001), crop*rate (P< 0.001), and date*depth (P<

0.001) were significant for WSP. The application of effluent caused an increase in WSP

content at all depths except the surface soil in 1998 and the change in WSP content was

significant for both rates (Table 5-1). The high effluent application rate showed a

decrease in the WSP content at the surface to about 30 cm then an increase down to the

100-cm depth (Table 5-3, Fig. 5-1). Similarly, WSP concentrations for the low effluent

application rate increased at lower soil depths (Table 5-4, Fig. 5-2). However, though the

trend of change in WSP content under the high and low rates effluent application at the

surface horizon were similar, the trend of change in WSP under low rate application at

the depths of 15-30, 30-45, and 45-60 cm was unexplainable. It was expected that such an

increase in WSP concentrations at these soil depths would be acceptable for the high

effluent rate application. Nevertheless, when WSP averages in all depths within the soil










Table 5-1. Mean water soluble P concentrations (WSP) in the soil profile prior to
application of effluent (1996) and after application (1998) (n = 12 profiles) compared to
native soil (n = 3 profiles). Values are least square means (LSM).
Depth 1996 1998 Native
(cm) mg/kg

0-15 19.6 13.9 0.4

15-30 16.2 22.2 0.1

30-45 9.10 23.2 <0.1

45-60 4.30 13.1 <0.1

60-80 2.80 8.10 <0.1

80-100 1.90 5.40 <0.1











Table 5-2. Mehlich I-extractable elements concentrations and total P (TP) in "native" soil
.(n = 1 profile) and study site soil profiles (n = 12profiles) prior to the start of the study.
Location Depth Ca Mg Al Fe P TP
(cm) mg/kg

Native 0-15 11.7 1.9 267 18.4 47 214
15-30 5.1 1.1 317 20.7 52 270
30-45 6.0 0.8 330 19.1 39 241
45-60 4.7 0.7 337 16.3 36 184
60-80 4.7 0.8 308 16.3 39 181
80-100 4.1 0.7 280 14.3 33 173

Study Site 0-15 968 115 301 23.5 283 328
15-30 522 69.3 280 22.8 184 254
30-45 208 34.1 203 19.6 75 154
45-60 135 25.7 161 17.9 37 254
60-80 103 22.9 133 15.9 20 218
80-100 75 19.2 117 14.5 12 192







88
















P. mg/kg
0 5 10 15 20 25 30
0-


20


40
S
80


80-
so- 4 H -


100-


120-1

-4-1996 -- 1998

Figure 5-1.Mean water soluble P (WSP) concentrations within the soil profile of the
study site under the high rate effluent application prior to the application of effluent in
1996 and after effluent application in 1998. Values are LSM Std. Error.




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PHOSPHORUS FORMS AND RETENTION IN A SANDY SOIL RECEIVING DAIRY
WASTE EFFLUENT
By
ABDULLAH AL-SHANKITI
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
2000

ACKNOWLEDGMENTS
Sincere appreciation and gratitude go to my major advisor, Dr. D. A. Graetz, for
giving me all the help I needed throughout the course of my study. I would also like to
thank my committee members-Dr. W. G. Harris, Dr. R. D. Rhue, and Dr. R. Nordstedt—
for their guidance, comments, and suggestions. I am grateful to Dr. V. Nair for her
insightful comments and suggestions, to Dr. K. R. Woodard for his help and support, and
to D. Lucas for her encouragement and support.
11

TABLE OF CONTENTS
page
ACKNOWLEDGMENTS iii
LIST OF TABLES vi
LIST OF FIGURES viii
ABSTRACT x
CHAPTERS
1 INTRODUCTION 1
Statement of the Problem 3
Objectives 4
Review of Literature 5
Soil Phosphorus 6
Phosphorus Accumulation 8
Phosphorus Forms and Fractionation 11
Phosphorus Retention 13
Downward P movement 20
Manure Management 22
Dissertation Format 23
2 PHOSPHORUS ACCUMULATION IN A SANDY SOIL RECEIVING DAIRY
WASTE EFFLUENT 25
Introduction 25
Materials and Methods 27
Experiment Location and Design 27
Soil Selection and Sampling 27
Soil Characterization 27
Effluent Application and Characterization 28
Statistical Analysis 28
Results and Discussion 30
Soil Properties Prior to Effluent Application 30
Effect of Application Rate and Cropping Systems 33
Summary and Conclusions 42
in

3PHOSPHORUS FORMS AND FRACTIONATION IN A SANDY SOIL
RECEIVING DAIRY WASTE EFFLUENT
44
Introduction 44
Materials and Methods 46
Experiment Location and Design 46
Soil Selection and Sampling 46
Fractionation Scheme 47
Statistical Analysis 48
Results and Discussion 48
Study Site 54
Summary and Conclusions 61
4PHOSPHORUS RETENTION IN A SANDY SOIL RECEIVING DAIRY WASTE
EFFLUENT 63
Introduction 63
Materials and Methods 65
Experiment Location and Design 65
Soil Selection and Sampling 65
Soil Characterization 65
Calculations 67
Statistical Analysis 68
Results and Discussion 68
Relative Phosphorus Adsorption (RPA) 68
Degree of Phosphorus Saturation (DPS) 71
Langmuir Adsorption Parameters 73
Summary and Conclusions 77
5DOWNWARD PHOSPHORUS MOVEMENT ASSESSMENT IN A SANDY SOIL
RECEIVING DAIRY WASTE EFFLUENT 81
Introduction 81
Materials and Methods 83
Experiment Location and Design 83
Soil Selection and Sampling 83
Soil Characterization 84
Statistical Analysis 84
Results and Discussion 85
Summary and Conclusions 95
6UTILIZATION OF DAIRY WASTE EFFLUENT THROUGH SEQUENTIAL
CROPPING
97

Introduction 97
Materials and Methods 98
Experiment Location and Design 98
Sampling and Analysis 99
Results and discussion 100
Summary and Conclusions 105
7 SUMMARY AND CONCLUSIONS 108
APPENDIX
SELECTION OF SOIL: SOLUTION RATIO 114
LIST OF REFERENCES 118
BIOGRAPHICAL SKETCH 126
v

LIST OF TABLES
Table Page
Table 2-1. Average annual concentrations (mg/L) of ammonium nitrogen (NH4 -N), total
Kjeldahl nitrogen (TKN), soluble reactive P (SRP), and total P (TP) in
effluent applied to the study site. Numbers in parentheses are standard
deviations 28
Table 2-2. Selected characteristics of typical Kershaw sand (Soil Survey Staff, Gilchrist
County, Florida, 1973) compared to the study site 31
Table 2-3. Mehlich I-extractable elements concentrations and total P (TP) in “native” soil
(n = 3 profiles) and study site (n = 12 profiles) soil profiles prior to beginning
of the study 32
Table 2-4. Statistical evaluation of TP data for the three-year study period 34
Table 2-5. Regression equation relating Mehlich I-P to the independent variables Mehlich
I-Ca, Mg, and Fe. (n=432) 42
Table 3-1. P values (mg/kg) in each fraction within a soil depth increment at the
beginning (1996) and end of the study period (1998) (n = 12 profiles). Values
are Least Square Means (LSM) 49
Table 3-2. Percentage of P in each fraction within a soil depth increment at the beginning
(1996) and end of the study period (1998)(n = 12 profiles). Values are Least
Square Means (LSM) 50
Table 3-3. Increases in each fraction within a soil depth increment between the beginning
(1996) and end of the study period (1998) 52
Table 3-4. Mean concentration of Mehlich I extractable elements (mg/kg) in the soil
profile of the study site in 1996 prior to the application of effluent (n = 12
profiles) 54
Table 3-5. P values (mg/kg) in each of the fractions within a soil depth increment at the
native site (n = 3 profiles). Values are Least Square Means (LSM) 55
vi

Table 3-6. Percentage of P in each of the fractions within a soil depth increment at the
native site (n = 3 profiles). Values are Least Square Means (LSM)
55
Table 4-1. RPA values within the soil profile of the study site (n = 12 profiles) prior and
after to application of effluent compared to the “native soil” (n = 1 profile).
Values are Least Square Mean (LSM) 69
Table 4-2. Multiple regression equations relating RPA to a) Mehlich I (DA) Al, Fe and P,
b) Oxalate Al, Fe, and P in 1996 (prior to the application of effluent) (n = 72). 72
Table 4-3. DPS - 1+ % values within the soil profile of the study site (n = 12 profiles)
prior and after to application of effluent compared to the “native” soil (n = 1
profile). Values are Least Square Means (LSM) 72
Table 4-4. DPS - 2+ % values within the soil profile of the study site (n = 12 profiles)
prior and after to application of effluent compared to the “native” soil (n = 1
profile). Values are Least Square Means (LSM) 74
Table 4-5. Comparison of Langmuir parameters (Smax, EPCo, k) and So mean values of
different horizons within the soil profile prior to the application of effluent in
1996 and after two years of effluent application in 1998 76
Table 5-2. Mehlich I-extractable elements concentrations and total P (TP) in “native” soil
(n = 1 profile) and study site soil profiles (n = 12 profiles) prior to the start of
the study 87
Table 5-3. Changes in WSP concentration within the soil profile under high application
rate after the application of effluent (1998) vs. prior to the application of
effluent (1996) 90
Table. 5-4. Changes in WSP concentration within the soil profile under the low
application rate after the application of effluent (1998) vs. prior to the
application of effluent (1996) 90
Table 6-1. P removed (kg/ha) by the com-forage sorghum-rye cropping system under
high and low application rates during the 1996-97 and 1997-98 seasons. (Data
obtained from Woodard et al. 2000) 101
Table 6-2. P removed (kg/ha) by the perennial peanut-rye cropping system under high
and low application rates during the 1996-97 and 1997-98 seasons. (Data
obtained from Woodard et al. 2000) 103
Table 6-3. Average dry matter yield of the com-forage sorghum-rye during the 1996-97
and 1997-98 seasons 106
Table 6-4. Average dry matter yield of the perennial peanut-rye during the 1996-97 and
1997-98 seasons 106
vii

LIST OF FIGURES
Figure Pag
Figure 2-1. Average total P (TP) concentrations in the soil profile under the high rate
application prior to application of effluent (1996) and after effluent
application (1997 and 1998). Values are LSM± Std. Error 36
Figure 2-2. Average total P (TP) concentrations in the soil profile under the low rate
application prior to application of effluent (1996) and after effluent
application (1997 and 1998). Values are LSM± Std. Error 37
Figure 2-3. Mehlich I-extractable P concentrations in the soil profile prior to start of the
study and after two years of effluent application (1998). Values are LSM±
Std. Error 38
Figure 2-4. Mehlich I-extractable P concentrations for cropping systems under the high
rate effluent application in 1998. Values are LSM± Std. Error 40
Figure 2-5. Mehlich I-extractable P concentrations for cropping systems under the low
rate effluent application in 1998. Values are LSM± Std. Error 41
Figure 3-1. Al-Fe-associated P (mg/kg) within the soil profile at the beginning 1996 and
end of the study period (1998). Values are LSM± Std. Error 51
Figure 3-2. Labile P values (mg/kg) within the soil profile at the beginning (1996) and
end of the study period (1998). Values are LSM± Std. Error 57
Figure 3-3. Ca-Mg associated P values (mg/kg) within the soil profile at the beginning
(1996) and end of the study period (1998). Values are LSM± Std. Error 58
Figure 3-4. Residual-P values (mg/kg) within the soil profile at the beginning (1996) and
end of the study period (1998). Values are LSM± Std. Error 60
Figure 4-1. Relationship between Degree of P saturation (DPS - 1) calculated from
oxalate extractable-P and Degree of P Saturation calculated from Mehlich I
(DPS - 2) for soil samples from the study site 75
viii

Figure 4-2. Relationship between Degree of P saturation calculated from oxalate
extractable-P (DPS -1) and equilibrium P concentration (EPCo) for soil
samples from the study site 78
Figure 4-3. Relationship between Degree of P saturation calculated from oxalate
extractable-P (DPS -1) and soluble P (P0) mg/L for soil samples from the
study site 79
Figure 5-1.Mean water soluble P (WSP) concentrations within the soil profile of the
study site under the high rate effluent application prior to the application of
effluent in 1996 and after effluent application in 1998. Values are LSM± Std.
Error 88
Figure 5-2. Mean water soluble P (WSP) concentrations within the soil profile of the
study site under the low rate effluent application prior to the application of
effluent in 1996 and after effluent application in 1998. Values are LSM± Std.
Error 89
Figure 5-3. Mean water soluble P (WSP) concentration within the soil profile of the study
site prior to the application of effluent in 1996 and after effluent application in
1998. Values are LSM± Std. Error 92
Figure 5-4. Labile-P concentration within the soil profile of the study site prior to the
application of effluent in 1996 and after effluent application in 1998. Values
are LSM± Std. Error 93
Figure 6-1. P removal (kg/ha) of com-forage sorghum-rye during the 1996-97 and 1997-
98 seasons 102
Figure 6-2. P removal (kg/ha) of perennial peanut-rye during the 1996-97 and 1997-98
seasons 104
IX

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
PHOSPHORUS FORMS AND RETENTION IN A SANDY SOIL RECEIVING DAIRY
WASTE EFFLUENT
By
Abdullah Alshankiti
May 2000
Chairman: D.A. Graetz
Major Department: Soil and Water Science
Currently there are major concerns about the potential negative effects of nutrient
losses from the waste of dairy farms on surface and ground water quality. In many
confined livestock production systems, manures are normally applied at a rate designed
to meet crop N requirements. However, this often results in a buildup of soil P above
amounts required for optimal crop yield and increases the chances for P losses from
source areas to water bodies.
This research, conducted at a dairy farm in north Florida, investigates the status of
soil P under two main treatments of dairy waste effluent and two cropping systems. The
N application rates were 448 and 896 kg/ha/yr which correspond to P loading of 112 and
224 kg/ha/yr. The cropping systems were perennial peanut-rye (P-R) and com- forage
sorghum-rye (C-FS-R). The objectives were to: (1) examine the accumulation of P in the
soil profile, (2) quantify and characterize P forms in the soil profile, (3) quantify and
x

characterize P retention in the soil profile, (4) determine P uptake by the cropping
systems, and (5) assess the downward movement of P.
The study site, mapped as Kershaw sand, appears to have been heavily loaded
with animal waste (47 mg/kg Mehlich I-extractable P (MI-P) in the native area vs. 283
mg/kg in the study site surface soils). The MI-P increased significantly with high effluent
rate application, particularly under the P-R cropping system, which suggests that the C-
FS-R cropping system may be more effective in P removal than the P-R cropping system.
Total P (TP) increased from 343 mg/kg in 1996 to 689 mg/kg in 1998. Water soluble P
(WSP) increased but primarily in the lower depths of the soil profile under both
treatments.
Al- and Fe-associated P constituted the major proportion (up to 60%) of the TP in
the soil profile. Labile-P accounted for 18 to 30%, and Ca- and Mg-associated P
accounted for about 10% of TP. Water soluble- and labile-P concentrations from 1996
and 1998 indicated a downward movement of P in the soil profile. These same data
coincided with a decrease in retention capacity as determined by “Relative Phosphorus
Adsorption” (RPA). Degree of P Saturation (DPS) data indicated that the surface horizon
is more likely to release P than the deeper depths. The conclusions drawn from DPS were
in agreement with the conclusions arrived at from the soil adsorption capacity and
equilibrium phosphorus concentration (EPCo).
Phosphorus removal was higher for the C-FS-R than for the P-R cropping system.
The removal values agreed with published P uptake for such crops, but crop uptake did
not alter the high level of soil P that was already present before application. When soil
test P levels in the soil exceed optimum values for crop production, the application of
xi

dairy waste based on estimated N requirement may not be appropriate on heavily P
loaded sandy soil such as the soil at the study site.
Xll

CHAPTER 1
INTRODUCTION
The impact of current agriculture management practices in farmland or animal-
related activity on water quality is well documented. Runoff from agricultural land is one
of the major sources of nonpoint-source pollution. The USEPA has identified agriculture
nonpoint-source pollution as the major source of stream and lake contamination that
prevents attainment of water quality goals identified in the Clean Water Act (Parry, 1998;
USEPA, 1996). The transport of phosphorus (P) to surface water can lead to accelerated
eutrophication of these waters, which limit their use for fisheries, recreation, industry, or
drinking. Although nitrogen (N) and carbon (C) are also associated with accelerated
eutrophication, most attention has focused on P because P often limits eutrophication and
its control is of prime importance in reducing the accelerated eutrophication of surface
water (Thomann and Mueller, 1987)
Most P in agriculture soils is found either as insoluble precipitates of Ca, Fe and/
or A1 or as a constituent of a wide range of organic compounds. Water moving across or
through soils removes both soluble P and sediments enriched with P, usually with the
lighter, fine sized particles such as clays and organic matter. The soluble or particulate P
then either can enter a flowing water body where it can be deposited as sediment or can
be carried directly into a lake or pond. Phosphorus can also leach downward in the soil,
perhaps to a tile drainage system or to ground water, where subsurface transport can then
discharge the P into a stream or lake (Sharpley and Halvorson, 1994).
1

2
Most of the P that enters aquatic ecosystems comes from agricultural use. Phosphorus is
added to lands as fertilizers, organic solids, wastewater, and feeds. It is estimated that
42,660 Mg of fertilizers was used during 1996 in Florida (Reddy et al., 1999). Fertilizer P
is primarily in inorganic form, which is bioavailabile and can be a major source of P for
many ecosystems. For example, fertilizer P accounted for 51% of P imports to the
Okeechobee Basin (Boggess et al., 1995). Another significant source of P input to the
lake was the dairy farming and beef cattle ranching north of the lake which accounted for
about 49% of the TP input to the lake (Federico et al., 1981). Thus, optimal dairy waste
management practices are more necessary than ever; more cows on limited land area
increase the likelihood of environmental problems resulting from mismanagement of
dairy farm wastes. A dairy waste management system should account for the fate of
nutrients that may be of environmental concern. The overall goal of sound agronomic
and environmental management programs for soil P is to maximize plant growth, while
minimizing losses of P to surface waters (Lanyon, 1994). It is important, therefore, to
understand the role of soil reactions in controlling the availability of soil P for plant
uptake or loss in erosion, surface runoff, and leaching. Amounts of P exported from
watersheds are tied to watershed hydrology, soil P content, and amount of P added as
fertilizer or manure. This assumes in most cases that P export from watersheds occurs in
surface rather than subsurface runoff, although it is recognized that in some regions of the
US dominated by sandy or organic soils P can be transported in subsurface drainage
waters. Generally, the P concentration in water moving through the soil profile is small
due to sorption of P, except in acid organic or peaty soils where the adsorption affinity
and capacity for P retention are low (Sims et al., 1998). Similarly, sandy soils with low P

3
sorption capacities, waterlogged soils, and soils with preferential flow through
macropores and earthworm holes are susceptible to P movement (Sharpley and Syers,
1979).
Statement of the Problem
In 1990, the Middle Suwannee River area was approved as a Hydrologic Unit
Area project based on data generated by the Florida Department of Environmental
Protection. These data showed an elevated concentration of nitrate-nitrogen in the
Floridan Aquifer in the Suwannee River Basin, especially in areas of intensive
agricultural activity. Phosphorus concentrations in the Suwannee River ranged from 0.40
to 0.49 mg/L which were 6.4 times the median regional value of north Florida streams.
The Hydrologic Unit Area program was developed to reduce or prevent water quality
degradation of the Floridan Aquifer and the Suwannee River resulting from agricultural
operations. Management of nutrients (potential contaminants) in dairy waste effluent
through spray field crop production systems is an important component in the overall
scheme for protecting ground and surface water from elevated levels of N and P. The use
of inappropriate crop management technology under a dairy effluent irrigation system
can lead to the loss of N to the ground water. Uptake of nutrients by agronomic crops
sequenced over time is an effective, economical, and environmentally sound means of
nutrient recovery. Cropping systems designs are needed to meet environmental demands
by maximizing nutrient uptake while meeting the needs of dairy producers.
The Use of Dairy Manure Effluent in A Rhizoma (Perennial) Peanut Based
Cropping Systems for Nutrient Recovery and Water Quality Enhancement is a research
project established under the Hydrologic Unit Area project (HU A). The objective of this

4
project was to evaluate five cropping systems grown under a dairy effluent disposal
irrigation system, comparing their effectiveness in nutrient recovery and maintenance of
acceptable levels of N and P in ground water. The cropping systems were com-forage
sorghum-rye, com-bermudagrass-rye, bermudagrass-rye, perennial peanut-rye, and corn-
perennial peanut-rye. The N application rates were 448, 672 and 896 kg/ha/yr which
correspond to P loadings of 112, 168 and 224 kg/ha/yr. My study was a component of
this project and addressed P forms and retention in the soil profile under two cropping
systems (com-forage sorghum-rye and perennial peanut-rye) and two N application rates
(448 and 896 kg/ha/yr) which correspond to P loadings of 112 and 224 kg/ha/yr.
In order to achieve the objectives mentioned below, two cropping systems were
chosen from the main study: com-forage sorghum-rye and perennial peanut-rye. The
workload associated with evaluating each treatment in the overall project would have
been prohibitive, therefore treatments were selected which provide representative data
with regard to the fate of P in the various cropping systems. The former is commonly
used by North Florida dairies (Staples, 1997). Recently, perennial peanut has been
identified as promising for its potential of continuous nutrient recovery over an extended
period of the year and for production of high quality forage
Objectives
The main objective of this research was to study the effect of dairy waste effluent
application on P accumulation, forms, and retention in the soil profile of a sandy soil
under two cropping systems. The cropping systems were com-forage sorghum-rye, which
represent the traditional crops for the Middle Suwannee River area, and perennial peanut-

5
rye, an improved cropping system to be introduce to the area. The specific objectives and
hypotheses of this research were as follow:
Objective 1: Quantify and characterize inorganic P forms in the soil profile of the
chosen cropping systems with increasing effluent P application.
Hypothesis: Application of dairy waste effluent will increase P levels in the soil
resulting in an accumulation of P in the soil profile.
Objective 2: Quantify and characterize P retention capacity in the soil profile.
Hypothesis: Soil retention capacity will decrease with continuous addition of
dairy waste effluent and may induce a downward movement of P.
Objective 3: Determine P uptake by the chosen cropping systems under two rates
of effluent application.
Hypothesis: P accumulation in soil profile will decrease with increasing plant
uptake.
Review of Literature
Phosphorus (P) is an integral and essential part of the food production system, but
P doesn’t occur abundantly in most soils. Total P concentration in surface soils varies
between about 0. 02 and 0.10% (Tisdale et al., 1993). The native P compounds are mostly
unavailable for plant uptake, some being highly insoluble. When soluble sources of (P) as
those in fertilizer and manure are added to soils, they are fixed or are changed to
unavailable forms and in time, react further to become highly insoluble forms. Farmers
commonly apply more P in fertilizers and manure than is removed by the crops. In time,
soil P levels increas often to high enough levels to reduce significantly future

6
requirements for P fertilizers and cause a buildup of P reserves in the soil profile (Brady,
1990).
Soil Phosphorus
Phosphorus in agriculture soils is found in inorganic and organic forms. Inorganic
forms represent 50-70% of soil P, although this fraction can vary from 10 to 90%
(Pierzynski et al., 1994). Inorganic forms are typically hydrous sesquioxides and
insoluble precipitates of Ca, Fe and/or Al. Organic P varies between 15 and 80% in most
soils (Tisdale et al., 1993). The quantity of organic P in soil generally increases with
increasing C and /or N. Many of the organic P compounds in soils have not been
characterized, but most are esters of orthophosphoric acid and have been identified
primarily as inositol phosphate, phospholipids, and nucleic acids. Organic P turnover in
soils is a result of P mineralization and immobilization reactions which, in general, are
similar to those of N as both processes occur simultaneously in soils. The initial source of
soil organic P is plant and animal residue, which is degraded through microbial activity to
produce other organic compounds and release inorganic P (Tisdale et al., 1993).
There is an interrelationship between the various forms of P in soils. The decrease
in soil solution P concentration with absorption by plant roots is buffered by both
inorganic and organic fractions in soil. Primary and secondary P minerals (nonlabile P)
dissolve to resupply H2PCV/ HPO42’ in solution. Inorganic P adsorbed on mineral and
clay surfaces as H2P04'or HPO42’ (labile inorganic P) also can desorb to buffer P in
solution P.
Numerous soil microorganisms digest plant residues containing P and produce
many organic P compounds in soil. These organic P compounds can be mineralized
through microbial activity to supply inorganic P. Soil solution P is often called the

7
‘intensity factor’, while the inorganic adsorbed P and organic labile P fractions are
collectively called the ‘quantity factor’. Maintenance of solution P concentration or
(intensity) for adequate P nutrition in the plant depends on the ability of labile P
(quantity) to replace soil solution P taken up by the plant. The ratio of quantity to
intensity is called the ‘capacity factor’ which expresses the relative ability of the soil to
buffer changes in soil solution P. Generally, the larger the capacity factor, the greater the
ability to buffer solution P. The P cycle can be simplified to the following relationship:
Soil solution Labile P<- nonlabile P
Labile P is the readily available portion of the quantity factor that exhibits a high
dissociation rate and rapidly replenishes solution P. Depletion of labile P causes some
nonlabile P to become labile, but at a slow rate. Thus, the quantity factor comprises both
labile and nonlabile fraction (Tisdale et al., 1993).
The division of P in the soil’s solid phase into the labile and nonlabile forms
comes about from a kinetic consideration. From a mechanistic point of view, P in the
soil’s solid phase can be classified by yet another way into adsorbed P and crystalline P.
The first refers to P adsorbed on active surfaces in the soil, and the second to distinct P
compounds either formed as reaction products, or inherently present in the soil matrix.
The two types of categorization (i.e., labile vs. nonlabile and adsorbed vs.crystalline) are
not synonymous, although a great deal of overlap exists between the two. The labile P
does not represent a precisely distinct phase of solid phase P, but one that has arbitrary
boundaries of time and other procedural factors. Any loss of precision in defining labile P
is paralleled by an equal uncertainty in defining the remaining P (Olsen and Khasawneh,
1980). Phosphorus amendments, in either organic or inorganic form, are needed to

8
maintain adequate available soil P for plant uptake. Once applied, P is either taken up by
the crop or becomes weakly or strongly adsorbed onto Al, Fe and Ca surfaces. With the
application of P, available soil P content increases as a function of certain physical and
chemical soil properties, such as clay, organic C, Fe, A1 and calcium carbonate content.
The continual application of P can result in an increase in soil test P above levels required
for crop uptake, which has an environmental ramifications.
Phosphorus Accumulation
In many parts of the world, concern and research focuses on manure application,
where the amount of P added often exceeds crop removal rate on an annual basis. Many
areas with intensive confined animal operations, such as the Netherlands, Belgium, north¬
eastern USA and Florida, now have soil P levels that are of environmental rather than
agronomic concern (Sharpley et al., 1994b). In 1994, Kingery et al. (1994) reported P
leaching to a depth of ~60 cm in tall fescue pastures in the Sand Mountain region of
northern Alabama that had received long term-application (15-28 yr) of poultry litter.
Soil test P (Mehlich I) values in topsoils were extremely high (~230 mg/kg) relative to
optimum values for crop production in this region (25 mg/kg) (Cope et al., 1981).
Similarly, Eghball et al. (1996) measured soil test P (Olsen P) in the profile of a Tripp
very fine sandy loam (a coarse-silty, mixed, mesic Aridic Haplustoll) that had received
long-term (>50 yr) application of cattle feedlot manure and/or fertilizer P. Crops grown
included sugarbeet, potato, and com. Increases in soil test P were reported and the
increases were associated with P leaching to ~75 cm with fertilizer P (superphosphate)
and to ~ 1.0 m for manure or manure plus fertilizer P. Mozaffari and Sims (1994)
measured soil test P (Mehlich I) values with depth in cultivated and wooded soils on
farms on a coastal plains watershed dominated by intensive poultry production and

9
frequent applications of poultry litter, and observed P leaching to depth of ~60 to 75 cm
in agricultural fields and a high soil test P values in topsoils relative to those considered
optimum for most agronomic crops (25 mg/Kg) (Sims and Gartley, 1996). In North
Carolina, King et al. (1990) examined the effect of 11 years of swine lagoon effluent
application on P distribution within the profile of a Paleudult soil used for coastal
bermuda grass pasture, and reported soil test P (Mehlich I) values much greater than
required for crop production (225-450 mg/kg as a function of effluent rate, vs. an
optimum soil test value of -20-25 mg/kg). Soil test P at the 15 to 30, 30 to 45, 45 to 60,
and 60 to 75 cm depths was <5 mg/kg in nearby unfertilized pasture. However, at the
same depths, soil test P was about 120, 75, 25, and 5 mg/kg at the lowest effluent rate
(335 kg N/ha per year) and 350, 175, 125, and 50 mg/kg at the highest effluent rate (1340
kg N/ha per year).
The same trend of P accumulation and leaching has also been shown in Florida
which has intensive agricultural activity, humid climate, frequent heavy rainfall, and
widespread use of irrigation and drainage. Several studies have shown the extent ofP
leaching that can occur in deep, sandy soils. For example, a study by Wang et al. (1995)
found that high levels of P could be leached from surface (Ap) horizons of four sandy
Florida soils heavily loaded with dairy manure despite high pH and abundant Ca2" in
solid and solution phases. Total P (TP) ranged from 3144 to 1595 mg/kg. Further
investigation on the composition of the same samples by Harris et al. (1994) showed that
the dominance of noncrystalline Si and lack of crystalline Ca-P in the intensive area Ap
horizons constitute an unfavorable environment for P retention in these soils. The
crystallization of Ca-P may be inhibited by manure-derived component such as Mg,

10
organic acids, and Si. Nair et al. (1995) also studied the forms of P in soil profiles from
dairies of south Florida. The dairies selected were active (still operating at the time of
sampling) and abandoned (dairies that had not been operating for 4, 12, 18 yr prior to
sampling). Three components of each active dairy were sampled: intensive areas (areas
next to the barn where cattle are held immediately prior to milking), pasture (areas used
for grazing), and forage areas (used for forage production). Their result showed a TP for
the A horizon ranging from 3028 mg/kg for the active-intensive areas to 2933 mg/kg for
the abandoned-intensive areas. Total P content of the unimpacted soils (native) was in the
range of 15-59 mg/ kg for all horizons, with low values observed in the E horizon and
high values in the Bh horizon. Labile P content (defined as P in sorbed phase, which is
potentially mobile and bioavailable) in the Bh horizon of native forage and pasture areas
were less than 2% of the TP, while up to 10% of TP was found as labile P in surface
horizons. In intensive areas, up to 40% of the P was in the labile pool. Soil P content
varied both with soil depth and land use. Total P stored in the soil profile increased with
intensity of land use, with native unimpacted areas containing 44 g P mf2 (average profile
depth 99 cm), followed by forage (46 g P m'2; soil depth 94 cm) pasture (102 g P m'2; soil
depth 119 cm) and intensive areas (766g P m‘2; soil depth 136 cm). Dairy lagoon effluent,
though its composition and P content is quite different from dairy manure could also
elevate the level of P in the soil. Dooley (1996) studied P accumulation and retention in a
wetland impacted by approximately 20 years of dairy lagoon effluent application and
showed that the wetland appeared to be exporting P to an adjacent stream. His study
concluded that in order to accomplish acceptable levels of treatment, the assimilative
capacity of the wetland must be considered.

11
Numerous studies on accumulation of P in soils amended with commercial
fertilizers and /or organic wastes, including some of the above-mentioned studies, have
been reviewed recently by Sims et al. (1998). He indicated clearly that the most common
agricultural situation associated with significant downward movement of P has been the
accumulation of P to “very high” or “excessive” levels in soils from continuous
application of organic wastes (manure, litter, and municipal or industrial wastes and
waste waters).
Phosphorus Forms and Fractionation
In order to understand the potential for P transport, P forms have to be examined
and evaluated to develop an understanding of the stability of P in the soil of the area
adjacent to the water body. The objectives of P fractionation in general are to provide
insight into the fate and transformation of P added to soils as fertilizers or manure,
estimate the availability of P to plants for agronomic purposes, estimate the potential for
P movement from erosion and through leaching, and provide information regarding the
interaction between P in sediments and the overlaying water in the case of aquatic
systems (Graetz and Nair, 1999). Fractionation schemes using various chemical extracts
have been developed through the years to quantify the different forms of P in soils. The
underlying assumption here is that inorganic P in soil consists of varying proportions of
three discrete classes of compounds, namely, phosphates of Fe, Al and Ca, some of which
could be occluded or enclosed within coatings of Fe oxides and hydrated oxides. These
chemical P forms are operationally defined and subject to broad interpretations.
Nevertheless, they offer a convenient means for obtaining significant information on P
chemistry of soils. For example, through a modification of Hieltjes and Lijklema (1980)
fractionation method Nair et al. (1995) examined soil phosphorus in soil from dairies of

12
south Florida and fractionated it into labile P, inorganic Fe/Al-P, Ca/Mg-P and residual-
P. This fractionation scheme offered significant information on the forms of P in soil
profiles from dairies of south Florida. The Hieltjies & Lijkiema (1980) scheme uses 1 M
NH4CI to extract loosely bound and labile P. This fraction is believed to contain the water
soluble portion and the plant- available portion of TP in the sample. Sodium hydroxide is
the next step in the fractionation procedure. This extract contains both organic and
inorganic P forms. The inorganic P portion of the extract is believed to be associated with
Fe and Al, while the organic portion is believed to be fulvic-and humic bound.
Hydrochloric acid is the third step to remove calcium-bound phosphate. The remaining
soil can then be digested to measure any residual P. This portion of P is considered to be
highly resistant, organically bound.
The forms of P in soil profiles from dairies of south Florida illustrate the fate and
transport of P in these systems Nair et al. (1995). They identified the P forms in the soil
profile of differentially manure-impacted soils in the Okeechobee watershed of south
Florida. All soils were Spodosols, and soils were collected by horizon, A, E, Bh, and Bw.
Their results showed no statistical differences in the percentage of labile P (NH4CI-
extractable P), the P that would most likely move from A horizon of the various
components. More P will be lost from the heavily manure-impacted intensive areas with
high TP values, than from the less impacted pasture, forage and native areas. They also
observed that the P would continue to be lost from dairies that have been abandoned for
considerable period of time. The P that leaves the surface horizon might be lost through
surface and subsurface drainage, and the portion that reaches the spodic (Bh) horizon will
be held as Al- and Fe-associated P, either in the inorganic or in the organic fraction. The

13
high percentage of HCl-extractable P (Ca- and Mg-associated P) in the A horizon of the
intensive dairy component was also of potential concern. This P could be continuously
extracted by NH4CI or by water (Graetz and Nair, 1995), suggesting that about 80% of
the total soil P had the potential to move eventually with drainage water into Lake
Okeechobee.
Fractionation of P forms has been particularly useful in understanding the
transformation of P added to soil, either in inorganic or organic amendments such as
manures. Zhang and Mackenzie (1997) used P fractionation and path analysis to compare
the behavior of fertilizer and manure-P in soils. Their results showed that P behaves
differently when added as manure, compared to inorganic fertilizer, which may affect the
depth of P movement through the soil profile. Simard et al. (1995) reported that a
significant portion of the P moving downward in soils receiving substantial amounts of
animal manure accumulated in labile forms such as water-soluble, Mehlich-3, and
NaHCCb extractable P forms. Eghball et al. (1996) found that P from manure moved
deeper in the soil than P from chemical fertilizer in long term (>50 yr) studies.
Phosphorus Retention
P retention in soils is a result of many soil physical and chemical properties, such
as mineralogy, clay content, pH and organic matter content, that influence the P solubility
and adsorption reactions. Consequently, these soil properties also affect solution P
concentration., P availability and recovery of P fertilizer by crop (Tisdale et al., 1993).
The term frequently used to describe surface adsorption and precipition reactions
collectively is P fixation or retention. The term adsorption and chemisorption also have
been used to describe P reaction with mineral surfaces, where chemisorption generally
represents a greater degree of bonding to the mineral surface. The term sorption has been

14
used to describe adsorption and chemisorption collectively. Adsorption is the preferred
term (Tisdale et al., 1993). There is considerable evidence suggesting that, P retention is a
continuous sequence of precipitation and adsorption. With low-solution P concentration,
adsorption probably dominates, while precipitation reaction proceed when the
concentration of P and associated cations in the soil solution exceeds that of the solubility
product (Ksp) of the mineral. Mineral solubility represents the concentration of ions
contained in the mineral that is maintained in solution. Each P mineral will support a
specific ion concentration which depends on the solubility product of the mineral. The
most common P minerals found in acid soil are Al-and Fe-P minerals, while Ca-P
minerals predominate in neutral and calcareous soils. But, the specific P minerals present
in the soil and the concentration of solution P supported by these minerals are highly
dependent on solution pH (Tisdale et al., 1993).
Phosphorus sorption may be determined by single point adsorption isotherm or
multi-point adsorption isotherms and can be described by several different adsorption
equations; all are based on the fundamental equation:
q = f(C)
where q is the quantity of P adsorbed at P concentration C.
One of the earliest equations used in soil studies is the Freundlich equation,
q= acb
The amount of P adsorbed per unit weight of soil is q, c is the P concentration in
solution, and a and b are constant which vary from soil to soil. The Freundlich equation
was introduced as a purely empirical equation. It implies that the energy of adsorption
decrease exponentially with increasing saturation of the surface. However, no maximum

15
capacity of adsorption can be calculated because the amount of adsorption increases with
the adsorbing ions in the solution (Yuan and Lucas, 1982). Therefore, it applies well only
over a limited concentration range of ions to be adsorbed. For this reason, the Langmuir
equation, which is based on the assumption that adsorption is on localized sites, the
energy of adsorption is constant, and the maximum adsorption possible corresponds to a
complete monomolecular layer is often preferred for the description of soil P adsorption.
In its linear form, the regression line would provide a means to calculate not only the
maximum adsorption but also a constant which is assumed to be related to the bonding
energy of the surface for P in solution. The equation describes a finite limit to adsorption
so that a maximum value may be obtained (Yuan and Lucas, 1982). Although there are
several linear forms, they are all derived from the basic expression:
q = kbc/(l+kc)
where q and c are as in the Freundlich equation, b is the “P adsorption maximum”, and k
is a constant related to bonding energy.
The Temkin equation, as proposed for use in soil-P system by Bache and
Williams (1971), also implies that the energy of adsorption decreases as the amount of P
sorbed increases. In the middle range of P sorption, the equation may be expressed as
q/b = (RT/B)ln Ac
where A and B are constant and b, c and q are as in the Langmuir equation. All three
equations require that equilibrium conditions exist, a state that is rarely achieved in soil-P
adsorption studies. Another assumption common to the three equations is that the
adsorption is reversible; however some portion of the P adsorbed by soil is irreversibly
adsorbed. Despite these and other disadvantages, the three equations have been useful in

16
describing the relationship between c and q over limited range of concentrations (Olsen
and Khasawneh, 1980).
In Florida, the P retention characteristics of upland and wetland soils and stream
sediment in the Lake Okeechobee Watershed (maximum P retention capacity [Smax] and
equilibrium P concentration [EPCo]) have been a point of interest for several studies
(Reddy et al., 1996). The Smax of Bh horizons was about three to four times higher than
the surface A and E horizons. High EPCo (equilibrium concentration when net adsorption
equal zero) values for soils in the A and E horizons suggest poor retention capacity, while
low EPCo values of the Bh horizon indicate strong affinity for P. The Smaxwas found to
be highly correlated with oxalate-extractable Fe and Al, and total carbonate of the soil.
Oxalate-extractable Fe and Al represent amorphous and poorly crystalline forms. Many
soils effectively retain P due to the presence of mineral components with high surface
affinity for orthophosphate. However, movement of P from dairy farms to aquatic
systems does occur under certain conditions, and has been linked to eutrophication of
surface water. This movement may be related to erosion or to subsurface transport.
Subsurface transport of P can be significant in sandy soils due a paucity of P-retaining
components (Reddy et al., 1996).
Sandy soils generally retain less P than finer textured soils because of a deficiency
of mineral components having surface affinity for orthophosphate. In a 1982 study by
Yuan and Lucas pertaining to the retention of phosphate by thirty Florida sandy soil as
evaluated by adsorption isotherms showed that the simple linear Freundlich equation
describe the P adsorption properties of sandy soil more successfully than the Langmuir
equation. The adsorption maximum values obtained from the Freundlich equation were

17
correlated with soil properties. A significant relationship was found with clay content but
not with double acid extractable Al, Fe, Ca and Mg, individually or combined. However,
for soils with a pH below 5.5, the adsorption maximum had a significant relationship with
extractable Al. A study on P retention as related to morphology and taxonomy of sandy
coastal plain soil materials by Harris et al (1996) distinguished between two groups of
uncoated Quartzipesamments (< 5% silt-plus-clay); those having “clean” (coating-free)
and “slightly-coated” grains. All clean samples readily desorbed P regardless of origin or
amount adsorbed. Sand-grain coatings significantly enhanced P adsorption and resistance
to desorption. Thus, clean sands pose a greater hazard for P leaching than sands with
grain coatings. Clay content was closely related to P adsorption, but silt content was not.
The P-retention distinction between clean and other Quartzipsamments is more marked
than uncoated vs. coated family criterion. The distinction between clean and other sandy
materials was more discrete and consistent for P desorption behavior than for adsorption.
A P-adsorption measurement such as the RPA (Rapid Chemical Assessment of Relative
Phosphorus Adsorption [single-point isotherm]) would provide a reasonably valid
assessment of P retention for slightly-coated and coated sand materials if appropriately
calibrated. The RPA effectively arrayed sandy Florida soil samples with respect to
relative P adsorption. A single-point isotherm could effectively index these sandy
materials. It does not directly provide values for maximum P adsorption, but it closely
relates to such values derived from P adsorption isotherm for the same sandy soil studied
(Harris et al., 1996).
A recent study by Nair et al. (1998) conducted on Spodosols in the Lake
Okeechobee basin to evaluate the P retention capacity of manure impacted Bh horizons

18
under aerobic and anaerobic conditions found that a high watertable decreased the P
retention for the majority of the soils in that study. High manure-impacted areas have Bh
horizons with high P concentrations as a result of P movement from the surface A
horizon through the eluted E horizon. The P appeared to be temporarily retained and
could be released upon prolonged contact with water. Another study by Nair et al. (1999)
of Spodosols in the same basin showed that the surface A and E horizons of manure-
impacted soils had essentially no sorbing capacity while the Bh (spodic) and Bw horizons
had mean Smax values 430 and 385 mg/kg, respectively. The P retention characteristics of
these soils were determined by using both single-point (1000 mg P/kg or 100 mg P/L)
and traditional Langmuir isotherms. Phosphorus sorption values using a single high P
solution had approximately a 1:1 relationship with values obtained for the maximum
retention capacity (Smax) obtained from Langmuir isotherms.
In response to the fact that the P sorption capacity of soils is not unlimited, and
based on documented accumulation and leaching of P in soils of areas dominated by
concentrated animal production, a new approach to sorption capacity was developed. The
concept of Degree of P Saturation (DPS) is based on the fact that the potential for soil-P
desorption increases as sorbed P accumulates in soil (Van der Zee et al., 1987;
Breeuwsma and Silva, 1992). Degree of P saturation is defined as the ratio of extractable
P to the sum of extractable Fe and Al expressed as an percentage. The critical DPS
threshold has been defined as the saturation percentage that should not be exceeded to
prevent adverse effect on ground water quality with the specific goal that the phosphate
concentration in the ground water should not exceed 0.01 mg/L of orthophosphate at the
level of the mean high watertable (Breeuswma et al., 1995). A critical DPS value of 25%

19
has been used in the Netherlands to determine the surplus of P that can be applied to
varying soil types before P saturation, and thus significant P export in subsurface runoff,
can be expected to occur.
Operationally, DPS is defined as oxalate-extractable P divided by the phosphate
sorption capacity of the soil that is estimated from equations including oxalate-
extractable Fe and A1 (Breeuwsma et al., 1995).
DPS = Extractable soil P X 100
P sorption maximum
The extractable P (Pox) is determined by extraction by 0.2 M ammonium oxalate
buffered to pH 3.0. Phosphorus sorption capacity is determined by standard P adsorption
isotherms or estimated by oxalate-extractable Al (Alox ) and Fe (Feox ) and the DPS
expressed as:
Pox
DPS = X 100
oc (Fe ox + Al ox)
The saturation factor a, as defined by Sjoerd et al. (1988), is the ratio of the
amount of P that is sorbed in laboratory experiments and the P already present as Pox to
(Feox+ Alox). Thus a is a variable that allows comparison of different soils with respect to
P saturation, and the result will then be normalized with respect to the reactive soil
constituents. However, as pointed out by Sjoerd et al. (1988), the proportionality factor a
is both concentration and time dependent. Pautler and Sims (1998) used an a value
ranging from 0.4-0.6 for soils of the Atlantic coastal plain.

20
An added advantage of the DPS approach is that it not only describes the potential
for P release from soil but also indicates how close the P-sorption sites of a soil are to
being saturated (Sibbesen and Sharpley, 1997). Citing data from numerous studies in the
Netherlands, showed that more than 80% of the soils in a watershed with intensive
livestock production were saturated with P (Breeuwsma et al., 1995). During winter
months, when groundwater discharge to surface waters was highest, concentration of TP
in the shallow groundwater to exceeded surface water quality standards (0.15 mg/L of
TP). Lookman et al. (1995) applied the DPS approach to a 700 Km2 area (primarily
grassland used for intensified animal agriculture) in northern Belgium. Based on a critical
DPS value of 25%, they estimated that >75% of the soils were considered to be saturated
with P to the depth of the highest average groundwater table. Lookman et al. (1996)
showed that the DPS of the same soils of their 1995 study (Lookman et al., 1995) at the
0-30 cm depth was highly correlated with soluble P in these soils. Sharpley (1995) also
found a single relationship (r2 of 0.86) describing the concentration of dissolved
phosphate (DP) as a function of P-sorption saturation for ten soils ranging from sandy
loam to clay in texture. He used Mehlich-3 as extractable soil P and the Langmuir P-
sorption maximum as P-sorption capacity in his calculation of P-sorption saturation.
Comparison of short-and long-term sorption kinetics in Atlantic coastal plain soils
showed that the potential for P loss from over-fertilized soils can be improved by a
knowledge of the degree of P saturation of the soils (Pautler and Sims, 1998).
Downward P movement
Loss of P from land can occur in three ways; as water-soluble and/or particulate P
in surface runoff, as water-soluble and/or particulate P in subsurface runoff (leaching),
and as water-soluble and/or particulate P in flow to groundwater, referring to P picked up

21
by water that passes to the water-table and which is subsequently discharged to streams,
rivers or lakes as seepage (Ryden et al., 1973). Phosphorus leaching has normally been
considered to be inconsequential in most soils, but recent studies show that there are
combinations of agriculture management practices, soil proporities, and climatic
conditions that can result in significant accumulation in subsoils. Whether or not P that
leaches into subsurface horizons is later transported to water bodies depends on the depth
of leaching and the hydrological connections of the watershed (Sims et al., 1998). As
mentioned above in the section on P accumulation, numerous studies on accumulation of
P in soils amended with commercial fertilizers and/or organic wastes have been reviewed
recently by Sims et al., (1998). This indicated clearly that the most common agricultural
situation associated with significant downward movement of P has been the accumulation
of P to “very high” or “excessive” levels in soils from continuous application of organic
wastes (manure, litter, and municipal or industrial wastes and waste waters). Studies by
Kingery et al. (1994), Eghball et al. (1996), Mozaffari and Sims (1994), and King et al.
(1990) report P leaching to~75 cm depending upon other factors such as soil type and P
accumulated in the surface horizon. Furthermore, Eghball et al. (1996) suggested a
greater downward mobility for organic forms of P. Previous studies from Florida also
illustrated the extent of P leaching that can occur in deep, sandy soils. One of the earliest
studies in Florida was of Bryan (1933) who reported P leaching to depths of at least 90
cm in heavily fertilized citrus groves of varying ages. Humpherys and Pritchett (1971), in
their study of six soil series in northern Florida, 6 to 10 years after applying
superphosphate, reported extensive P leaching and subsequent accumulation in the spodic
horizon of a Leon fine sand and that all fertilizer P had leached below a depth of 50 cm in

22
Pomello and Myakka soil series. A study by Wang et al. (1994) found that high levels of
P could be leached from surface (Ap) horizons of four sandy Florida soils heavily loaded
with dairy manure despite high pH and abundant Ca2+ in solid and solution phases.
Graetz and Nair (1995), Nair et al. (1995), Nair et al. (1998), and Nair et al. (1999), in a
series of studies on Spodosols in the Lake Okeechobee basin of Florida, concluded that P
that leaves the surface (A) horizon might be lost through surface and subsurface drainage,
and the portion that reaches the spodic (Bh) horizon will be held as Al- and Fe-associated
P, either in the inorganic or in the organic fraction. The high percentage of HC1-
extractable P (Ca- and Mg-associated P) in the A horizon of the intensive dairy
component was also of potential concern. This P could be continuously extracted by NH4
Cl or by water, suggesting that about 80% of the total soil P had the potential to move
eventually with drainage water into Lake Okeechobee (Graetz and Nair, 1995).
Recently, Sims et al. (1998) reviewed some current research on P leaching and
loss in subsurface runoff in Delaware, Indiana, and Quebec and concluded that the
situation most commonly associated with extensive P leaching, and thus the increased
potential for P loss via subsurface runoff, has been the long-term use of animal manures.
Manure Management
Developing manure management plans that are agronomically, economically, and
environmentally sound is a challenge because issues like accelerated eutrophication, P or
N limitation, transport mechanisms, source management, soil P level, environmental soil
testing for P, manure management and land application of manure have to be considered.
This review of the literature shows the urgent need for research especially in areas of
intensified dairy production and deep, coated sandy soil. Many factors can be involved in
developing an environmentally sound plan for manure management. Animal manure can

23
be a valuable resource if it can be integrated in cost effective best management practices.
Uptake of nutrients by agronomic crop sequenced over time is an effective, economical,
and environmentally sound means of nutrient recovery, especially if the cropping system
met the environmental concerns. The environmental concerns can be meet by maximizing
nutrient uptake by the crops while meeting the need of dairy producers.
A recent two years study on the use of dairy manure effluent in a rhizoma
(perennial) peanut based cropping system (French et. al. 1995) suggests that, if N
pollution is the major concern in a particular area, then the PP-R cropping system (year-
round perennial peanut and rye) would be a good choice since it performed as well or
better than the C-FS-R (com, forage sorghum, and winter rye) and C-PP-R (com planted
into a perennial peanut sod, perennial peanut, and rye) systems. However, if P is the
major concern, the C-FS-R and C-PP-R systems would be better choices. The C-FS-R
and C-PP-R systems were superior to the PP-R rotation in P removal values. Though P
level in perennial peanut forage were generally higher than those in com and forage
sorghum, they were not high enough to compensate for the much lower annual dry matter
yield of the perennial peanut system.
Dissertation Format
The subsequent chapters in this dissertation were prepared as individual
manuscripts. In this chapter, a general introduction, statement of the problem, review of
literature, and research objectives were presented. In chapter 2, the accumulation of P in a
sandy soil receiving dairy waste effluent was investigated. In chapter 3, the forms and
fractionation of P in the area under study were examined. In chapter 4, the retention
capacity of the soil was evaluated. In chapter 5, downward P movement was examined.

24
In chapter 6, plant uptake of the cropping systems under study was investigated. Chapter
7 provides a summary and conclusion of results presented in previous chapters.

CHAPTER 2
PHOSPHORUS ACCUMULATION IN A SANDY SOIL RECEIVING DAIRY
WASTE EFFLUENT
Introduction
The number of soils with plant-available P exceeding the levels required for
optimum crop yield has increased in areas of intensive agriculture and livestock
production (Sims, 1992; Snyder et al., 1993). In many parts of the world, concern and
research focuses on manure application, where amounts of P added often exceeded crop
removal rate on an annual basis. Many areas with intensive confined animal operations,
such as the Netherlands, Belgium, north-eastern USA and Florida, now have soil P levels
that are of environmental rather than agronomic concern (Sharpley et al., 1994b). In
1994, Kingery et al. (1994) reported P leaching to a depth of ~60 cm in tall fescue
pastures in the Sand Mountain region of northern Alabama that had received long term-
application (15-28 yr) of poultry litter. Soil test P (STP) (Mehlich I) values in topsoils
were extremely high (-230 mg/kg) relative to optimum values for crop production in this
region (25 mg/kg) (Cope et al., 1981). Similarly, Eghball et al. (1996) measured STP
(Olsen P) in the profile of a Tripp very fine sandy loam (a coarse-silty, mixed, mesic
Aridic Haplustoll) that had received long-term (>50 yr) application of cattle feedlot
manure and/or fertilizer P. Crops grown included sugarbeet, potato, and corn. Increases in
STP were reported and the increases were associated with P leaching to -75 cm with
fertilizer P (superphosphate) and to -1.0 m for manure or manure plus fertilizer P.
Mozaffari and Sims (1994) measured STP (Mehlich I) values with depth in cultivated and
25

26
wooded soils on farms in a coastal plains watershed dominated by intensive poultry
production and frequent applications of poultry litter, and observed P leaching to depth of
~60 to 75 cm in agricultural fields. STP (Mehlich I)values in these soils were very high
in topsoils relative to those considered optimum for most agronomic crops (25 mg/kg)
(Sims and Gartley, 1996). In North Carolina, King et al. (1990) examined the effect of 11
years of swine lagoon effluent application on P distribution within the profile of a
Paleudult used for coastal bermudagrass pasture. They reported STP (Mehlich I) values
much greater than required for crop production 225-450 mg/kg vs. an optimum soil test
value of -20-25 mg/kg. Soil test P at the 15 to 30, 30 to 45, 45 to 60, and 60 to 75 cm
depths was <5 mg/kg in nearby unfertilized pasture. However at the same depths, STP
was about 120, 75, 25, and 5 mg/kg at the lowest effluent rate (335 kg N/ha per year) and
350, 175, 125, and 50 mg/kg at the highest effluent rate (1340 kg N/ha per year).
Phosphorus loading from dairy lagoon effluent to soils in the Lake Okeechobee Basin,
Florida resulted in significant accumulation of P. In some cases; P concentrations were
about 50 times that of unimpacted areas (Graetz and Nair, 1995).
A considerable body of research now shows that STP levels influence the amount
ofP in runoff water and subsurface drainage (Pote et al., 1996 ; Sharpley et al., 1977;
Heckrath et al., 1995). Therefore, STP could help identify areas of potential losses of P.
This study was initiated to investigate the accumulation of P in the soil profile
during application of dairy waste effluent to two cropping sequences at two N rates in a
deep sandy soil.

27
Materials and Methods
Experiment Location and Design
The study was located at the North Florida Holstein Dairy facility, which is two
miles south of Bell, Florida. A randomized block design containing three blocks and
arranged as a split plot was used as the experimental design. Main plots were N loading
rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste effluent
was used as the N source. The N application rates were 448 and 896 kg/ha/yr which
correspond to P loadings of 112 and 224 kg/ha. The cropping systems were com- forage
sorghum-rye and perennial peanut-rye.
Soil Selection and Sampling
The soil was mapped as a Kershaw sand (sandy, thermic, uncoated Typic
Quartzipsamments). Soil profile samples (0-15, 15-30, 30-45, 45-60, 60-80, 80-100 cm)
were collected from each treatment in 1996 (prior to effluent application) and in 1997 and
1998 (after effluent application). Soil from three profiles in each subplot was collected,
composited, mixed thoroughly and a 1-kg subsample was brought to the laboratory for
analysis. Soil samples were air-dried and sieved (2mm) prior to analysis. Soil samples
were also collected in a similar manner from an adjacent native area believed to be
unimpacted by manure or fertilization application.
Soil Characterization
Texture was determined using the pipette method (Day, 1965). Total phosphorus
(TP) was determined by ashing 1.0 g of soil for 3 hours and then solubilizing with 6 M
HC1 (Anderson, 1976). Double-acid (Mehlich I)-extractable P, Al, Fe, Ca and Mg were
obtained with a 1:4 soil/double acid ratio (Mehlich, 1953). Phosphorus (P) in solution
was analyzed by the molybdenum-blue method (Murphy and Riley, 1962). Soil pH was

28
determined on 1:2 soil/water ratio, and the organic carbon content of the air-dried
samples was determined by combustion (Broadbent, 1965).
Effluent Application and Characterization
Effluent was taken directly from the dairy waste pond on the farm in which the
manure flushed from the milking parlor and feed barn is collected. The effluent was
applied to the experimental area through a center pivot irrigation system. The annual
application of effluent ranged between 355 to 500 mm depending on N application rate
and the concentration of N in the effluent. The average annual concentration of TP
ranged from 56 mg/L in 1996 to 49 mg/L in 1998, and the soluble reactive phosphorus
(SRP) from 44 in 1996 to 47 mg/L in 1998 (Table 2-1).
Table 2-1. Average annual concentrations (mg/L) of ammonium nitrogen (NKU -N), total
Kjeldahl nitrogen (TKN), soluble reactive P (SRP), and total P (TP) in effluent applied to
the study site. Numbers in parentheses are standard deviations.
NH4-N TKN SRP TP
YEAR
mg/L
1996
172(48)
258(84)
44(14)
56(20)
1997
176(40)
302(75)
44(12)
55(18)
1998
192(51)
280(69)
47(6)
49(20)
Statistical Analysis
Data analyses were done using SAS program (SAS Institute Inc. 1985) (PROC
MIXED) procedure (SAS Institute Inc. 1992). The PROC MIXED procedure was
selected based on the fact that it is designed for a mixed effect model where random

29
terms are incorporated into inference from the outset. Contrast, least square means and
estimates of linear combinations are reported with correct standard errors. The GLM
(General linear Model) which is designed for a fixed effect model, with allowance for
certain adjustments in the presence of random terms, needs special attention to be given
to least square means and contrast since their standard errors are not necessarily correct.
This is true, for example, for split-plot design as is the case for the experimental design in
this study (Schabenberger, 1996).
The main difference between of PROC MIXED and PROC GLM is that PROC
MIXED estimation of variance is based on maximum likelihood while PROC GLM is
based on method of moments estimation (ANOVA method) of solving expected mean
squares for the variance components (Schabenberger, 1996). Another advantage of PROC
MIXED is that it allows data that are missing at random while PROC GLM requires
balanced data, and ignore subjects with missing data (Wolfinger and Chang, 1996). This
criteria for PROC MIXED was of interest in handling the analysis of this study. This
study is a component of a larger project, which include three main treatments (effluent
application rate) and five cropping systems as a sub treatments in a split plot design with
the aim of comparing their effectiveness in nutrient recovery and maintenance of
acceptable levels of N and P in ground water. However, for the purpose of this study, two
effluent application rate and two cropping systems were selected under the original
experimental design. The selection of PROC MIXED to analyze data of the study offered
a means of dealing with unbalanced data. The model used in the analysis included: date,
block, rate, crop, and depth and their interactions such as date*rate, date*crop, crop*rate,

30
date*depth, rate*depth, crop*depth, date*crop*rate, date*rate*depth, date*crop*depth,
crop*rate*depth, and date*crop*rate*depth.
Results and Discussion
The study site soil was mapped as Kershaw sand (sandy, thermic, uncoated Typic
Quartzipsamments) in the Gilchrist County soil survey report (Soil Survey Staff, Gilchrist
County, Florida, 1973). Since the publication of the report, the criterion for coated vs.
uncoated family placement has been changed for the USDA soil taxonomic system (Soil
Survey Staff, 1999). The sandy materials sampled in this study would meet the criterion
for coated (5 percent silt plus 2 times the clay content), based on the particle size analysis
(Table 2-2). Also, some auger borings to 2 m revealed spodic horizons which indicated
inclusions of Spodosols, and dark colors in the surface horizon in some areas qualify it to
be an Umberic epipedon, which would result in classification as an Inceptisol (Umbrept)
rather than a Psamment. Nevertheless, the soil was consistently sandy and similar to
Kershaw sand with respect to use and management.
Soil Properties Prior to Effluent Application
The soil from the study site prior to effluent application had a different chemical
composition than a soil samples from a native site (Table 2-3). Double acid (Mehlich I)-
extractable elements and TP concentrations for the study site prior to the application of
effluent were higher than the concentrations in soil from the native site (Table 2-3). For
example, Mehlich I-extractable Ca for the study site ranged from 968 mg/kg at the
surface horizon to 75 mg/kg at the lower depth of the profile (100 cm). Comparable
values for the native site were 12 and 4 mg/kg, respectively (Table 2-3). Differences in
Ca and Mg content between the native site and the study site prior to the application of

31
Table 2-2. Selected characteristics of typical Kershaw sand (Soil Survey Staff, Gilchrist
County, Florida, 1973) compared to the study site.
^V^WV>Vr^nWrrXvVVVV%%V,W«1rtVVVYWVVVYyYVVY»VWV»VVVyYV\VVyVVVVVW>tvVV>»Y»Y»YVVVyVVVVVVVV.V»W«VV^YWVVYMV^VrtWVVVWY>VIV>VrtVWMYVYV%VVVV
Location Horizon Depth pH Org. C SAND SILT CLAY
cm
%
Native
A
0-18
4.8
0.99
96.5
1.1
2.4
Cl
18-76
5.0
0.39
96.1
1.8
2.1
C2
76-147
4.9
0.16
97.3
0.4
2.3
C3
147-203
5.0
0.10
96.1
2.0
1.9
Studv Site
A1
0-15
6.2
1.54
93.1
4.8
2.0
A2
15-30
6.0
0.79
94.1
4.2
1.7
Cl
30-45
6.5
0.71
95.3
3.1
1.6
Cl
45-60
6.5
1.58
95.0
3.8
1.2
C2
60-80
6.6
0.54
95.4
2.7
1.9
C2
80-100
6.5
0.43
95.9
2.4
1.7

32
Table 2-3. Mehlich I-extractable elements concentrations and total P (TP) in “native” soil
(n = 3 profiles) and study site (n = 12 profiles) soil profiles prior to beginning of the
study.
Location
Depth
Ca
Mg
A1
Fe
P
TP
cm
(mg/ Kg;
Native
0-15
11.7
1.9
267
18.4
47
214
15-30
5.1
1.1
317
20.7
52
270
30-45
6.0
0.8
330
19.1
39
241
45-60
4.7
0.7
337
16.3
36
184
60-80
4.7
0.8
308
16.3
39
181
80-100
4.1
0.7
280
14.3
33
173
Studv
0-15
968
115
301
23.5
283
328
Site
15-30
522
69.3
280
22.8
184
254
30-45
208
34.1
203
19.6
75
154
45-60
135
25.7
161
17.9
37
254
60-80
103
22.9
133
15.9
20
218
80-100
75
19.2
117
14.5
12
192

33
effluent were also reflected in a higher pH in all horizons in the study site. The higher
pH and organic C in all horizons of the soil from the study site prior to effluent
application could be attributed to a previous manure application. Dairy manure can
appreciably elevate not only the P, but also other components in soils (Dantzman et al.,
1983; Wang et al., 1995). The elevated level of P (TP and Mehlich I- extractable P) in the
soil of the study site indicated a previous manure application (Table 2-3). The site
appeared to havebeen heavily loaded with animal waste prior to the start of this study (47
mg/kg Mehlich I-extractable P in the native area vs 283 mg/kg Mehlich I-extractable P in
study site surface horizon soils). Several studies (Sims, 1992; Snyder et al., 1993;
Sharpley et al., 1994b; Kingery et al., 1994; Graetz & Nair, 1995; Wang et al., 1995)
have shown that manure application usually results in an increase in TP, STP and other
components in soil.
Effect of Application Rate and Cropping Systems
Statistical evaluation of TP data (Table 2-4) shows that date and depth were
significant at the 0.0001 probability level, but date*depth and date*crop was also
significant at 0.0001. However, neither the single effect of crop (cropping system), nor
the rate (effluent application rate) was significant. Therefore, a higher level of
significance such as date*depth and date*crop will be reported and interpreted, when it
was appropriate. Means comparison was done when there was a significant interaction by
SAS code (pdiff) for differences between least squares means (LSM).
Total P (TP) increased over time (1996 vs. 1998). The effect of date*depth was
significant (P <0.01) to the depth of 45 cm which reflects a buildup of total P in the soil
profile. Also, the effect of date*crop was significará (P<0.01) which might imply a role

Table 2-4. Statistical evaluation of TP data for the three-year study period.
Source
NDF
DDF
Type III F
Pr > F
Date
2
96
36.31
0.0001
Block
2
2
0,46
0.6867
Rate
1
2
0.37
0.6063
Date*Rate
2
96
2.65
0.0760
Crop
1
44
0.15
0.7001
Date*Crop
2
96
7.47
0.0010
Crop*Rate
1
44
1.18
0.237
Date*Crop*Rate
2
96
0.83
0.4412
Depth
5
44
46.25
0.0001
Date*Depth
10
96
15.82
0.0001
Rate*Depth
5
44
1.21
0.3226
Date*Rate*Depth
10
96
1.14
0.3395
Crop*Depth
5
44
0.84
0.5263
Date*Crop*Depth
10
96
1.69
0.0937
Crop*Rate*Depth
5
44
0.6
0.6410
Date*Crop*Rate*Depth
10
96
1.08
0.3853

35
for the cropping system on P removal. The application of effluent at both rates (448 and
896 kg N/ha per year) increased TP content of the Soil and the increase was dependent on
the effluent application rate. Total P in the surface horizon increased from 312 to 753
mg/kg at the end of the study under the high application rate (Fig. 2-1) and from 343 to
485 mg/kg under the low application rate (Fig. 2-2). A higher TP content in soil impacted
f
by dairy waste application is common. Graetz and Nair (1995) reported up to 1885 mg/kg
of TP in the soil surface horizon of dairy intensive areas.
The application of effluent also had an effect on Mehlich I-extractable P. The
effect of date*depth (P<0.05) and rate*crop (P<0.01) on Mehlich I-extractable P were
significant. During the two year of effluent application, Mehlich I-extractable P
decreased in the surface horizon but increased in the lower horizons (Fig. 2-3). The
decrease of Mehlich I-extractable P in the surface horizon and the increase in the lower
depths of the profile may be attributed to both crop uptake of P and the leaching effect of
effluent irrigation. Mozaffari and Sims (1994) measured soil test P (Mehlich I) values
with depth in cultivated and wooded soils on farms impacted by poultry litter
applications, and observed leaching to depth of ~ 60 to 75 cm. Soil test P values were
very high in topsoils relative to those considered optimum for most crops. Also, King et
al. (1990) examined the effect of 11 years of swine lagoon application on P distribution
and reported soil test P (Mehlich I) values much greater than required for crop production
(225-450) mg/kg. Soil test P at the 15-30, 30-45, 45-60, and 60-75 cm depth was 120,
75,25, and 5 mg/kg at the lowest effluent rate (335 kg N/ha per year) and 350, 175, 125,
and 50 mg/kg at the highest effluent rate (1340 kg N/ha per year). Soil test P (Mehlich I)
values for soil samples from the study site at 15-30, 30-45, 45-60, and 60-80 cm depth

36
TP, mg/kg
0 100 200 300 400 500 600 700 800 900
Figure 2-1. Average total P (TP) concentrations in the soil profile under the high rate
application prior to application of effluent (1996) and after effluent application (1997 and
1998). Values are LSM± Std. Error.

37
TP, mg/kg
0 100 200 300 400 500 600 700
Figure 2-2. Average total P (TP) concentrations in the soil profile under the low rate
application prior to application of effluent (1996) and after effluent application (1997 and
1998). Values are LSM± Std. Error.

38
Figure 2-3. Mehlich I-extractable P concentrations in the soil profile prior to start of the
study and after two years of effluent application (1998). Values are LSM± Std. Error.

39
were 197, 93, 55, and 32 mg/kg at the highest rate (896 kg N/ha per year) and 157, 62, 41
and 22 at the lowest rate (448 kg N/ha per year). These values of soil test P for the soil
samples from the study site after two year of effluent application should be looked at in
the context of high Mechlich I extractable P existing prior to the start of the study (Table
2-3). However, as for the rate*crop effect, Mehlich I-extractable P concentration was
• - r- ■
> * ■* J . . • * 1
higher for P-R (perennial peanut-rye) than for C-FS-R (corn-forage sorghum-rye)
cropping system under the high rate application (Fig. 2-4). This finding suggests that the
C-FS-R (corn-forage sorghum-rye) cropping system may be more effective in P removal
than the P-R cropping system. Only a slight change in Mehlich I-extractable P between
the two cropping systems was observed under the low application rate (Fig. 2-5). In spite
of the suggested higher P removal by the C-FS-R cropping system than the P-R cropping
system, the level of double acid (Mehlich I)-extractable P concentration in the study prior
to effluent application is considered to be extremely high relative to the optimum for crop
production when compared to levels reported by other studies (Kingery et al., 1994;
Mozaffari and Sims, 1994) and the removal by the cropping systems did not alter the high
level of STP. Such high level of STP can lead to leaching to a deeper depth in the soil
profile.
Although double acid may not extract the total amounts of reactive elements for P
retention, double-acid (Mehlich I)- extractable P was highly correlated with Ca, Mg, Al,
and Fe extracted by Mehlich I solution, with 93% of variability explained by this
relationship (Table 2-5).

40 - v < 1
P, mg/kg
0 50 100 150 200 250 300 350 400 450 500
Figure 2-4. Mehlich I-extractable P concentrations for cropping systems under the high
rate effluent application in 1998. Values are LSM± Std. Error.

Depth, cm
41
P, mg/kg
0 50 100 150 200 250 300
Figure 2-5. Mehlich I-extractable P concentrations for cropping systems under the low
rate effluent application in 1998. Values are LSM± Std. Error.

42
Table 2-5. Regression equation relating Mehlich I-P to the independent variables Mehlich
I-Ca, Mg, and Fe. (n=432).
Equation
Model R2
M I-P = -56.9 + 0.272 M I-Ca*** - 0.284 M I-Mg* + 0.233 M I-A1*** +
1.55 MI-Fe***
0.932***
***, *, Significant atp< 0.001, andp< 0.05 respectively. N.S. Not significant.
Summary and Conclusions
The soil at the study site has been mapped as Kershaw sand and is considered
uncoated. However, some coatings are evident based on the color of the sand grain and
the USD A taxonomic criterion of >5% silt plus (2 times the clay content) for coated
family placement (Soil Survey Staff, 1999). Sands that retain coating components should
have a higher affinity to retain P than do bare quartz grains (Harris et al., 1996), a
criterion that is favorable for this study. The soil at the study site appeared to have been
heavily loaded with animal waste prior to the start of this study. Mehlich I-extractable P
in the surface horizon of the native area was 47 mg/kg vs. 283 mg/kg Mehlich I-
extractable P in the study site surface horizon soils. Mehlich I-extractable P levels in
topsoils at the study site was high relative to those considered optimum for agronomic
crops and raise the question about the suitability of the effluent application rates used.
The effluent application rates selected were based mainly on estimated N removal for the
forage crops within the cropping systems and experimental purposes outlined in the main
project objectives.
The previous application of dairy manure to the study site prior to the start of the
study resulted also in a higher Ca~2 and Mg^2 content throughout the soil profile

43
compared to the native site, although the amount and date could not be established. The
application of dairy waste effluent at both rates (448 and 896 kg N/ha per year) over a 2-
year period increased the TP content in the soil profile to the 45 cm depth. The increase
in TP was significant and dependent on the effluent application rate. The application of
effluent also had an effect on the Mehlich I-extractable P. The effect of date*depth and
rate*crop on Mehlich 1-extractable P were significant. During the two year of effluent
application Mehlich I-extractable P decreased in the surface horizon but increased in the
lower horizons. The decrease of Mehlich I-extractable P in the surface horizon and the
increase in the lower depths of the profile may be attributed to both crop uptake of P and
the leaching effect of effluent irrigation. However, as for the rate*crop effect, Mehlich I-
extractable P concentrations were higher for P-R (perennial peanut-rye) than for C-FS-R
(corn-forage sorghum-rye) cropping system under the high rate application. This finding
suggests that the C-FS-R (corn-forage sorghum-rye) cropping system may be more
effective in P removal than the P-R cropping system. Only a slight change in Mehlich I-
extractable P between the two cropping systems was observed under the low application
rate. However, the removal by the cropping systems did not alter the high level of STP
that already existed. Thus, to prevent an accumulation of excessive P content in the soil
profile, history of the land, application rate, and cropping systems estimated removal ofP
should be considered.

CHAPTER 3
PHOSPHORUS FORMS AND FRACTIONATION IN A SANDY SOIL RECEIVING
DAIRY WASTE EFFLUENT
Introduction
Sequential extraction schemes using various chemical extracts have been
developed through the years to quantify and fractionate the different forms of P in soils.
The objectives of P fractionation in general are to provide insight into the fate and
transformation of P added to soils as fertilizers or manure, estimate the availability of P to
plants for agronomic purposes, estimate the potential for P movement from erosion and
through leaching, and provide information regarding the interaction between P in
sediments and the overlaying water in the case of aquatic systems (Graetz and Nair,
1999). The underlying assumption here is that inorganic P in soil consists of varying
proportion of three discrete classes of compounds, namely, Fe, A1 and Ca phosphate,
some of which could be occluded or enclosed within coating of Fe oxides and hydrated
oxides. These chemical P forms are operationally defined on the basis of reactivity of a
particular phase in a given extractant and subject to several interpretations. Nevertheless,
they offer a convenient means for obtaining significant information on P chemistry of
soils (Nair et al., 1995). Fractionation of P forms has been particularly useful in
understanding the transformation of P added to soil, either in inorganic or organic
amendments such as manures. Zhang and Mackenzie (1997) used P fractionation and
path analysis to compare the behavior of fertilizer and manure-P in soils. Their results
showed that P behaves differently when added as manure, compared to inorganic
44

45
fertilizer, which may affect the depth of P movement through the soil profile. Simard et
al. (1995) reported that a significant portion of the P moving downward in soils receiving
substantial amounts of animal manure accumulated in labile forms such as water-soluble,
Mehlich-3, and NaHCCb extractable P forms. Eghball et al. (1996) found that P from
manure moved deeper in the soil than P from chemical fertilizer in long term (>50 yr)
studies. Nair et al. (1995) studied the forms of P in soil profiles from dairies of south
Florida and illustrated the fate and transport of P in these systems. They identified the P
forms in the soil profile of differentially manure-impacted soils in the Okeechobee
watershed, Florida. All soils were Spodosols, and soils were collected by horizon, A, E,
Bh, and Bw. Their results showed no statistical differences in the percentage of labile P
(NFL* Cl-extractable P), the P that would most likely move from the A horizon of the
various components. The labile P form for the A horizon of all dairy components
averaged 9%. However, more P will be lost from the heavily manure-impacted intensive
areas with high total P values, than from the less impacted pasture, forage and native
areas. They also observed that the P would continue to be lost from dairies that have been
abandoned for a considerable period of time. The P that leaves the surface horizon might
be lost through surface and subsurface drainage, and the portion that reaches the spodic
(Bh) horizon will be held as Al- and Fe-associated P, either in the inorganic or in the
organic fraction. The high percentage of HCl-extractable P (Ca- and Mg-associated P) in
the A horizon of the intensive dairy component was also of potential concern. Such P
could be continuously extracted by NH4CI or by water, suggesting that about 80% of the
total soil P had the potential to move eventually with drainage water into Lake
Okeechobee (Graetz and Nair, 1995).

46,
Recently, other watersheds in Florida such as the Middle Suwannee River area
have become the focus of attention. Soils in this area include Entisols; soils lacking
diagnostic horizons and other features that are specifically defined and required for other
orders of the USDA taxonomic system (Soil Survey Staff, 1994). Quartzipsamments, the
only Psamment Great Group which occurs in Florida, are in central northern peninsular
Florida and most prevalent on well to excessively drained landscapes (Harris and Hurt,
1999). The sandy nature of Quartzipsamments result in relatively low P retention or
capacity. Therefore, an understanding of P forms in such soil receiving dairy manure
effluent application could help identify areas of potential losses of P.
Materials and Methods
Experiment Location and Design
The study site was located at North Florida Holstein Dairy facility, which is two
miles south of Bell, Florida. A randomized block design containing three blocks and
arranged as a split plot was used as the experimental design. Main plots were N and P
loading rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste
effluent was used as the N source. The N application rates were 448 and 896 kg/ha/yr,
which correspond to P loading of 112 and 224 kg/ha/yr. The cropping systems were corn-
forage sorghum-rye and perennial peanut-rye.
Soil Selection and Sampling
The soil was mapped as Kershaw (sandy, thermic, uncoated Typic
Quartzipsamments). Soil profile samples (0-15, 15-30, 30-45, 45-60, 60-80, 80-100 cm)
were collected in 1996 (prior to effluent application) and in 1997 and 1998 (after effluent
application). Soil from three profiles in each subplot was collected, composited, mixed

47
thoroughly and a 1 -kg subsample was brought to the laboratory for analysis. Soil samples
were air-dried and sieved (2mm) prior to analysis. In addition to soil samples from the
study site, soil samples were also collected in a similar manner from an adjacent native
area believed to be unimpacted by manure or fertilization application.
Fractionation Scheme
The scheme used to fractionate soil-P was a modification of that of Hieltjes and
Lijklema (1980) by Nair et al., (1995). A 1-g air dried sample was sequentially extracted
twice with 25 mL of 1 A/NH4CI (adjusted to pH 7.0) with two hours shaking, 0.1 M
NaOH with seventeen hours shaking, and 0.5 A/HC1 with 24 hours shaking. The 1: 25
soil: solution ratio was selected based on preliminary investigations as shown in
APPENDIX. After each extraction, the content were centrifuged for 15 min at 3620 x g
and filtered through a 0.45-pm filter. All extractions were carried out at room
temperature. Residual P was determined by ashing previously extracted soil sample for
three hours and then solubilizing with 6MHC1 (Anderson, 1976). A 5 mL of the NaOH
extract was also digested by persulfate-sulfuric acid mixture at 380°C (APHA, 1985) to
determine moderately labile organic P as the difference between P in digested and
undigested NaOH extract. NFLjCl-extractable P was defined as labile P (Petterson and
Istvanovics, 1988), NaOH-extractable P as Fe-Al-associated P, and HCl-extractable P as
Ca-Mg-associated P. Residual P is the P that is not readily removed by any of the above
chemical extractants. Total phosphorus (TP) was determined by ashing 1.0 g of soil for 3
hours and then solubilizing with 6MHC1 (Anderson, 1976). Double-acid (Mehlich I)-
extractable P, Al, Fe, Ca and Mg were obtained with a 1:4 soil/double acid ratio
(Mehlich, 1953). Phosphorus (P) in solution was analyzed by the molybdenum-blue

48
method (Murphy and Riley, 1962) on a spectrophotometer at wavelength of 880 nm.. Soil
pH was determined on 1:2 soil/water ratio, and the organic carbon content of the air-dried
samples was determined by combustion procedure (Broadbent, 1965). Texture was
determined using the pipette method (Day, 1965).
Statistical Analysis
Data analyses were done using SAS program (SAS Institute Inc. 1985) (PROC
MIXED) procedure (SAS Institute Inc. 1992). Relationships among parameters were
evaluated using linear correlation. Multiple regression was used to examine the strength
of the relationships between parameters.
Results and Discussion
Inorganic Fe/Al associated P constituted the major proportion of TP in the soil
profile of the study site prior to effluent application. As concluded from Chapter 2, the
soil at the study site appeared to have been heavily loaded with animal waste prior to the
start of this study, although amount and dates could not be established. Phosphorus
originally present in the soil profile in 1996 (prior to effluent application) was largely in
the form of inorganic Fe/Al-associated P, which ranged from 292 mg/kg in the surface
horizon to 76 mg/kg in lower depth (100 cm) (Table 3-1). These values of Fe/Al- P
corresponded to 62% and 49% of TP, respectively (Table 3-2). The application of
effluent increased this fraction to 362 mg/kg in the surface horizon in 1998 with smaller
increase throughout the soil profile (Fig. 3-1). A comparison of Fe/Al-P mean
concentration in each depth within the soil profile at the beginning (1996) and end of the
study period (1998) showed that the increase was statistically significant (JP <0.001-
P<0.05) at the surface and down to the 45 cm depth (Table 3-3). The predominance of

49
Table 3-1. P values (mg/kg) in each fraction within a soil depth increment at the
beginning (1996) and end of the study period (1998) (n = 12 profiles). Values are Least
Square Means (LSM).
Depth Labile Al-Fe Ca-Mg Residual
(cm) - mg/kg ■ —
1996
0-15
85
292
50
36
15-30
61
221
30
22
30-45
36
146
21
16
45-60
44
106
12
25
60-80
37
87
09
29
80-100
37
76
12
25
1 QQ8
1770
0-15
97
362
52
59
15-30
93
317
30
40
30-45
80
205
17
28
45-60
77
137
13
23
60-80
71
101
07
23
80-100
69
81
07
19

50
Table 3-2. Percentage of P in each fraction within a soil depth increment at the beginning
(1996) and end of the study period (1998)(n = 12 profiles). Values are Least Square
Means (LSM).
Depth Labile-P Al-Fe-P Ca-Mg-P Residual-P Sum of
(cm) % P fraction
mg/kg
1996
0-15
18.3
62.6
10.8
8.30
463
15-30
18.4
65.3
9.20
7.10
334
30-45
16.8
64.5
10.5
8.20
219
45-60
24.8
54.9
7.00
13.3
187
60-80
24.3
52.3
5.80
17.0
162
80-100
26.3
49.4
8.20
16.1
150
1998
0-15
17.0
63.5
9.1
10.3
570
15-30
19.4
66.0
6.2
8.30
480
30-45
24.2
62.1
5.1
8.50
330
45-60
30.8
54.8
5.2
9.20
250
60-80
35.1
50.0
3.5
11.4
202
80-100
39.2
46.0
4.0
10.8
176

Depth,cm
51
P, mg/kg
0 50 100 150 200 250 300 350 400 450
Figure 3-1. Al-Fe-associated P (mg/kg) within the soil profile at the beginning 1996 and
end of the study period (1998). Values are LSM± Std. Error.

52
Table 3-3. Increases in each fraction within a soil depth increment between the beginning
(1996) and end of the study period (1998).
Depth
(cm)
Labile
mg/kg
Al-Fe
mg/kg
Ca-Mg
mg/kg
Residual
mg/kg
0-15
11.75*
69.76**
NS
22.31**
15-30
31.62**
95.69**
NS
17.69**
30-45
44.55**
59.03**
NS
23.9**
45-60
33.38**
31.0*
NS
NS
60-80
34.52**
NS
NS
NS
80-100
31.44**
NS
NS
NS
*, ** Significant at the .05 and .001 probability levels, respectively; NS = none
significant.

53
Fe/Al-associated P in surface horizon and throughout the profile was a reflection of the
properties of soil and the dairy waste effluent used. The soil at the study site, as
mentioned in Chapter 2, was classified as coated sand with low clay content, low organic
matter, pH of 6-6.5, and a higher Mehlich I- extractable P (Table 3-4) in comparison to
soil from a native area (283 vs. 47 mg/kg). The soil from the native area, which has a low
content of clay, organic matter, moderately low pH (4-4.5), and a high Mehlich I-
extractable Al/Fe, compared to the rest of cations in the soil, was a typical example of
predominance of P retention by Al/Fe oxides. Further more, P fractionation of soil
samples from the native area showed that up to 62% of TP was in the form of Al/Fe-
associated P (Tables 3-5 and 3-6).
The predominance of Al/Fe-associated P in the soil samples from the study site
was a reflection of its original properties, and its increase after effluent application could
be a consequence of adsorption under continuous application of a soluble P. The dairy
waste effluent contained 55 mg P/kg, 78% of which was soluble reactive P (SRP). The
difference between pH values of soil sample from the study site and native area, and the
presence of a higher Mehlich I-extractable Ca content in soil samples from the study area
did not seem to alter the predominance of Al/Fe-associated P in the P fractionation
scheme.
Labile-P or easily removable P as defined by (Petterson and Istvanovics, 1988)
constituted 18-40% of TP in the soil profile of the study site. Prior to effluent application
in 1996, labile-P ranged from 85 mg/kg in the surface horizon to 37 mg/kg in the lower
depth (100 cm) (Table 3-1) which corresponds to 26 and 18% of TP, respectively (Table
3-2). The application of effluent increased this fraction to 97 mg/kg in surface horizon

54
Table 3-4. Mean concentration of Mehlich I extractable elements (mg/kg) in the soil
profile of the study site in
1996 prior to the application of effluent (n =
12 profiles).
Mehlich I Extractable Elements (mg/kg)
Location
Depth
(cm)
Ca
Mg
A1
Fe
Studv Site
0-15
968
115
301
23
15-30
522
69
280
23
30-45
208
34
203
20
45-60
135
26
161
18
60-80
103
23
133
16
80-100
75
19
117
14

55
Table 3-5. P values (mg/kg) in each of the fractions within a soil depth increment at the
native site (n = 3 profiles). Values are Least Square Means (LSM).
Depth Labile Al-Fe Residual Ca-Mg Sum of P
(cm) P P P P Fractions
mg/kg — mg/kg
0-15
68
125
3
6
202
15-30
59
195
20
12
26
30-45
58
166
4
13
241
45-60
58
136
17
8
219
60-80
58
150
17
9
234
80-100
61
149
16
9
235
Table 3-6. Percentage of P in each of the fractions within a soil depth increment at the
native site (n = 3 profiles). Values are Least Square Means (LSM).
Depth Labile Al-Fe Ca-Mg Residual
(cm) P P P P
%
0-15
33
62
3
2
15-30
20
68
4
7
30-45
23
69
5
2
45-60
26
62
4
8
60-0
24
64
4
7
80-100
26
63
4
7

56
and 69 mg/kg in the lower depth (100 cm) (Table 3-1) and (Fig. 3-2). Labile-P (Fig. 3-2)
increased in the surface horizon and throughout the profile over time (1996 vs. 1998)
with a substantial increase in the lower depth accounting for 40% of TP in 1998 (Table 3-
2). A comparison of labile-P mean concentration in each depth within the soil profile at
the beginning (1996) and end of the study period (1998) showed that the increase was
statistically significant (P <0.001- P<0.05) at the surface and throughout the profile
(Table 3-3). The previous mentioned studies by Nair et al. (1995) and Graetz and Nair
(1995) has reported that labile P form for the A horizon of Spodosol in all dairy
components averaged 9% in a single NH4CI extraction and 1:10 soil: solution ratio. The
higher percentage of labile P form in this study throughout the profile and its substantial
increase in the lower depth after effluent application is likely due to rapid movement of P
through the profile.
In this study, the Ca and Mg-associated P fraction was the only fraction that
remained constant and did not show change with the application of effluent over time
(Table 3-1 and 3-2); (Fig. 3-3) in spite of considerable Mehlich I extractable-Ca content
throughout the soil profile as shown in Table 3-4. Though the stability of P forms is not
addressed in this study, Harris et al. (1994) reported an absence of Ca-P minerals despite
high pH and years of high Ca and P additions in soils from intensive areas of dairies in
south Florida. The lack of crystalline Ca-P could be related to kinetics, or to a poisoning
effect of component such as Mg, Si and organic acids in the dairy soil system (Wang et
al., 1995). The absence of a significant change in the Ca/Mg-associated P pool, in this
study, could be due to the factors mentioned by Wang et al., 1995 or due to analytical

Depth, cm
57
P, mg/kg
-■-1996 -♦-1998
Figure 3-2. Labile P values (mg/kg) within the soil profile at the beginning (1996) and
end of the study period (1998). Values are LSM± Std. Error.

Depth,cm
58
P, mg/kg
0 10 20 30 40 50 60
Figure 3-3. Ca-Mg associated P values (mg/kg) within the soil profile at the beginning
(1996) and end of the study period (1998). Values are LSM± Std. Error.

59
limitation. Nair et al. (1995) noticed that the labile P fraction increased if the soil was
repeatedly extracted with the 1 MNH4CI solution, with a corresponding decrease being
noted for the HC1P fraction (Ca/Mg-associated P pool).
Residual-P, the P fraction that is not readily removed by any of the chemical
extractants, constituted 7 to 17% of TP in the soil profile of the study site in 1996 prior to
the application of effluent (Table 3-1). This percentage corresponded to 25 and 36 mg
P/kg, respectively (Table 3-2). The application of effluent increased this fraction to 59
mg P/kg at the surface horizon in 1998 (Table 3-1) and (Fig. 3-4). However, as a
percentage of TP this amount constituted 10% of total P (Table 3-2). Bowman et al.,
1998 used both terms resistant P and residual P to mean that pool which is extracted with
great difficulty, or by difference from the whole when a soil residue yields essentially no
more acid- and base-extractable inorganic P (Pi) and organic P[ Po, as determined by
difference (Pt - Pi)]. They reported an average of about 26% of TP as resistant, with the
more weathered soil containing about 50% resistant P. Nair et al. (1995) studied the
distribution of P forms of two abandoned dairies (12 and 18 yr) compared with the
youngest active (8 yr) dairy and reported an increase in Ca/Mg-associated P (61-74 %)
and a decrease in residual P (20 to 11%) in the A horizon of the abandoned dairies in
south Florida. They related this trend to a possible gradual mineralization of the residual
P, if the residual P is primarily recalcitrant organic P. However, the trend of increasing
residual P content in this study could be related to certain components in the effluent
used. The fractionation scheme used in this study did not offer a way of fractionating
residual P into organic and inorganic forms.
The trend of distribution of different P pools in this two year study was

60
P, mg/kg
0 10 20 30 40 50 60 70
Figure 3-4. Residual-P values (mg/kg) within the soil profile at the beginning (1996) and
end of the study period (1998). Values are LSM± Std. Error.

61
that Al-Fe- associated P constituted the major proportion of TP in soil profile followed
by labile-P (prior to effluent application) and that both showed an increase with the
application of effluent. The increase of labile-P in the lower depth of the soil profile after
effluent application could be an indication of downward P movement in the soil profile.
Previous research in forms of P in soil profile from dairies of south Florida by
Graetz and Nair (1995) reported a predominance of Al/Fe-P (49% of TP) in the A
horizon of Spodosol soils from nonimpacted areas. However, the predominant form of P
in the A horizon of highly manure-impacted areas (active dairies for up to 32 years) was
Ca/Mg-P which reflect the predominance of Ca/Mg in cattle manure in their case. They
also reported that high percentage of HCl-extractable P (Ca/Mg-associated P) in the A
horizon of the intensive dairy component was of potential concern. This P could be
continuously extracted by NH4 Cl or by water, suggesting that about 80% of the total soil
P had the potential to move eventually with drainage water into Lake Okeechobee (Nair
et al„ 1995).
Summary and Conclusions
Most of P in the soil profile of the study site (prior to effluent application)
consisted of Fe/Al-associated P, which accounted for 49-62% of TP. The application of
effluent resulted in an increase in this fraction throughout the soil profile. Labile-P
constituted 18-26% of TP in the soil profile of the study site prior to effluent application,
and the application of effluent increased this fraction significantly up to 40% of TP at the
lower depth of the profile (100-cm). The increase in labile-P at the lower depth (100-cm)
of the soil profile after two years of effluent application could be an indication of
downward P movement in the soil profile. Ca/Mg-associated P was the only fraction that

62
remained constant and did not show change with the application of effluent over time.
However, the absence of a significant change in Ca/Mg-associated P in this study could
be due to analytical limitation. Nair et al. (1995) noticed that the labile P fraction
increased if the soil was repeatedly extracted with the 1 M NH4CI solution, with a
corresponding decrease being noted for the HC1- P fraction (Ca/Mg-associated P pool).

CHAPTER 4
PHOSPHORUS RETENTION IN A SANDY SOIL RECEIVING DAIRY WASTE
EFFLUENT
Introduction
Sandy soils generally retain less P than finer textured soils because of a deficiency
of mineral components having surface affinity for orthophosphate. Thus, subsurface
transport of P can be significant in sandy soils due to low surface area or a paucity of P-
retaining components (Reddy et al., 1996). However, sand-grain coatings could
significantly enhance P adsorption and resistance to desorption (Harris et al., 1996).
Phosphorus retention in such soil has been the focus of a number of studies due to its
relevant environmental consideration in areas of intensified animal-based agriculture
(Mozaffari and Sims, 1993; Harris et al., 1994; Graetz and Nair, 1995; Nair et al., 1998;
Nair et al., 1999). Furthermore, attempts has been made to use a single-point isotherm to
characterize P retention in such soils (Mozaffari and Sims, 1993; Harris et al., 1996; Nair
et al., 1998). A single point isotherm indexing approach, termed the relative phosphorus
adsorption (RPA) index, effectively arrayed sandy Florida soil samples with respect to
relative P adsorption (Harris et al., 1996).
Although the equilibrium P concentration in the soil solution is generally
relatively low, recent studies have shown that the P concentration in the soil solution can
increase significantly well before the soil adsorption maximum has been reached
(Breeuwsma and Silva, 1992). The Dutch have developed a test referred to as the
63

64
“Degree of P Saturation” (DPS) which relates the soil P sorption capacity to an
extractable P concentration as follows:
DPS = Extractable soil P x 100
P sorption maximum
Operationally, DPS can be defined as oxalate-extractable P divided by the
phosphate sorption capacity of the soil that is estimated from equations including oxalate-
extractable Fe and A1 (Breeuswma et al., 1995) as follows:
DPS = Pox x 100
Fe ox + Alox
The Dutch used a reference soil solution concentration of 0.1 mg P/L as a critical
concentration based on water quality studies. They found that a DPS value of 25% would
generally result in soil solution concentration equal to greater than 0.1 mg P/L. Pautler
and Sims (1998) study on comparison of short-and long-term sorption kinetics in Atlantic
coastal plain soils concluded that the potential for P loss from over-fertilized soils can be
improved by a knowledge of DPS of soils.
Sharpley (1995) found a single relationship (r2 of 0.86) to describe the
concentration of dissolved phosphate (DP) as a function of P-sorption saturation for ten
soils ranging from sandy loam to clay in texture. The Mehlich-3 extractant was used for
extractable soil P and the Langmuir P-sorption maximum as P-sorption capacity in the
calculation of DPS.
This study was conducted to evaluate the P retention of a sandy soil under dairy
effluent application using traditional multipoint isotherms, RPA, and DPS.

65
Materials and Methods
Experiment Location and Design
The site of the study was located at North Florida Holstein Dairy facility, which is
two miles south of Bell, Florida. A randomized block design containing three blocks and
arranged as a split plot was used as the experimental design. Main plots were N loading
rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste effluent
was used as the N source. The N application rates were 448 and 896 kg/ha/yr which
correspond to P loading of 112 and 224 kg/ha/yr. The cropping systems were corn-forage
sorghum-rye, and perennial peanut-rye.
Soil Selection and Sampling
The soil was mapped as a Kershaw sand (sandy, thermic, uncoated Typic
Quartzipsamments). Soil profile samples (0-15, 15-30, 30-45, 45-60, 60-80, 80-100 cm)
were collected in 1996 (prior to effluent application) and in 1997, and 1998 (after effluent
application). Soil from three profiles in each subplot was collected, composited, mixed
thoroughly and a 1-kg subsample was brought to the laboratory for analysis. Soil samples
were air-dried and sieved (2mm) prior to analysis. Soil samples were also collected in a
similar manner from an adjacent native area believed to unimpacted by manure or
fertilization application.
Soil Characterization
Rapid chemical assessment of relative phosphorus adsorption (RPA) was done by
procedure developed by Harris et al., (1996). Ten- gram samples of air-dry soil were
weighed into 20-mL scintillation vial and 2 mL of a 2000 mg/L P solution was added.
The content of the vials were mixed by vigorous shaking, and allowed to equilibrate for
24 hours at room temperature. The contents was transferred from the vials to centrifuge

66
tubes, and centrifuged at 1500 g for 5 min. The centrifuge tubes had small holes drilled
through the bottom. During centrifugation, solution passed through the holes into small
cups attached to the bottom of the centrifuge tubes. Solution was removed from the cups
and passed through a 0.45-p.m syringe filter. Phosphorus in the solution was determined
by the method of Murphy and Riley (1962) at an absorbance at 880 nm. The relative P
adsorption capacity was quantified by dividing the absolute amount of P adsorbed by the
maximum possible under these conditions, which was 400 mg/kg.
Phosphorus multipoint adsorption isotherms were measured using 2 g of an air-
dried soil treated with 20 mL of 0.01MKC1 solution containing various levels of P (0,
0.2, 0.5,1, 5, 10, 40, and 100 mg/L) in 50-mL centrifuge tubes. The tubes were placed on
a mechanical shaker for 24 hours equilibration period. At the end of 24 hours period, the
soil was centrifuged at 3620 x g for 10 min. The supernatant was then filtered through a
0.45-pm membrane filter and the filtrate analyzed for P (Murphy and Riley, 1962).
Total phosphorus (TP) was determined by ashing 1.0 g of soil for 3 hours and
then solubilizing with 6 MHC1 (Anderson, 1976). Double-acid (Mehlich I)-extractable P,
Al, Fe, Ca and Mg were obtained with a 1:4 soil/double acid ratio (Mehlich, 1953).
Phosphorus in solution was analyzed by the molybdenum-blue method (Murphy and
Riley, 1962). Soil pH was determined on 1:2 soil/water ratio, and the organic carbon
content of the air-dried samples was determined by combustion (Broadbent, 1965).
Texture was determined using the pipette method (Day, 1965).
Oxalate-extractable P, Al, and Fe were determined by extraction with an
ammonium oxalate (0.1 M oxalic acid + 0.175 M ammonium oxalate) solution adjusted to
pH 3.0 (McKeague and Day, 1966). The suspension was equilibrated for 4 hours with

67
continuous shaking, centrifuged, filtered through a 0.45-p.m filter and analyzed for P, Al,
and Fe.
Calculations
Degree of P saturation (DPS) was calculated as oxalate-extractable P divided by
the P sorption capacity of the soil, which is estimated as the sum of oxalate-extractable Fe
and Al (Breeuwsma et al., 1995). This DPS is referred to in this study as (DPS - 1). Also,
DPS was calculated as double acid (Mehlich I)-extractable P divided by the P sorption
capacity of the soil, estimated from the sum of oxalate-extractable Fe and Al. This DPS is
referred to as (DPS - 2).
Extractable soil P x 100
DPS = P- sorption capacity
P sorption capacity was estimated from oxalate-extractable Al and Fe.
Adsorption parameters were calculated using the Langmuir adsorption equation:
C/S = l/kSmax + C/Smax
Where
S = S’ + So the total amount of P sorbed, mg/kg
S’ = P sorbed by the solid phase, mg/kg
So = originally sorbed on the solid phase, mg/kg
C = concentration of P after 24 h equilibration, mg/L
Smax = P sorption maximum, mg/kg
k = constant related to the bonding strength, L/mg P
So was estimated using a least square fit of S’ measured at low equilibrium
concentration, C. At these concentrations, the linear relationship between S’ and C can be

68
described by S’ = K C - So where K is the linear adsorption coefficient (Graetz and Nair,
1995). P0 ( soluble P) referred to P in solution after a 24-h equilibrium period when no P
was added.
Equilibrium P concentration (EPC), was defined as the concentration of P in
solution where adsorption equal desorption and was the value of C when S’ = 0.
Statistical Analysis
Data analyses were done using SAS (SAS Institute Inc. 1985) program (PROC
MIX) procedure (SAS Institute Inc. 1992). Relationships among parameters were
evaluated using linear correlation. Multiple regression was used to examine the strength
of the relationships between parameters.
Results and Discussion
Relative Phosphorus Adsorption (RPA)
After two years of effluent application, RPA values of soil samples from the study
site did not show any significant change and remained in the same range reported before
effluent application (Table 4-1). The absence of significant differences in RPA values pre
and after effluent application, indicated that effluent application did not influence P
sorption capacity for this soil which has been heavily loaded with animal manure prior to
the start of the study.
The RPA values of soil samples from the study site ranged from 0.5 to 0.6
throughout the profile pre-and post effluent application (Table 4-1). The samples from
native area adjacent to the study site showed an RPA value of 0.8 to 0.9 through out the
soil profile (Table 4-1). However, part of this difference could be due to differences in
clay content between native and study site samples as shown in Chapter 2 (Table 2-3).

69
Table 4-1. RPA values within the soil profile of the study site (n = 12 profiles) prior and
after to application of effluent compared to the “native soil” (n = 1 profile). Values are
Least Square Mean (LSM).
Depth
1996
1997
1998
Native
0-15
0.47
0.57
0.58
0.82
15-30
0.52
0.58
0.60
0.93
30-45
0.54
0.59
0.61
0.93
45-60
0.62
0.60
0.61
0.93
60-80
0.63
0.60
0.57
0.90
80-100
0.64
0.63
0.57
0.89

70
In the study by Rhue et al., 1994, RPA for Quartzipsamment was correlated with clay
content (R2 = 0.87).
RPA = -10.076 + 128.769 log (clay + 1)
Assuming that the relationship would apply to the soil at the study site and using the clay
contents in (Table 2-3), the RPA for native soil should have been about 0.60 while that
for the study site soil should have been about 0.45, showing the relative effect of clay
content on RPA. Why these measured RPA values were higher than those predicted by
the equation of Rhue et al., (1994) is not known. The effect of P loading on RPA has not
yet been explored. The relative contribution of clay and P loading cannot be related from
this data. The lower RPA values of the study site compared to the RPA values of the
native site indicated lower relative P adsorption capacity of the study site. Single-point
isotherm has been used to effectively index sandy materials. For example, Harris et al.
(1996) stated that RPA effectively arrayed sandy Florida soil samples with respect to
relative P adsorption. Their soil samples included five taxonomic groups for sandy
surface and subsurface horizon groupings. The RPA values were 0.74 and 0.69 for A and
Bt horizons of Paleudults, 0.54 for coated Quartzipsamments (defined as coated) in the
surface horizon and 0.58 in the subsurface, 0.48-0.47 for uncoated Quartzipsamments
(defined as slightly coated) surface and subsurface horizons, 0.26-0.08 for uncoated
Quartzipsamments (defined as clean) surface and subsurface, and 0.05-0.01 for Alaquods
surface and subsurface horizons, respectively. They also pointed out that RPA does not
directly provide values for maximum P adsorption, but it closely relates to such values
derived from P adsorption isotherms. Mozaffari and Sims (1994) also have evaluated
single-point isotherms after Bache and Williams P sorption index (PSI) and indicated

71
that PSI may be a viable alternative to sorption isotherms for the purpose of a rapid
means to assess the ability of a soil profile to retain additional P. The PSI in their case
was found to be highly correlated (r2 = 0.94) with the Langmuir P sorption maxima
except when PSI exceeded 1400 mg/kg, where significant non-linearity was observed.
Recently, Nair et al., (1998) found that single point sorption values measured at 1000 mg
P/kg for soils of the Bh and Bw horizons from a low manure-impacted (pasture) and a
high manure impacted (holding) areas were comparable (r2 = 0.98) to the Smax values
calculated using a Langmuir equation and concluded that a single point sorption value
was a very convenient and quick means of characterizing the soils for maximum P
sorption capacity.
In this study, values of RPA for soil samples from the study site compared to the
RPA values from a native site indicated clearly a low sorption capacity for the soil
samples from the study site throughout the profile to lm depth. The absence of
significant differences in RPA values for different horizons within the profile could be
due to the absence of differences in soil constituents known to be responsible for P
sorption, such as clay content, between horizons within the profile. However, RPA values
were correlated r2 = 0.65 with double acid (Mehlich I)-extractable P, and Al (Table 4-2).
Similarly, RPA also correlated with oxalate-extractable P, Al, and Fe (r2 = 0.63, n = 72).
Degree of Phosphorus Saturation (DPS')
Degree of phosphorus saturation (DPS - 1) values of soil samples in the study site
varied with depth in the soil profile. DPS - 1 indicated a 50% saturation in surface
horizon, 26% at the 30-45 cm depth, 13-17 % at the 45-60 cm depth, and about 10-13%
at lower depths of 80 and 100 cm pre-and post effluent application (Table 4-3). However,

72
Table 4-2. Multiple regression equations relating RPA to a) Mehlich I (DA) Al, Fe and P,
b) Oxalate Al, Fe, and P in 1996 (prior to the application of effluent) (n = 72),
No.
Equation
Model
R2
a)
RPA = 0.314+ 0.0022DA-A1*** + 0.01181 DA-Fe
- 0.00021 DA-P***
0.65***
b)
RPA = 0.515 + 0.0015 OX-A1*** - 0.00167 OX-Fe**
-0.00087 OX-P***
0.63***
Table 4-3. DPS - lf % values within the soil profile of the study site (n = 12 profiles)
prior and after to application of effluent compared to the “native” soil (n = 1 profile).
Values are Least Square Means (LSM).
Depth, cm
1996
1997
1998
Native
0-15
49.63
40.14
48.25
18.70
15-30
42.46
41.00
41.52
15.30
30-45
26.53
26.02
25.12
12.43
45-60
13.30
21.95
17.89
10.94
60-80
9.98
12.03
13.93
12.43
80-100
9.07
10.24
11.82
10.89
t DPS - 1 % = (Pox / (Feox + Alox)) x 100

73
the soil samples from native area adjacent to the study site showed DPS - lvalue of about
19% to 11% through out the soil profile (Table 4-3).
The DPS - 2 values for soil samples of the study area ranged from about 37% at
the surface to 4% at a depth of 100 cm compared to 9% to 5% for soil samples from the
native area, respectively (Table 4-4). Values of DPS - 1 and DPS - 2 for soil samples of
the study area were highly correlated in strong relationship (r2 =0.92, n = 144) (Fig. 4-1).
These results indicated that the surface horizon is more likely to release P than the deeper
depths. Sharpley (1995) found that a P saturation of 25%, the critical value used in the
Netherlands, would support a DP (Dissolved-P) concentration in surface runoff of 0.69
mg/L using Mehlich-3. Phosphorus sorption saturation, in his study, was calculated from
Mechlich-3 extractable-P and Langmuir P-sorption maximum. However, in Florida,
Mehlich I is the common soil P-test and the use of a common STP to express the DPS
might be practically useful. If the DPS can be determined by a standard soil test
procedure and commonly used as Mehlich I, the DPS can become a useful tool for
evaluating and comparing areas of potential P losses. Also, the strong relationship
between DPS - 1 and DPS - 2 suggested by this study, could be used to compare values
of both DPS if this relationship is similar enough in other soils.
Langmuir Adsorption Parameters
Surface horizons from the study site prior to the application of effluent showed a
lower Langmuir P- sorption maximum (55 mg/kg) associated with higher equilibrium P
concentration (EPCo) and a higher P originally sorbed (So) compared to subjacent
horizons (Table 4-5). These differences were significant (P<0.01) for equilibrium P

74
Table 4-4. DPS - 21’ % values within the soil profile of the study site (n = 12 profiles)
prior and after to application of effluent compared to the “native” soil (n = 1 profile).
Values are Least Square Means (LSM).
Depth, cm
1996
1998
Native
0-15
36.08
37.07
8.79
15-30
31.29
29.68
6.63
30-45
10.98
15.59
4.85
45-60
9.32
7.975
3.94
60-80
5.57
5.57
4.85
80-100
3.58
3.77
4.49
t DPS - 2 % =
(Mehlich I extractable-P / (Feox
+ Alo*)) x 100

DPS-
75
Figure 4-1. Relationship between Degree of P saturation (DPS - 1) calculated from
oxalate extractable-P and Degree of P Saturation calculated from Mehlich I (DPS - 2) for
soil samples from the study site.

76
Table 4-5. Comparison of Langmuir parameters (Smax, EPCo, k) and So mean values of
different horizons within the soil profile prior to the application of effluent in 1996 and
after two years of effluent application in 1998.
Year
Horizon
Smax
mg/kg
So
mg/kg
EPCo
mg/L
k
L/mg
1996
A
0-15cm
55
(13.2-76.3)
28.39a*
(14.9-39.6)
8.81a
(2.31-14.89)
0.15
(0.04-0.40)
Cl
30-45cm
100
(72.5-154)
5.16a
(1.1-8.8)
1.19b
(0.05-3.87)
0.37
(.048-0.64)
C2
45-60 cm
95
(37-142.8)
4.23b
(0-4.23)
0.79b
(0-0.79)
0.54
(0.2-0.99)
1998
A
0-15 cm
88
(70.5-97.1)
25.63a
(18.11-31.4)
5.02a
(3.85-6.18)
0.12
(0.04-0.42)
Cl
30-45 cm
95
(27.7-153)
10.05b
(2.29-25.8)
1.64b
(0.5-4.0)
0.68
(0.07-2.8)
C2
45-60 cm
96
(18.9-175)
4.67b
(2.1-8.34)
0.57b
(0.04-2.0)
0.74
(0.09-2.44)
* LS mean values for given parameters followed by the same latter are not significantly
different (p<0.01). Numbers in parentheses are the highest and lowest value for the
parameter (n = 18).

77
concentration (EPCo) and P originally sorbed (So). There were no significant difference in
Langmuir parameters between 1996 and 1998. The same trend of a lower Langmuir P-
sorption maximum associated with higher equilibrium P concentration (EPCo) and a
higher P originally sorbed (So) continued in 1998 after the application of effluent. The
absence of differences in Langmuir parameters at the beginning and end of the study
period could be attributed to the variability usually associated with such measurements,
the study time limitation, and the fact that this site was heavily loaded with animal
manure prior to the start of the study. However, equilibrium P concentration (EPCo)
showed a strong relationship (r2 = 0.94) with DPS - 1 (Fig. 4-2). Based on this
relationship, a DPS - 1 value of 20 % corresponds to an EPCo value of approximately 1
mg/L. Another parameter, from the isotherm study Po (P in solution after a 24-h
equilibrium period when no P was added (soluble P)), also showed a strong relationship
(r2 =0.92) with DPS - 1 (Fig. 4-3). Based on this relationship, a DPS - 1 value of 20%
corresponds to a Po of approximately 5 mg/L. Such correlation between DPS and
Langmuir parameters suggests that an integration of such tools could be used in the study
of the assessment of the tendency of this soil to release P.
Summary and Conclusions
This study demonstrated the possibility of integrating a numbers of tools to
characterize soil P retention at the study site. The use of a single point isotherm such as
relative P adsorption (RPA) showed that the soil at the site has a lower relative adsorption
for P compared to soils samples from a native site. After two years of effluent
application, RPA values of soil samples from the study site did not show any significant
change and remained in the same range reported before effluent application. The absence

78
Figure 4-2. Relationship between Degree of P saturation calculated from oxalate
extractable-P (DPS -1) and equilibrium P concentration (EPCo) for soil samples from the
study site.

79
Figure 4-3. Relationship between Degree of P saturation calculated from oxalate
extractable-P (DPS -1) and soluble P (Po) mg/L for soil samples from the study site.

80
of differences in RPA values pre-and post effluent application, indicated that effluent
application did not influence P sorption capacity for this soil which has been heavily
loaded with animal manure prior to the start of the study.
The degree of phosphorus saturation (DPS) showed that soil samples from the
study site were 50% saturated at the surface compared to about 19% for the surface soil
samples from the native site. These results indicated that the surface horizon is more
likely to release P than the deeper horizons.
The isotherm study for this soil was also in agreement with the above finding
where surface horizon showed a lower Langmuir P- sorption maximum (55 mg/kg)
associated with higher equilibrium P concentration (EPCo) and a higher P originally
sorbed at the solid phase (So) compared to subjacent horizons. The same trend of a lower
langmuir P- sorption maximum associated with higher equilibrium P concentration
(EPCo) and a higher P originally sorbed at the solid phase (So) continued in 1998 after the
application of effluent, however no significant changes were observed between the two
years.
Values of degree of P saturation (DPS - 1) and (DPS - 2) were highly correlated
(r2 =0.92), which suggest the possibility of integrating the most common STP in the
region (Mehlich I) into the useful approach of degree of P saturation. Also, DPS -1 was
highly correlated with equilibrium P concentration (EPCo) (r2 = 0.94), and with soluble P
(Po) (r2 =0.92). However, further research is needed to determine whether these
relationships are similar enough in other sandy soils to be valuable as a tool in predicting
the tendency of soil to release P.

CHAPTER 5
DOWNWARD PHOSPHORUS MOVEMENT ASSESSMENT IN A SANDY SOIL
RECEIVING DAIRY WASTE EFFLUENT
Introduction
Loss of P from land can occur in three ways; as water-soluble and/or particulate P
in surface runoff, as water-soluble and/or particulate P in subsurface runoff (leaching),
and as water-soluble and/or particulate in flow to groundwater, referring to P picked up
by water that passes to the water-table and which is subsequently discharged to streams,
rivers or lakes as seepage (Ryden et al., 1973). P leaching has normally been considered
to be inconsequential in most soils, but recent studies have found that there are a
combination of agriculture management practices, soil properties, and climatic conditions
that can result in significant P accumulation in subsoils. Whether or not P that leaches
into subsurface horizons is later transported to water bodies depends on the depth of
leaching and the hydrological connections of the watershed (Sims et al., 1998). The
association of P accumulation with its downward movement has been the subject of
numerous studies in soils amended with commercial fertilizers and /or organic wastes.
Studies by King et al. (1990), Kingery et al. (1994), Mozaffari and Sims (1994), and
Eghball et al. (1996) reported P leaching to ~75 cm depending on factors such as soil
type and the amount of P accumulated in the surface horizon. Furthermore, Eghball et al.
(1996) suggested a greater downward mobility for organic forms of P. Previous studies
from Florida also illustrated the extent of P leaching that can occur in deep, sandy soils.
One of the earliest studies in Florida was that of Bryan (1933) who reported P leaching to
81

82
depths of at least 90 cm in heavily fertilized citrus groves of varying ages. Humphreys
and Pritchett (1971), in their study of six soil series in northern Florida, 6 to 10 years
after applying superphosphate, reported extensive P leaching and subsequent
accumulation in the spodic horizon of a Leon fine sand. They noted that all fertilizer P
had leached below a depth of 50 cm in the Pomello and Myakka soil series. A study by
Wang et al. (1994) found that high levels of P could be leached from surface (Ap)
horizons of four sandy Florida soils heavily loaded with dairy manure despite high pH
and abundant Ca2" in solid and solution phases. Graetz and Nair (1995), Nair et al.
(1995), Nair et al. (1998), and Nair et al. (1999), in a series of studies on Spodosols in the
Lake Okeechobee basin of Florida, concluded that the P that leaves the surface (A)
horizon might be lost through surface and subsurface drainage. The P portion that reaches
the spodic (Bh) horizon will be held as Al-and Fe-associated P, either in the inorganic or
in the organic fraction. The high percentage of HCl-extractable P (Ca-and Mg-associated
P) in the A horizon of the intensive dairy component was also of potential concern. The
HC1 extractable P could be continuously extracted by NH4 Cl or by water (Graetz and
Nair, 1995), suggesting that about 80% of the total soil P had the potential to move
eventually with drainage water into Lake Okeechobee. Recently, Sims et al. (1998)
reviewed current research on P leaching and loss in subsurface runoff in Delaware,
Indiana, and Quebec. They concluded that the situation most commonly associated with
extensive P leaching, and thus the increased potential for P loss via subsurface runoff, has
been the long-term use of animal manures.
The most common soil P tests used to assess P status are the traditional agronomic
soil tests for P such as Mehlich I, Mehlich 3, Bray I, and Olsen. These tests are often well

83
correlated with environmentally oriented P tests such as biologically available P (BAP)
and dissolved reactive P (DRP) in runoff (Pote et al., 1996). Water soluble P (WSP) in
particular has been characterized as an appropriate environmental soil P test (Sharpley et
al., 1996, Moore et al., 1998). Therefore, this study was initiated to assess the vertical
movement of P in the soil profile during application of dairy waste effluent to two
cropping sequences in a deep sandy soil, using WSP and labile P concentrations within
the profile as indicators of downward P movement.
Materials and Methods
Experiment Location and Design
The study site was located at North Florida Holstein Dairy facility, which is two
miles south of Bell, Florida. A randomized block design containing three blocks and
arranged as a split plot was used as the experimental design. Main plots were N loading
rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste effluent
was used as the N source. The N application rates were 448 and 896 kg/ha/yr which
correspond to P loading of 112 and 224 kg/ha/yr. The cropping systems were corn-forage
sorghum-rye, and perennial peanut-rye.
Soil Selection and Sampling
The soil was mapped as Kershaw sand (sandy, thermic, uncoated Typic
Quartzipsamments). Soil profile samples (0-15, 15-30, 30-45, 45-60, 60-80, 80-100 cm)
were collected in 1996 (prior to effluent application) and in 1997, and 1998 (after effluent
application). Soil from three profiles in each subplot was collected, composited, mixed
thoroughly and a 1-kg subsample was brought to the laboratory for analysis. Soil samples
were air-dried and sieved (2mm) prior to analysis. Soil samples were also collected in a

84
similar manner from an adjacent native area believed to unimpacted by manure or
fertilization application.
Soil Characterization
Texture was determined using the pipette method (Day 1965). Total phosphorus
(TP) was determined by ashing 1.0 g of soil for 3 hours and then solubilizing with 6 M
HC1 (Anderson, 1976). Double-acid (Mehlich I)-extractable P, Al, Fe, Ca and Mg were
obtained with a 1:4 soil/double acid ratio (Mehlich, 1953). Phosphorus (P) in solution
was analyzed by the molybdenum-blue method (Murphy and Riley, 1962). Soil pH was
determined on 1:2 soil/water ratio, and the organic carbon content of the air-dried
samples was determined by combustion (Broadbent, 1965).
Water soluble P was extracted using a 1: 10 (soil: 0.01 A/Ca CI2) ratio, by
shaking the sample end- over-end for 1 hour, centrifuging for 20 min (1000 g), and
filtering (0.45 um). Phosphorus in solution was analyzed by the molybdenum-blue
method (Murphy and Riley, 1962). Labile P was obtained using a fractionation scheme.
The scheme used to fractionate soil-P was a modification by Nair et al. (1995) of that of
Hieltjes and Lijklema (1980). A 1-g air- dried sample was extracted twice with 25 mL of
1 MNH4CI (adjusted to pH 7.0) (two hours shaking). After each extraction, the content
were centrifuged for 15 min at 3620 x g and filtered through a 0.45-p.m filter. All
extractions were carried out at room temperature. P determination was done using the
procedure of Murphy and Riley (1962) on a spectrophotometer at wavelength of 880 nm.
NFLCl-extractable P was defined as labile P (Petterson and Istvanovics, 1988).
Statistical Analysis
Data analyses were done using SAS program (PROC MIXED) procedure (SAS
Institute Inc. 1985). Relationships among parameters were evaluated using linear

85
correlation. Multiple regression was used to examine the strength of the relationships
between parameters.
Results and Discussion
The soil from the study site showed a higher content of WSP prior to the
application of effluent in 1996 compared to the WSP in the soil profile of the native soil
collected from an adjacent site. WSP for soil samples from the study site ranged from
19.6 mg/kg at the surface to 1.9 mg/kg at 100 cm compared to 0.4 mg/kg at the surface
and <0.1 mg/kg at lower depths of the native soil (Table 5-1). This higher content of
WSP in the soil samples of the study site was associated with higher Mehlich I-
extractable P as shown in (Table 5-2).
The effect of date*rate (P< 0.001), crop*rate (P< 0.001), and date*depth (P<
0.001) were significant for WSP. The application of effluent caused an increase in WSP
content at all depths except the surface soil in 1998 and the change in WSP content was
significant for both rates (Table 5-1). The high effluent application rate showed a
decrease in the WSP content at the surface to about 30 cm then an increase down to the
100-cm depth (Table 5-3, Fig. 5-1). Similarly, WSP concentrations for the low effluent
application rate increased at lower soil depths (Table 5-4, Fig. 5-2). However, though the
trend of change in WSP content under the high and low rates effluent application at the
surface horizon were similar, the trend of change in WSP under low rate application at
the depths of 15-30, 30-45, and 45-60 cm was unexplainable. It was expected that such an
increase in WSP concentrations at these soil depths would be acceptable for the high
effluent rate application. Nevertheless, when WSP averages in all depths within the soil

86
Table 5-1. Mean water soluble P concentrations (WSP) in the soil profile prior to
application of effluent (1996) and after application (1998) (n = 12 profiles) compared to
native soil (n = 3 profiles). Values are least square means (LSM).
Depth
(cm)
1996
1998
Native
mg/kg
0-15
19.6
13.9
0.4
15-30
16.2
22.2
0.1
30-45
9.10
23.2
<0.1
45-60
4.30
13.1
<0.1
60-80
2.80
8.10
<0.1
80-100
1.90
5.40
<0.1

87
Table 5-2. Mehlich I-extractable elements concentrations and total P (TP) in “native” soil
(n = 1 profile) and study site soil profiles (n = 12 profiles) prior to the start of the study.
Location Depth Ca Mg Al Fe P TP
(cm) —
Native
Study Site
0-15
11.7
1.9
267
18.4
47
214
15-30
5.1
1.1
317
20.7
52
270
30-45
6.0
0.8
330
19.1
39
241
45-60
4.7
0.7
337
16.3
36
184
60-80
4.7
0.8
308
16.3
39
181
80-100
4.1
0.7
280
14.3
33
173
0-15
968
115
301
23.5
283
328
15-30
522
69.3
280
22.8
184
254
30-45
208
34.1
203
19.6
75
154
45-60
135
25.7
161
17.9
37
254
60-80
103
22.9
133
15.9
20
218
80-100
75
19.2
117
14.5
12
192

88
P. mg/kg
0 5 10 15 20 25 30
Figure 5-1.Mean water soluble P (WSP) concentrations within the soil profile of the
study site under the high rate effluent application prior to the application of effluent in
1996 and after effluent application in 1998. Values are LSM± Std. Error.

89
P, mg/kg
0 5 10 15 20 25 30 35 40
Figure 5-2. Mean water soluble P (WSP) concentrations within the soil profile of the
study site under the low rate effluent application prior to the application of effluent in
1996 and after effluent application in 1998. Values are LSM± Std. Error.

90
Table 5-3. Changes in WSP concentration within the soil profile under high application
rate after the application of effluent (1998) vs. prior to the application of effluent (1996).
Depth (cm)
1996 vs. 1998
0-15
-9.78**
15-30
NS
30-45
NS
45-60
NS
60-80
NS
80-100
NS
** Significant at the 0.001 probability levels, NS = none significant.
Table. 5-4. Changes in WSP concentration within the soil profile under the low
application rate after the application of effluent (1998) vs. prior to the application of
effluent (1996),
Depth (cm)
1996 vs. 1998
0-15
NS
15-30
13.8**
30-45
23.4**
45-60
10.8**
60-80
5.3**
80-100
NS
** Significant at the 0.001 probability levels, NS = none significant.

91
profile in 1998 was compared to those of 1996 (Fig. 5-3), it showed a trend similar to that
found for Mehlich I-extractable P (Chapter 2). The trend may mimic vertical P
movement in the soil profile and suggested that the decrease in the surface horizon may
be attributed to both crop uptake of P and the leaching effect of effluent irrigation.
The labile P fraction or easily removable P as defined by (Petterson and
Istvanovics, 1988) behaved similarly to WSP regarding its increase in the lower depth of
the profile. As mentioned in Chapter 3, a comparison of labile P mean concentrations in
each depth within the soil profile at the beginning (1996) and end of the study period
(1998) showed that the increase was statistically significant (P < 0.001- P < 0.05) at all
depths. Labile-P constituted 18-40% of TP in the soil profile. Labile-P in 1996 ranged
from 85 in the surface horizon to 37 mg/kg at the lower depth (100 cm) which
corresponded to 26 and 18% of TP, respectively. The application of effluent increased
this fraction to 97 mg/kg in the surface horizon and 69 mg/kg at the lower depth (100 cm)
in 1998. Labile-P increased at the surface horizon and throughout the profile over time
with substantial increases in the lower depth accounting for 40% of TP in 1998 (Fig. 5-4).
Previous research has shown that traditional agronomic soil P tests are often correlated
with dissolved P and /or bioavailable P in runoff waters and subsurface drainage. Wolf et
al. (1985) reported that the equilibrium P concentration at zero sorption (EPCo) and algal-
available P (extracted by a 0 .lMNaOH + INNaCI solution) could be accurately
predicted in a wide range of U.S. soils by the Bray Pi, Mehlich 1, and Olsen soil P tests.
Pote et al. (1996) also reported that water soluble P (WSP) was well correlated with
runoff P in a field study with tall fescue.

Depth, cm
92
WSP mg/kg
-5 0 5 10 15 20 25
Figure 5-3. Mean water soluble P (WSP) concentration within the soil profile of the study
site prior to the application of effluent in 1996 and after effluent application in 1998.
Values are LSM± Std. Error.

93
P, mg/kg
-■-1996 -»-1998
Figure 5-4. Labile-P concentration within the soil profile of the study site prior to the
application of effluent in 1996 and after effluent application in 1998. Values are LSM±
Std. Error.

94
In this study, a number of correlations were investigated to determine the
strongest relationship between parameters. Labile P correlated with Mehlich I-P (r =
0.84, PO.OOl) and WSP correlated with Mehlich I-P (r2 = 0.49, PO.OOl) in 1996. The
low r2 value for WSP is due to high variability in WSP data. The significant relationships
(r2 = 0.84) between Mehlich I-P and labile P and Mehlich I-P and WSP (r2 = 0.49)
showed that Mehlich I-P is a good indicator of leachable P and/or P in the runoff. Pote et
al. (1996) reported a significant relationship (r2 = 0.82, P0.001) between WSP in surface
soil and dissolved reactive P (DRP) in runoff and between Mehlich-3 in surface soil and
dissolved reactive P (DRP) in runoff (r2 = 0.72, P0.001).
The results of this study also showed a significant relationship between labile P
and degree of phosphorus saturation. Labile P correlated with DPS - 2 (r2 = 0.71,
P0.001) and DPS - 1 (r2 = 0.62, P0.001) in 1996. In contrast, WSP did not correlate as
well as labile P with DPS - 1 (r2 = 0.57, P0.001) and DPS - 2 (r2 = 0.49, P0.001).
These significant relationships between labile P and DPS and WSP and DPS showed the
link between easily removable P and degree of P saturation. Pote et al. (1996) reported a
significant relationship (r2 = 0.75, P0.001) between DPS - 1 and dissolved reactive P
(DRP) in runoff. The link between P concentration in soil solution and the degree of P
saturation was suggested by Breeuwsma and Silva (1992), and results from the study site
agree with this conclusion.
The correlation between labile P and DPS - 1 held true after two years of effluent
application (r2= 0.76, PO.OOl), however in the case of labile P and DPS - 2, the
correlation coefficient decreased to 0.23. In the case of WSP, there was also a decrease in
correlation coefficient for DPS-1 (r2 = 0.13) and DPS-2 (r2 = 0.22). This trend was also

95
noted for the relationship between Mehlich I-P, labile P, and WSP. The correlation
coefficients between labile P and Mehlich I-P was r2 = 0.31 and between WSP and
Mehlich I-P r2 = 0.12. The results of the significant linear relationship between soil test P
(Mehlich I), labile P and WSP, and labile P and WSP and DPS-1 and DPS-2 under the
conditions of this study could be useful for future comparison with similar results of other
soils. Downward (vertical) movement of P in this soil was suggested by both labile P and
WSP data. During the two years of effluent application, both parameters showed either a
decrease or a non significant change at the surface horizon, but a significant increase at
the lower depths.
Summary and Conclusions
The association of P accumulation and downward movement has been the subject
of numerous studies in soils amended with commercial fertilizers and/or organic wastes.
Sims et al. (1998) indicated that the most common agricultural situation associated with
significant downward movement of P has been the accumulation of P to “very high” or
“excessive” levels in soils from continuous application of organic wastes.
Phosphorus leaching has normally been considered to be inconsequential in most
soils but recent studies find that there are combinations of agriculture management
practices, soil properties, and climatic conditions that can result in significant P
accumulation in subsoils. Downward P movement in this soil was suggested by both
labile P and WSP data. During the two years of effluent application, both parameters
showed a significant increase at the lower depths of the soil profile. Phosphorus that
leaches into subsurface horizons is later transported to water bodies depending on the
depth of leaching and the hydrological connections of the watershed. Labile P increased

96
form 37 mg/kg at the start of the study to 69 mg/kg at 100 cm by the end of the study in
1998. Water soluble P showed a decrease at the surface horizon but increased in the
lower depths of the soil profile by the end of the study period.
The results of the significant linear relationship between Mehlich I-extractable P
and labile P (r2 = 0.84), and Mehlich I-extractable P and WSP (r2 = 0.49) 1996 could be
useful for future comparison with similar results of other soils. If this relationship
between soil test P (Mehlich I) and easily removable P proven to be valid for similar
soils, it could be helpful in relating soil test P (Mehlich I) levels in soils to P movement
within the soil profile.
Labile P and WSP also showed a significant relationships with DPS - 1 and DPS
- 2 1996 which suggests a link between P concentration in soil solution and DPS reported
by Breeuwsma and Silva (1992). The correlation between labile P and DPS - 1 held true
(r2= 0.76) after two years of effluent application , but the other correlations decreased
after two years of effluent application .

CHAPTER 6
UTILIZATION OF DAIRY WASTE EFFLUENT THROUGH SEQUENTIAL
CROPPING
Introduction
Developing manure utilization plans that are agronomically, economically, and
environmentally sound is a challenge. Issues like accelerated eutrophication, P or N
limitation, transport mechanisms, source management, soil P level, environmental soil
testing for P, and manure management have to be considered. Animal manure can be a
valuable resource if it can be integrated into cost effective best management practices.
However, the need for such plan supported by research, especially in areas of intensified
dairy production and deep, sandy soil is urgent. Many factors may be involved in
developing an environmentally sound plan for manure utilization management.
Uptake of nutrients by agronomic crop sequenced over time is an effective,
economical, and environmentally sound means of nutrient recovery especially if the
cropping system meets the environmental demand. The environmental demand can be
meet by maximizing nutrient uptake by the crops while meeting the need of dairy
producers. Sweeten et al. (1995) reported that irrigation with dairy lagoon effluent
enhanced forage quality yield and did not impair quality of runoff or vadose zone
percolate under the conditions tested for two complete cropping years. Their cropping
systems were summer-only coastal bermudagrass and a summer-winter coastal/wheat
rotation. Land application of lagoon effluent at rates that were at or below soil test
recommendations for total or available nitrogen resulted in runoff quality and vadose
97

98
zone percolate quality that were 94-99% lower in volatile solids, COD, N and P than
concentration in the applied lagoon effluent.
A research report of two years of study on the use of dairy manure effluent in a
rhizoma (perennial) peanut based cropping system (French et. al. 1995) suggested that if
N pollution is the major concern in a particular area, then the PP-R (year-round perennial
peanut and rye) would be a good choice since it performed as well or better than the C-
FS-R (corn, forage sorghum, and winter rye) and C-PP-R (corn planted into a perennial
peanut sod, perennial peanut, and rye) systems. However, if P were the major concern,
the C-FS-R and C-PP-R systems would be better choices. The C-FS-R and C-PP-R
systems were superior to the PP-R rotation in P removal values. Though P concentration
level in perennial peanut forage were generally higher than those in com and forage
sorghum, they were not high enough to compensate for the much lower annual dry matter
yield of the perennial peanut system.
This study was initiated to evaluate the effectiveness of the cropping systems,
corn-forage sorghum-rye and perennial peanut-rye in P removal under two dairy waste
effluent application rates.
Materials and Methods
Experiment Location and Design
The study site was located at the North Florida Holstein Dairy facility, which is
two miles south of Bell, Florida. A randomized block design containing three blocks and
arranged as a split plot was used as the experimental design. Main plots were N loading
rates and subplots were cropping systems. Subplot area was 232 m2. Dairy waste effluent

99
was used as the N source. The N application rates were 448 and 896 kg/ha/yr, which
correspond to P loading of 112 and 224 kg/ha/yr.
Sampling and Analysis
Two cropping systems (corn-forage sorghum-rye and perennial peanut-rye) and
two N application rates (448 and 896 Kg/ha/yr) which correspond to P loading of (112
and 224 Kg/ha/yr) respectively were sampled. The various crops were harvested at the
appropriate times. In the corn-forage sorghum-rye (C-FS-R) system, com was no-till
planted into rye stubble and harvested in July. Forage sorghum was then no-till planted
into existing com stubble. Following sorghum harvest, rye was planted for the winter
season using a no-till grain drill. For the perennial peanut-iye (P-R) system, the perennial
peanut was harvested three times during the warm- growing season. Rye was overseeded
into the peanut sod in late fall for the cool season crop.
Within each plot, a 9.3 m2 portion was harvested, weighed and subsampled.
Ground forage subsamples were sent to the Forage Evaluation Support Laboratory
(FESL) at the University of Florida, Gainesville for analysis. Parameters measured
include dry matter yield, N, and P concentration. N and P analysis involved a
modification of the standard Kjeldahl procedure (Gallaher et al., 1975), followed by
automated colorimetry (Hambleton, 1977) using a Technicon Auto Analyzer.
The data and the statistical analysis were provided by Woodard et al. (2000) and
are used herein to relate crop uptake to P accumulation in the soil. Responses were
analyzed by fitting mixed effect models using the PROC MIXED procedure of SAS
(SAS Institute Inc., 1992) and years were considered as repeated measures.

100
Results and discussion
Mean P removal in the 1996-97 and the 1997-98 seasons from the corn-forage
sorghum-rye (C-FS-R) cropping system was significantly higher compared to the
perennial peanut-rye cropping system (Fig. 6-1 and 6-2). Mean P removal in the 1996-97
season from the corn-forage sorghum-rye (C-FS-R) cropping system was the highest 67.2
kg/ha (Table 6-1) compared to the perennial peanut-rye cropping system (Table 6-2).
Mean P removal in (1997-98) season for the corn-forage sorghum-rye (C-FS-R) cropping
system accounted for about 62 kg P/ha (Table 6-1) with no significant difference in P
removal between 1996-97 and 1997-98 seasons. However, the perennial peanut-rye
cropping system removed only about 35-39 kg P/ha in (1996-97) season and 45-54 kg/ha
in (1997-98) season (Table 6-2). The higher P removal of the corn-forage sorghum-rye
cropping system than perennial peanut-rye was reflected in the soil data reported in
Chapter 2. Mehlich I-extractable P concentrations in soil from perennial peanut-rye
cropping system plots was higher than those of the corn-forage sorghum-rye. This
difference in Mehlich I-extractable P concentrations was significant (P < 0.05) under the
high application rate.
The difference in dry matter yield between the cropping systems was significant
in both seasons (Wooodard et el., 2000). Dry matter yield of the corn -forage sorghum-
rye cropping system was 27 Mg/ha in both seasons (Table 6-3), while the perennial
peanut-rye cropping system dry matter yield was 12 Mg/ha in 1996-97 season and 18
Mg/ha in the 1997-98 season (Table-6-4).
The effect of effluent application rate/year on P removal of the corn-forage
sorghum-rye was not significant for both seasons, while the effect of effluent application

101
Table 6-1. P removed (kg/ha) by the corn-forage sorghum-rye cropping system under
high and low application rates during the 1996-97 and 1997-98 seasons. (Data obtained
from Woodard et al. 2000).
Application rate Corn Forage Rye Total
sorghum
kg/ha
1996-97
High
30.2
17.9
16.8
65
Low
32.5
19.0
15.7
67
1997-98
High
31.4
17.9
14.6
64
Low
31.4
19.0
10.0
60

P removal (kg/ha)
102
Crop
Figure 6-1. P removal (kg/ha) of corn-forage sorghum-rye during the 1996-97 and 1997-
98 seasons.

103
Table 6-2. P removed (kg/ha) by the perennial peanut-rye cropping system under high
and low application rates during the 1996-97 and 1997-98 seasons. (Data obtained from
Woodard et al. 2000).
Application
rate
P. peanut
Rye
Total
kg/ha
1996-97
2nd
yd
High
9
8
18
35
Low
8
8
23
39
1997-98
1Ü
2nd
3rd
High
13
15
07 19
56
Low
13
15
07 10
54

104
Figure 6-2. P removal (kg/ha) of perennial peanut-rye during the 1996-97 and 1997-98
seasons.

105
rate/year on P removal of the perennial peanut-rye was significant in both seasons
(Wooodard et el., 2000). The average removal of P for forage crops in this study,
including perennial peanut in the second season, were in agreement with the reported P
removal for such crops by French et al. (1995), and published book value (NRCS Manure
Master, 1999). However, despite the higher P removal by the C-FS-R than the P-R
cropping system, P removal by the cropping system did not alter the high level of the soil
P that was already present before application of the effluent (Chapter 2). After a high
level of soil test P has been attained, considerable time is required for significant P
depletion as reported by McCollum (1991).
Summary and Conclusions
Uptake of nutrients by agronomic crops sequenced over time is an effective,
economical, and environmentally sound means of nutrient recovery. Cropping systems
are needed to maximize nutrient uptake while meeting the needs of dairy producers. In
this study, higher P removal was recorded for the corn-forage sorghum-rye in both
seasons. The higher P concentration in dry matter of perennial peanut and rye was not
high enough to offset the lower dry matter yield. The perennial peanut-rye cropping
system removed less P than corn-forage sorghum-rye cropping system. However, despite
the higher P removal by C-FS-R than the P-R cropping system, P removal by the
cropping system did not alter the high level of soil P that was already present before
application of the effluent. After a high level of soil test P have been attained,
considerable time is required for significant P depletion. Further investigation is needed
to determine the best application rate based on N or P after taking in consideration the

106
Table 6-3. Average dry matter yield of the corn-forage sorghum-rye during the 1996-97
and 1997-98 seasons.
Crop
Dry matter yield (Mg/ha)
1996-97
1997-98
Com
15
12
Forage
sorghum
08
11
Rye
04
04
Total
27
27
Table 6-4. Average dry matter yield of the perennial peanut-rye during the 1996-97 and
1997-98 seasons.
Crop Drymatter yield(Mg/ha)
1996-97
1997-98
P. Peanut
07
13
Rye
05
05
Total
12
18

107
soil P that was already present in the soil before application, and the needs of dairy
producers.

CHAPTER 7
SUMMARY AND CONCLUSIONS
The study site soil was mapped as Kershaw sand (sandy, thermic, uncoated Typic
Quartzipsamments) in the Gilchrist County soil survey report (Soil Survey Staff, Gilchrist
County, Florida, 1973). Since the publication of the report, the criterion for coated vs.
uncoated family placement has been changed for the USD A soil taxonomic system (Soil
Survey Staff, 1999). The sandy materials sampled in this study would meet the criterion
for coated family (5 percent silt plus 2 times the clay content), based on the particle size
analysis Also, some auger borings to 2 m revealed spodic horizons which indicated
inclusions of Spodosols, and dark colors in the surface horizon in some areas qualify it to
be an Umberic epipedon, which would result in classification as an Inceptisol (Umbrept)
rather than a Psamment. Nevertheless, the soil was consistently sandy and similar to
Kershaw with respect to use and management.
Loss of P from land can occur in three ways; as water-soluble and/or particulate P
in surface runoff, as water-soluble and/or particulate P in subsurface runoff (leaching),
and as water-soluble and/or particulate P in flow to groundwater, referring to P picked up
by water that passes to the water-table and which is subsequently discharged to stream,
rivers or lakes as seepage (Ryden et al., 1973). P leaching has normally been considered
to be inconsequential in most soils, but recent studies find that there are combinations of
agriculture management practices, soil properties, and climatic conditions that can result
in significant P accumulation in subsoils. Whether or not P that leaches into subsurface
horizons is later transported to water bodies depends on the depth of leaching and the
108

109
hydrological connections of the watershed (Sims et al., 1998). However, the most
common agricultural situation associated with significant downward movement of P has
been the accumulation of P to “very high” or “excessive” levels in soils from continuous
application of organic wastes (manure, litter, and municipal or industrial wastes and
waste waters) (Sims et al., 1998). The trend of P accumulation and leaching has also been
shown in Florida, which has intensive agricultural activity, humid climate, frequent heavy
rainfall, and widespread use of irrigation and drainage. Several studies have shown the
extent of P leaching that can occur in deep, sandy soils.
In 1990, the Middle Suwannee River area was approved as a Hydrologic Unit
Area project based on data generated by the Florida Department of Environmental
Protection. These data showed an elevated concentration of nitrate-nitrogen in the
Floridan Aquifer in the Suwannee River Basin, especially in areas of intensive
agricultural activity. Phosphorus concentrations in the Suwannee River ranged from 0.40
to 0.49 mg/L which were 6.4 times the median regional value of north Florida streams.
The Hydrologic Unit Area program was developed to reduce or prevent water quality
degradation of the Floridan Aquifer and the Suwannee River resulting from agricultural
operations. Management of nutrients (potential contaminants) in dairy waste effluent
through spray field crop production systems is an important component in the overall
scheme for protecting ground and surface water from elevated levels of N and P. The use
of inappropriate crop management technology under a dairy effluent irrigation system
can lead to the loss of N to the ground water. Uptake of nutrients by agronomic crops
sequenced over time is an effective, economical, and environmentally sound means of

110
nutrient recovery. Cropping systems designs are needed to meet environmental demands
by maximizing nutrient uptake while meeting the needs of dairy producers.
The Use of Dairy Manure Effluent in A Rhizoma (Perennial) Peanut Based
Cropping Systems for Nutrient Recovery and Water Quality Enhancement was a research
project established under the Hydrologic Unit Area project (HUA). The objective of this
project was to evaluate five cropping systems grown under a dairy effluent disposal
irrigation system, comparing their effectiveness in nutrient recovery and maintenance of
acceptable levels of N and P in ground water. The cropping systems were corn-forage
sorghum-rye, com-bermuda grass-rye, bermuda grass-rye, perennial peanut-rye, and
corn-perennial peanut-rye and the N application rates were (448,672 and 896 kg/ha/yr)
which correspond to P loadings of (112, 168 and 224 kg/ha/yr). My study was a
component of this project and addressed P forms and retention in the soil profile under
two cropping systems (corn-forage sorghum-rye and perennial peanut-rye) and two N
application rates (448 and 896 kg/ha/yr) which correspond to phosphorus loadings of
(112 and 224 kg/ha/yr). The corn-forage sorghum-rye cropping system represents
traditional crops for the Middle Suwannee River area and the perennial peanut-rye system
is an improved cropping system recently introduced to the area.
The main objective of this research was to study the effect of dairy waste effluent
application on P accumulation, forms, and retention in the soil profile of a sandy soil
under two cropping systems. The specific objectives and hypotheses of this research were
as follows:
Objective 1: Quantify and characterize inorganic P forms in the soil profile of the
chosen cropping systems with increasing effluent P application.

Ill
Hypothesis: Application of dairy effluent will increase P levels in the soil
resulting in an accumulation of P in the soil profile.
Objective 2: Quantify and characterize P retention in the soil profile.
Hypothesis: Soil retention capacity will decrease with continuous addition of
dairy effluent and may induce a downward movement of P.
Objective 3: Determine P uptake by the chosen cropping systems under two rates
of effluent application.
Hypothesis: P accumulation in soil profile will decrease with increasing plant
uptake.
The effect of effluent application on P accumulation was discussed in Chapter 2.
Phosphorus forms and fractionation data are presented in Chapter 3 while P retention was
discussed in Chapter 4. Downward P movement was assessed in Chapter 5 and P removal
by the cropping systems was presented in Chapter 6. In this chapter, the most important
finding of this research are summarized according to the objectives and hypotheses
mentioned above. In addition, future research topics are identified.
Investigation of the P levels at the study site indicated that the soil appears to have
been heavily loaded with animal waste prior to the start of this study, although amounts
and dates could not be established. The application of dairy effluent during the study
period resulted in increased TP level through out the soil profile. Soil test P (Mehlich I)
increased for the P-R cropping system under the high application rate. Soil test P
(Mehlich I) was highly correlated with Ca, Mg, A1 and Fe extracted by Mehlich I
solution, with 93% of the variability explained by this relationship.

112
Al- and Fe-associated P constituted the major proportion (62%) of the TP in the
soil profile. Labile-P constituted 18 to 40% of TP throughout the profile with an
increasing trend at the lower depth of the soil profile by the end of the study period.
Labile P is defined as easily removable P and its increase in the lower depths is a clear
indication of a vertical P movement. In fact, the application of dairy effluent during the
study period increased all P pools significantly throughout the soil profile except Ca- and
Mg-associated P which remained constant.
The ability of the soil at the study site to retain P was low in comparison to soil
from the native site. The relative P adsorption (RPA) for the study site soil was 0.5 to 0.6
while the native soil RPA was 0.8 to 0.9. The lower retention of P for this soil was
associated with about 50% P saturation at the surface soil. The Degree of P Saturation
(DPS) for the surface soil from the native site was about 17%. Higher DPS values for the
surface soil suggests that the surface horizon is more likely to release P than the deeper
soil depths. Degree of P Saturation showed a strong relation with EPCo and Po which
suggests that DPS can be used in the assessment of the tendency of this soil to release P.
Downward P movement in the soil profile suggested by water soluble phosphorus (WSP)
and labile P data. Both parameters, during the two years of effluent application showed a
significant increase in the lower soil depths.
Phosphorus removal by the cropping systems was higher for the C-FS-R than the
P-R cropping system. However, P uptake by the cropping systems did not reduce the high
level of soil P that was already present before effluent application. This study suggests
that when STP levels in the soil exceed optimum values for crop production, the

113
application of dairy waste based on estimated crop N requirements may not be
appropriate on heavily P loaded sandy soil such as at the study site.
Further research is needed in the area of linking traditional soil test P with
environmentally oriented P tests such as WSP. The results of the significant linear
relationship between soil test P (Mehlich I), labile P and WSP, and labile P and WSP and
DPS-1 and DPS-2 under the conditions of this study could be useful for future
comparison with similar results of other soils. Also, DPS is another area for future
research. Values of DPS -1, calculated from oxalate extractable-P and DPS - 2,
calculated from Mehlich I for soil samples from the study site were highly correlated (r2
= 0.92) which suggest the possibility of integrating the DPS to the most common soil test
P in the region. Other correlations, such as equilibrium P concentration (EPCo) and DPS -
1 (r2 = 0.94), and soluble P (Po) and DPS - 1 (r2 =0.92) suggest that an integration of such
tools could be used in the study of the assessment of the tendency of this soil to release P.

APPENDIX
SELECTION OF SOIL: SOLUTION RATIO
The solid: solution ratio is critical in sequential extraction. The use of excess solid
can result in incomplete dissolution of target phases due to saturation of the solution with
respect to the target phase (Ruttenberg 1990). A modification for solid: solution is always
needed for a specific sample (Ruttenberg 1992). Therefore, prior to the selection of the
soil: solution ratio used in this study, three soil samples from the study site were used for
comparison with three different soil: solution ratios. The soil samples (lc, 3c, and 6c)
were from three different depths; 0-15, 30-45, and 80-100 cm, respectively. The soil:
solution ratio tried were; 1/10, 1/25, and 1/50. All samples were subjected to a complete
fractionation scheme, as explained below, with two modified procedures. The first,
include the complete procedure with three 1 MNH4CI (adjusted to pH 7.0) extractions,
and the second include the complete procedure with one 1 MNH4CI (adjusted to pH 7.0)
extractions.
In a third trial, the same soil samples were subjected to a complete fractionation
scheme with two soil; solution ratios (1/50 and 1/100) and three 1 MNH4CI (adjusted to
pH 7.0) extractions. Total P (TP) for the three samples used in these trials were determine
by ashing 1.0 g of soil for 3 hours and then solubilizing with 6 M HC1 (Anderson, 1976).
Their TP were 816, 304, and 111, respectively.
The preliminary data of the two trials were shown in the tables (3-1, 3-2, and 3-3)
below. A careful examination of the data in term of P concentration in each trial and
114

115
extraction suggested that the 1/25 soil: solution ratio and two 1 A/NH4CI (adjusted to pH
7.0) extractions seem to be appropriate for this soil.
Table 1-1. Data of trial (1), soil: solution ratio selection
Sample
Ratio
NH4CI1
NH4CI2
NH4C13
P (mg/kg)
NaOH
HC1
lc
1/10
14
16
16
551
277
lc
1/10
14
16
16
581
272
lc
1/25
24
13
17
654
93
lc
1/15
24
24
17
804
90
lc
1/50
21
22
18
566
76
lc
1/50
23
18
10
561
74
3c
1/10
6
4
9
219
138
3c
1/10
6
4
4
216
133
3c
1/25
9
1
5
353
29
3c
1/15
7
2
1
338
36
3c
1/50
4
0
1
323
38
3c
1/50
4
0
0
309
34
6c
1/10
0
0
0
88
17
6c
1/10
0
0
0
84
18
6c
1/25
0
0
0
86
22
6c
1/15
0
0
0
94
22
6c
1/50
0
0
0
105
32
6c
1/50
0
0
0
97
31

116
Table 1-2. Data of trial (2), soil: solution ratio selection
Sample Ratio NH4CI1 NaOH HC1
P (mg/kg)
lc
1/10
15
207
584
lc
1/10
15
566
241
lc
1/25
27
599
325
lc
1/15
26
746
260
lc
1/50
22
596
97
lc
1/50
23
659
102
3c
1/10
7
333
71
3c
1/10
7
319
90
3c
1/25
10
380
41
3c
1/15
3
384
40
3c
1/50
0
356
39
3c
1/50
0
385
36
6c
1/10
0
63
29
6c
1/10
0
93
16
6c
1/25
0
89
22
6c
1/15
0
88
21
6c
1/50
0
115
33
6c
1/50
0
111
30

117
Table 1-3. Data of trial (3), soil: solution ratio selection
Sample
Ratio
NH4CI1
NH4CI2
NH4CI3
NaOH
HC1
r (mg/Kg;
lc
1/50
49
39
28
610
47
lc
49
36
26
602
44
3c
31
20
14
432
23
3c
29
19
15
388
19
6c
4
4
4
126
12
6c
4
4
4
118
12
lc
1/100
70
51
27
695
54
lc
77
49
33
374
218
3c
42
29
19
415
21
3c
37
24
19
398
20
6c
7
7
6
145
12
6c
7
7
6
143
13

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BIOGRAPHICAL SKETCH
Abdullah Alshankiti was bom on February 13, 1956, in Alqunfodah, Saudi
Arabia. He completed his elementary school in his hometown of Alqunfodah. He moved
to Riyadh, Saudi Arabia, to finish high school, and in 1979 he received a bachelor of
science degree in agriculture from Riyadh University. In the same year, he joined the
Department of Soil and Irrigation at the National Agriculture and Water Research Center,
Riyadh, as a research assistant. In 1989, he obtained a Master of Science in Agriculture
degree from California State University, Chico, and returned to work at the National
Agriculture and Water Research Center, Riyadh. After earning his doctoral degree in soil
and water science from the University of Florida in May 2000, he will return to his job at
the National Agriculture and Water Research Center, Riyadh, Saudi Arabia.
126

I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
.DrxM JÜu&é?
Donald A. Graetz, Chair
Professor of Soil and Water Science
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
Professor of Soil and Water Science
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
WH: ¿ /U
Willie G. Harris, Jr.
Professor of Soil and Water Science
I certify that I have read this study and that in my opinion it conforms to
acceptable standards of scholarly presentation and is fully adequate, in scope and quality,
as a dissertation for the degree of Doctor of Philosophy.
Roger A. Nordstedt
Professor of Agricultural and Biological
Engineering
This dissertation was submitted to the Graduate Faculty of the College of
Agricultural and Life Sciences and to the Graduate School and was accepted as partial
fulfillment of the requirements for the degree of Doctor of Philosophy.
May 2000
Dean, Graduate School

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